process for the regeneration of a catalyst

专利摘要:
REGENERATION OF A ZEOLITE CONTAINING TITANIUM. Catalyst, comprising a zeolite containing titanium, said catalyst, having been used in a process for the preparation of an olefin oxide and having phosphate deposited in it, said regeneration process comprising the steps: (a) separating the reaction mixture from the catalyst , (b) washing the catalyst obtained from (a) with a liquid aqueous system; (c) optionally drying the catalyst obtained from (b) in a gas stream, comprising an inert gas, at a temperature of less than 300 ° C; (d) calcining the catalyst obtained from (c) in a gas stream comprising oxygen, at a temperature of at least 300 ° C.
公开号:BR112016001518B1
申请号:R112016001518-5
申请日:2014-07-16
公开日:2020-12-29
发明作者:Philip Kampe；Daniel Urbanczyk；Alexander Schröder；Joaquim Henrique Teles；Dominic RIEDEL；Markus Weber；Ulrich Müller；Andrei-Nicolae PARVULESCU；Bianca Seelig；Peter Resch；Christian Bartosch；Ulrike Wegerle
申请人:Basf Se；Dow Global Technologies Llc；
IPC主号:

专利说明:

[001] The present invention is related to a process of regeneration of a catalyst, comprising a zeolite containing titanium, said catalyst, having been used in a process for the preparation of an olefin oxide and having a phosphate salt deposited in it, said regeneration process comprising the steps: (a) separating the reaction mixture from the catalyst, (b) washing the catalyst obtained from (a) with an aqueous liquid system; (c) optionally drying the catalyst obtained from (b) in a gas stream, comprising an inert gas, at a temperature below 300 ° c; (d) calcining the catalyst obtained from (c) in a gas stream comprising oxygen, at a temperature of at least 300 ° C. In addition, the present invention relates to a regenerated catalyst, comprising a zeolite containing titanium as material catalytically active, obtainable or obtained by the process of the present invention.
[002] In recent years, several titanium-containing zeolites have been developed that are useful in catalyzing organic reactions such as the conversion of olefins to epoxides. For example, WO-A 98/55229 and WO-A 2011/064191 disclose the production and further use of zeolites containing heterogeneous titanium in epoxidation.
[003] Zeolites containing heterogeneous titanium are of great industrial interest and in this context economic and environmental considerations are of significant relevance. An efficient regeneration of such zeolites for later reuse in the catalysis of organic reactions would be strongly preferable over their replacement with fresh catalyst.
[004] EP-A 0 934 116 discloses a process for the regeneration of a spent catalyst composed of titanium silicalite, resulting from the synthesis of an epoxide, by the reaction between an olefin peroxide and hydrogen. The spent catalyst treatment comprises washing with methanol, followed by drying in a stream of nitrogen gas at 75 ° C and additionally followed by the regeneration step itself, which is heated to 300 ° C for 7 hours. Methanol, which must be supplied in large quantities and of sufficiently high purity, is a valuable organic compound and requires expensive and time-consuming recovery for reuse.
[005] EP-A 1 371 414 discloses a process for the regeneration of a silicon oxide catalyst containing titanium following cumene epoxidation, comprising passing liquid propylene through the spent catalyst at a temperature not lower than the maximum reaction of the epoxidation reaction. Propene is also a valuable organic compound and using it in large quantities on an industrial scale would be economically unfavorable.
[006] 1 221 442 EP-A discloses the regeneration of a titanium zeolite catalyst used in an olefin epoxidation with hydrogen peroxide, the process comprising carrying out the epoxidation reaction, in which the regeneration of the spent catalyst is carried out with peroxide of hydrogen in the presence of the olefin through which the epoxidation reaction is continued and in which regeneration is achieved by reversing the hydrogen peroxide feed direction. Hydrogen peroxide is also a valuable educt and as such difficult to deal with, due to its tendency to decompose spontaneously.
[007] WO-A 2005/000827 discloses the regeneration of a titanium silicalite catalyst according to a process for the continuous epoxidation of propene with hydrogen peroxide. The catalyst is periodically regenerated with a methanol solvent at a temperature of at least 100 ° C. As indicated above, methanol is a valuable organic compound that requires expensive and time-consuming recovery. Also, after regeneration, epoxidation has to be restarted at a higher temperature compared to the fresh catalyst in WO-A 2005/000827.
[008] WO-A 2007/013739 discloses the regeneration of a titanium containing molecular sieve, in which, after a pretreatment of the spent catalyst with water or alcohol, the catalyst thus pretreated is brought into contact with a mixture comprising hydrogen peroxide, water and alcohol. Thus, this process includes two mandatory and subsequent steps in which the spent catalyst is brought into contact with two different solutions.
[009] US 2003/0187284 A1 discloses a method for producing an epoxide in the presence of a zeolite catalyst and regenerating the catalyst by treating it with a solution of an acid with a pKa value of less than 6.
[010] US 2012/142950 A1 discloses a continuous process for the production of propylene oxide comprising reacting propene with hydrogen peroxide in methanolic solution in the presence of siliconite-1 titanium catalyst to obtain propylene oxide.
[011] WO 2011/115234 A1 discloses a method for regenerating titanosilicate catalysts.
[012] US 2004/058798 A1 discloses a method for the regeneration of titanium-containing silicone oxide catalysts by heating the used catalysts to a temperature of at least 400 ° C in the presence of an oxygen-containing gas stream.
[013] US 5 916 835 A discloses a method of regenerating used non-zeolitic heterogeneous catalysts.
[014] Therefore, it was an object of the present invention to provide a simple and economical process for the regeneration of a catalyst, comprising a zeolite containing titanium as a catalytically active material used in an olefin epoxidation. It was an additional object of the present invention to provide a regenerated catalyst, comprising a zeolite containing titanium as a catalytically active material that can be easily reused in the catalysis of the olefin epoxidation.
[015] In this way, the present invention preferably relates to a process of regeneration of a catalyst, comprising a zeolite containing titanium as a catalytically active material, said catalyst, having been used in a process for the preparation of an olefin oxide comprising ( i) providing a mixture comprising an organic solvent, an olefin, an epoxidating agent and at least partially dissolved potassium, comprising salt; (ii) subjecting the mixture provided in (i) in a reactor to conditions of epoxidation in the presence of catalyst, obtaining a mixture comprising the organic solvent and the olefin oxide and obtaining the catalyst having a potassium salt deposited in said process for regeneration comprising (a) separating the mixture obtained from (ii) the catalyst; (b) washing the catalyst obtained from (a) with an aqueous liquid system; (c) optionally drying the catalyst obtained from (b) in a gas stream comprising an inert gas, at a temperature of less than 300 ° c; (d) calcining the catalyst obtained from (b) or (c) in a gas stream comprising oxygen, at a temperature of at least 300 ° C.
[016] Interestingly, according to the regeneration process of the present invention, which comprises washing spent spent catalyst, comprising a zeolite containing titanium with an aqueous liquid system, combined with optional drying and additional calcination, a regenerated catalyst comprising a zeolite containing titanium with excellent catalytic properties is obtained which can be easily reused, for example in the process for the preparation of an olefin oxide.
[017] In this regard, the inventors discovered that after submitting the spent catalyst, comprising a zeolite containing titanium as a catalytically active material for the regeneration of the present invention, its activity and selectivity is, in the long run, comparable to the activity of the fresh catalyst respective comprising a zeolite containing titanium. Such a favorable result can be obtained after performing only one cycle of regeneration steps (a) to (d).
[018] Furthermore, surprisingly, it was found that even repeated cycles of steps (a) to (b) did not adversely affect the activity and selectivity of the catalyst comprising a zeolite containing titanium as a catalytically active material. The regeneration according to steps (a) to (b) of the previously sent invention, proved to be, in this way, a light process to which the same catalytic material can be presented several times, since no deteriorating effect on the catalytic activity thus as, presumably, in the zeolitic structure it was observed after several repetitions of steps (a) to (b). STEP (A)
[019] The first regeneration step (a) requires separating the reaction mixture resulting from the epoxidation reaction of an olefin from the catalyst comprising a zeolite containing titanium as a catalytically active material.
[020] This separation of the spent catalyst reaction mixture comprising a zeolite containing titanium can be achieved in any appropriate manner, such as pumping, draining, settling, filtration and the like. Preferably, if the epoxidation reaction is carried out in batch mode, it is preferable to separate the mixture obtained from (ii) from the spent catalyst by filtration. In case the epoxidation reaction is carried out continuously, it is preferable to separate the mixture obtained from (ii) from the spent catalyst when stopping submitting the mixture provided in (i) to epoxidation conditions according to (ii) and submitting the spent catalyst to the regeneration step (b) once all the mixture obtained (ii) has left the reactor in which the epoxidation was carried out, either in the reactor or in any other appropriate container after having removed the spent catalyst from the reactor.
[021] If the spent catalyst comprising a zeolite containing titanium is removed from the reactor after steps (i) and (ii) and regenerated in a separate container, only a short interruption of the production process can be performed since the reactor can be refilled quickly with a second charge of catalyst, allowing the epoxidation reaction to restart immediately. STEP (B)
[022] After separation in (a), the spent catalyst comprising a zeolite containing titanium is washed with a liquid aqueous system according to (b).
[023] Liquid aqueous system used in (b) contains at least 75% by weight, preferably at least 90% by weight, more preferably at least 95% by weight, more preferably at least 99% by weight, most preferably at least 99.9% by weight of water, more preferably at least 99.99% by weight of water, more preferably at least 99.999% by weight of water, based on the total weight of the liquid aqueous system. According to an embodiment of the present invention, the liquid aqueous system employed in (b) is water, preferably deionized water.
[024] In the present process, the temperature and pressure conditions in step (b) are chosen so that the aqueous system is maintained in a liquid state of matter by at least 90%, preferably at least 95%, more preferably at least 99% washing time. Preferably, the aqueous system is in its liquid state during the wash time.
[025] Preferably, washing in (b) with a liquid aqueous system is carried out at a pressure in the range of 0.5 to 2 bar, more preferably from 0.8 to 1.5 bar, more preferably from 1.0 to 1.4 bar. Preferably, washing in (b) with a liquid aqueous system is performed at a temperature of the liquid aqueous system in the range 25 to 95 ° C, more preferably 40 to 90 ° C, more preferably 60 to 80 ° C. More preferably, washing in (b) with a liquid aqueous system is carried out at a pressure in the range of 0.8 to 1.5 bar, preferably from 1.0 to 1.4 bar and a temperature in the range of 40 to 90 ° C, preferably from 60 to 80 ° C. More preferably, washing in (b) with a liquid aqueous system is performed at a pressure in the range of 1.0 to 1.4 bar and a temperature in the range of 60 to 80 ° C.
[026] In this way, the present invention preferably relates to the process as described above, in which in (b), the catalyst obtained from (a) is washed with an aqueous liquid system containing at least 99.9% by weight of water more preferably at least 99.99% by weight, more preferably at least 99.999% by weight of water, based on the total weight of the liquid aqueous system, at a pressure in the range of 0.8 to 1.5 bar , preferably from 1.0 to 1.4 bar and a temperature in the range of 40 to 90 ° C, preferably from 60 to 80 ° C.
[027] In general, the pH of the liquid aqueous system according to (b) is not subject to specific restrictions. Depending on the preferred water content of the liquid aqueous system, the pH value can be in the range of 4 to 10, preferably in the range of 5 to 9, more preferably in the range of 6 to 8. Preferably, the pH is in the range of 6.5 to 7.5, more preferably from 6.6 to 7.4, more preferably from 6.7 to 7.3, more preferably from 6.8 to 7.2. The pH should be understood as being determined using a pH-sensitive glass electrode in which the liquid aqueous system is in an inert atmosphere that prevents, for example, the liquid aqueous system from coming into contact with atmospheric carbon dioxide which, if absorbed in the liquid aqueous system, it would reduce the pH.
[028] Preferably, no acid catalyst treatment is carried out in (b). Thus, it is preferable that the liquid aqueous system is free of compounds with a pKa value of 8 or less, preferably 6 or less. By "free of compounds with a pKa value of" is to be understood in the context of the present invention, so that the liquid aqueous system comprises less than 0.1% by weight of such compounds, preferably less than 0.01% by weight, preferably less than 0.001 % by weight, more preferably less than 0.0001% by weight, more preferably less than 0.00001% by weight and more preferably less than 0.000001% by weight.
[029] More preferably, no acid treatment of the catalyst is carried out in the entire process for regeneration according to the present invention. Thus, it is preferable that no compound with a pKa value of 8 or less, preferably 6 or less, is employed throughout the regeneration process according to the present invention.
[030] Preferably, the liquid aqueous system in (b) comprises less than 10% by weight of methanol, more preferably less than 5% by weight of methanol, more preferably less than 1% by weight of methanol, preferably less than 0, 1 wt% methanol, more preferably less than 0.01 wt% methanol and more preferably less than 0.001 wt% methanol, based on the total weight of the liquid aqueous system.
[031] Interestingly, it was found that, under these conditions of step (b), washing the catalyst comprising a zeolite containing titanium with an aqueous system results in essentially no change in the zeolitic structure of the zeolite containing titanium. Thus, it was found that contact, according to (b), does not have disadvantageous effects on the catalytic activity of the catalyst comprising a zeolite containing titanium. CONTINUOUS MODE
[032] According to a preferred embodiment of the present invention, washing in (b) is carried out in a continuous mode, in which the catalyst is continuously contacted by a stream of the liquid aqueous system which is passed over the catalyst.
[033] Preferably, washing in continuous mode is performed at a mass hourly space velocity (WHSV) in the range of 1 to 20 h-1, more preferably from 5 to 15 h-1, more preferably from 5 to 10 h-1 . The hourly mass space velocity in (b) is defined by the mass flow rate of the liquid aqueous system divided by the mass of the catalyst comprising a zeolite containing titanium undergoing regeneration.
[034] According to this modality, it is possible to wash the catalyst in the reactor where the epoxidation reaction was carried out according to (ii). In this case, as mentioned above, it is preferable to stop submitting the mixture provided in (i) to epoxidation conditions according to (ii) and to submit the spent catalyst to the regeneration step (b) in a continuous mode, since all the mixture obtained (ii) has left the reactor where epoxidation was carried out in the reactor. It is also possible to remove the spent catalyst, once the entire mixture obtained from (ii) has left the reactor, from the reactor, fill the catalyst in another appropriate container, in which a continuous wash can be performed and submit the catalyst for a wash. continuous according to (b).
[035] In this way, the present invention preferably relates to the process as described above, in which in (b), the catalyst obtained from (a) is washed continuously with an aqueous liquid system containing at least 99 , 9% by weight of water more preferably at least 99.99% by weight, more preferably at least 99.999% by weight of water, based on the total weight of the liquid aqueous system, at a pressure in the range of 0.8 to 1 , 5 bar, preferably from 1.0 to 1.4 bar and a temperature in the range of 40 to 90 ° C, preferably from 60 to 80 ° C, in which continuous washing is carried out in the reactor according to (ii ). LOT MODE
[036] According to another embodiment of the present invention, washing in (b) is carried out in batch mode in which the catalyst comes into contact once or several times with a specific amount of liquid system. For example, it is preferable that the washing in (b) is carried out by immersing the catalyst in the liquid aqueous system. During regeneration, it is possible to subject the mixture obtained in (ii), including or excluding the catalyst, to agitation. It is conceivable that when washing in (b) is carried out in batch mode, the liquid aqueous system can be replaced one or more times.
[037] According to this modality, it is possible to wash the catalyst in the reactor where the epoxidation reaction was carried out according to (ii). In this case, as mentioned above, it is preferable to stop subjecting the mixture provided in (i) to epoxidation conditions according to (ii) and to subject the spent catalyst to the regeneration step (b) in batch mode, since all the mixture obtained (ii) has left the reactor where epoxidation was carried out in the reactor. It is also possible to remove the spent catalyst, once the entire mixture obtained from (ii) has left the reactor, from the reactor, fill the catalyst in another appropriate container, in which a batch wash can be carried out and subject the catalyst to a batch washing according to (b).
[038] In this way, the present invention preferably relates to the process as described above, in which in (b), the catalyst obtained from (a) is washed in batch mode with an aqueous liquid system containing at least 99.9% by weight of water more preferably at least 99.99% by weight, more preferably at least 99.999% by weight of water, based on the total weight of the liquid aqueous system, at a pressure in the range of 0.8 to 1.5 bar, preferably from 1.0 to 1.4 bar and a temperature in the range of 40 to 90 ° C, preferably from 60 to 80 ° C, where washing in batch mode is carried out outside the reactor according to with (ii).
[039] Preferably, the washing according to (b) is carried out until the potassium content of the liquid aqueous system after having contacted the catalyst is at most at 1000 weight-ppm, preferably at most 250 weight-ppm, more preferably not more than 25 ppm weight.
[040] Preferably, washing in (b) is carried out until the potassium content of the liquid aqueous system after having contacted the catalyst in relation to the potassium content of the aqueous liquid system before having had contact with the catalyst being in the maximum at 333: 1, preferably at most 100: 1, most preferably at most 10: 1, most preferably 1.2: 1.
[041] Generally, if deionized water is used as the liquid aqueous system, it is preferable to subject the catalyst to washing according to (b) until the conductivity of the liquid aqueous system, after being contacted with the catalyst, understand a zeolite containing titanium as a catalytically active material is a maximum of 500 microSiemens, preferably a maximum of 400 microSiemens, more preferably a maximum of 300 microSiemens. STEP C)
[042] After washing according to (b), the catalyst, comprising a zeolite containing titanium obtained can be optionally dried in a step (c) in a gas stream, comprising an inert gas, at a temperature below 300 ° ç.
[043] Preferably, the temperature is in the range of 20 ° C to 200 ° C, more preferably from 25 ° C to 100 ° C, more preferably from 30 ° C to 50 ° C.
[044] Therefore, the present invention preferably relates to the process described above, in which (c), drying is carried out, preferably at a temperature in the range of 25 to 100 ° C, preferably from 30 to 50 ° C. Furthermore, the present invention preferably relates to the process as described above, wherein in (b), the catalyst obtained from (a) is washed with a liquid aqueous system containing at least 99.9% by weight of water, more preferably at least 99.99% by weight of water, more preferably at least 99.999% by weight of water, based on the total weight of the liquid aqueous system, at a pressure in the range of 0.8 to 1.5 bar , preferably from 1.0 to 1.4 bar and a temperature in the range of 40 to 90 ° C, preferably from 60 to 80 ° C, and in which (c), the catalyst obtained from (b) is dried in a gas stream, comprising an inert gas, at a temperature in the range 25 to 100 ° C, preferably 30 to 50 ° C.
[045] The duration of drying in (c) is dependent on the amount of catalyst comprising a titanium-containing zeolite to be dried in the gas stream, comprising an inert gas at elevated temperatures. It is conceivable that large amounts of catalyst, comprising a zeolite containing titanium, will require a long period of time compared to a small amount of catalyst, comprising a zeolite containing titanium. It is preferred that the drying in (c) is carried out for a period of time in the range of 5 to 350 hours, preferably 10 to 250 hours, more preferably 12 to 100 hours.
[046] The hourly mass space velocity (WHSV) of the gas stream, comprising a gas inert in (c) is not subject to specific restrictions and is typically in the range of 100 to 2000 h-1, preferably from 500 to 1500 h- 1, more preferably from 500 to 1000 h -1. The hourly mass space velocity in (b) is defined by the mass flow rate of the gas stream comprising an inert gas divided by the mass of the catalyst comprising a titanium-containing zeolite in the reactor.
[047] Preferably, at least 90% by volume, preferably at least 95% by volume, more preferably at least 99% by volume of the gas stream comprising an inert gas, according to (c) consists of at least one inert gas . Preferably, the at least one inert gas is selected from the group consisting of nitrogen, helium, argon and a mixture of two or more of these. Preferably, at least 90% by volume, preferably at least 95% by volume, more preferably at least 99% by volume, more preferably at least 99.9% by volume of the gas stream comprising an inert gas, according to (c ) consists of nitrogen, preferably technical nitrogen.
[048] Therefore, the present invention preferably relates to the process described above, in which (c), drying is carried out, preferably at a temperature in the range of 25 to 100 ° C, preferably from 30 to 50 ° C. Furthermore, the present invention preferably relates to the process as described above, wherein in (b), the catalyst obtained from (a) is washed with a liquid aqueous system containing at least 99.9% by weight of water, more preferably at least 99.99% by weight of water, more preferably at least 99.999% by weight of water, based on the total weight of the liquid aqueous system, at a pressure in the range of 0.8 to 1.5 bar , preferably from 1.0 to 1.4 bar and a temperature in the range of 40 to 90 ° C, preferably from 60 to 80 ° C, and in which (c), the catalyst obtained from (b) is dried in a gas stream, comprising an inert gas, at a temperature in the range 25 to 100 ° C, preferably 30 to 50 ° C, at least 99% by volume, preferably preferably at least 99.9% by volume of the gas stream consists of nitrogen, preferably technical nitrogen.
[049] For satisfactory results, it is preferable to perform the drying according to (c) until the water content in the gas stream comprising an inert gas, after having come in contact with the catalyst comprising a zeolite containing titanium is similar to water content of the gas stream comprising an inert gas before it has come into contact with the catalyst. Preferably, drying in (c) is carried out until the water content of the gas stream comprising an inert gas after coming into contact with the catalyst in relation to the water content of the gas stream comprising an inert gas before it has entered in contact with the catalyst is at most 1.10: 1, preferably at most 1.08: 1, more preferably at most 1.05: 1, most preferably at most 1.03: 1.
[050] Alternatively, drying in (c) can preferably be carried out until the volume fraction of water in the gas stream comprising an inert gas after having come in contact with the catalyst comprising a zeolite containing titanium is at most 500 ppmV , preferably at most 400 ppmV, preferably at most 300 ppmV, more preferably at most 250 ppmV in relation to the total volume of the gas stream comprising an inert gas. STEP D)
[051] According to step (d) the catalyst obtained from (b) or (c), preferably from (c), is subjected to calcination in a gas stream comprising oxygen, at a temperature of at least 300 ° C .
[052] Preferably, the calcination according to (d) is carried out at a temperature in the range of 300 to 600 ° C, preferably from 325 to 575 ° C, more preferably from 350 to 550 ° C, more preferably from 375 to 525 ° C, more preferably 400-500 ° C.
[053] Therefore, the present invention preferably relates to the process described above, in which (c), drying is carried out, preferably at a temperature in the range of 25 to 100 ° C, preferably from 30 to 50 ° C. Furthermore, the present invention preferably relates to the process as described above, wherein in (b), the catalyst obtained from (a) is washed with a liquid aqueous system containing at least 99.9% by weight of water, more preferably at least 99.99% by weight of water, more preferably at least 99.999% by weight of water, based on the total weight of the liquid aqueous system, at a pressure in the range of 0.8 to 1.5 bar , preferably from 1.0 to 1.4 bar and a temperature in the range of 40 to 90 ° C, preferably from 60 to 80 ° C, and in which (c), the catalyst obtained from (b) is dried in a gas stream, comprising an inert gas, at a temperature in the range of 25 to 100 ° C, preferably from 30 to 50 ° C, and in which (d), the catalyst obtained of (c) is calcined in a gas stream comprising oxygen at a temperature in the range of 375 to 525 ° C, preferably 400 to 500 ° C.
[054] Preferably, the gas stream comprising oxygen employed in (d) has an oxygen content of at least 1% by volume, such as at least 5% by volume, at least 10% by volume, at least 15% by volume or at least 20% by volume. More preferably, the gas stream comprising oxygen employed in (d) has an oxygen content in the range of 1 to 50% by volume, more preferably 3 to 40% by volume, more preferably from 5 to 30% by volume. If the gas stream comprising oxygen employed in (d) has an oxygen content of less than 100% by volume, the gas stream may contain one or more additional gases such as nitrogen, argon, helium, carbon dioxide, water or a mixture of two or more of these. More preferably, the gas stream comprising oxygen employed for the calcination of the catalyst comprising a zeolite containing titanium in (d) is air or poor air.
[055] Therefore, the present invention preferably relates to the process described above, in which (c), drying is carried out, preferably at a temperature in the range of 25 to 100 ° C, preferably from 30 to 50 ° C. Furthermore, the present invention preferably relates to the process as described above, wherein in (b), the catalyst obtained from (a) is washed with a liquid aqueous system containing at least 99.9% by weight of water, more preferably at least 99.99% by weight of water, more preferably at least 99.999% by weight of water, based on the total weight of the liquid aqueous system, at a pressure in the range of 0.8 to 1.5 bar , preferably from 1.0 to 1.4 bar and a temperature in the range of 40 to 90 ° C, preferably from 60 to 80 ° C, and in which (c), the catalyst obtained from (b) is dried in a gas stream, comprising an inert gas, at a temperature in the range of 25 to 100 ° C, preferably from 30 to 50 ° C, and in which (d), the catalyst obtained of (c) is calcined in a gas stream comprising oxygen at a temperature in the range of 375 to 525 ° C, preferably 400 to 500 ° C, in which the gas stream comprising oxygen employed in (d) contains oxygen in the range from 3 to 40% by volume, preferably from 5 to 50% by volume.
[056] It is preferred that the hourly mass space velocity (WHSV) of the gas stream, comprising an inert gas in (d) is in the range of 100 to 2000 h-1, preferably from 500 to 1500 h-1, more preferably from 500 to 1000 h-1. The hourly mass space velocity in (d) is defined by the mass flow rate of the gas stream comprising oxygen divided by the mass of the catalyst comprising a zeolite containing titanium in the reactor.
[057] Preferably according to (d), the catalyst obtained from (c) or (d), preferably from (c), is heated to the calcination temperature at a rate in the range of 0.5 to 5 K / min, preferably from 1 to 4 K / min, more preferably from 2 to 3 K / min.
[058] Preferably, the calcination in (d) is carried out for a period of time in the range of 1 to 15 hours, more preferably from 2 to 10 hours, more preferably from 3 to 7 hours.
[059] The drying according to (c), as well as the calcination according to (d) can be carried out in the reactor according to (ii) or outside the reactor according to (ii). If the washing according to (b) is carried out in the reactor according to (ii), it may be advantageous to carry out the drying according to (c), if carried out, also in the reactor according to (ii). Regarding the calcination according to (d), it may be advantageous to carry it out in the reactor according to (ii) if the washing according to (b) and the drying according to (c), if carried out, are also carried out in the reactor according to (ii), possibly depending on the material and layout of the reactor.
[060] According to the present invention, steps (b) to (d) can be repeated at least once. Therefore, after calcination according to (d), the calcined catalyst can be subjected to (b) again for other step sequences (b), optionally, (c) and (d). In a given cycle, the respective conditions of the stages can be changed in comparison to another cycle. Therefore, for example, in a given sequence (b) to (d), drying according to (c) is performed while, in another sequence from (b) to (d), said drying according to (c) does not is realized. According to the present invention, the sequence of steps (b) to (d) can be repeated 1 to 5 times, such as once, two, three times, four times, five times, under the same or different conditions in the respective steps (b) to (d). Due to the median regeneration conditions according to the present invention, it has been found that not even repeating the sequence of steps (b) to (d) several times has a negative impact on the zeolytic structure of the catalyst, and such repetition can lead to a very effective potassium removal from the catalyst.
[061] According to the present invention, it is preferable that, in the course of a sequence (a) to (d), the spent catalyst is washed with the liquid aqueous system according to (b) in which this washing step ( b) it is the only treatment with a liquid system. Compared to WO-A 2007/013739, there is no such combination of a pre-treatment step and a further treatment with another liquid mixture. In particular, according to the preferred process of the present invention, the liquid aqueous system employed in step (b) essentially consists of water and compared to the process of WO-A 2007/013739, the treatment of water as a single treatment with a mixture liquid is a much smoother regeneration than a hydrogen peroxide treatment.
[062] Therefore, the present invention relates to the process described above, in which the washing according to (b) is the only treatment with a liquid system during the regeneration process comprising (a), (b), and, optionally, (c) and (d). STEP (I)
[063] According to the present invention, the spent catalyst, comprising a zeolite containing titanium to be subjected to regeneration steps (a) to (d) is obtained by a process for the preparation of an olefin oxide, comprising: ( i) providing a mixture comprising an organic solvent, an olefin, an epoxidating agent and at least partially dissolved potassium, comprising salt; (ii) subjecting the mixture provided in (i) in a reactor to conditions of epoxidation in the presence of catalyst, obtaining a mixture comprising the organic solvent and the olefin oxide and obtaining the catalyst having a potassium salt deposited in it
[064] Organic solvents to be used in (i) are, in principle, all solvents known for this purpose. Preference is given to the use of organic solvents such as alcohols, nitriles and mixtures thereof, optionally also water. It is particularly preferred that the organic solvent is selected from the group consisting of methanol and acetonitrile.
[065] The amounts of organic solvent used can be varied within wide limits. Possible amounts of organic solvent used are 5 to 25 g of organic solvent per gram of epoxidating agent used. For example, the organic solvent is used in an amount of 8 to 16 g of organic solvent per gram of epoxidating agent used, or 10 to 14 g of organic solvent per gram of epoxidating agent used.
[066] Where the olefin employed (i) is preferably selected from the group consisting of ethylene, propene, 1-butene, 2-butene, isobutene, butadiene, pendenos, piperylene, hexenes, hexadienes, heptenes, octenes, diisobutene, trimethylpentene, nonenos, dodecene, tridecene, tetradecene eiconsenes, tripropene, tetrapropene, polybutadienes, polyisobutenon, isoprenes, terpenes, geraniol, linalool, linalyl acetate, methylene cyclopropane, cyclopentene, cyclohexene, cyclohexene, cyclohexene, vinylcyclohexane, vinylcyclo cycloctadiene, vinylnorbornene, indene, tetrahydroindene, methylstyrene, dicyclopentadiene, divinylbenzene, cyclododecene, cyclododecatriene, stilbenes, diphenylbutadiene, vitamin A, beta-carotene, vinylidene fluoride, ayl halides, alcohol, chloride, chloride, chloride butenols, butenodiols, cyclopentenodiols, pentenols, octadienols, tridecenols, unsaturated steroids, ethoxyethene, isoeugene l, anethole, carbocyclic unsaturated acids, such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, vinylacetic acid, unsaturated fatty acids, such as oleic acid, linoleic acid, palmitic acid, natural oils and fats and their mixtures. It is particularly preferred that the olefin is propene.
[067] It is preferable that the epoxidation agent used in (i) is hydrogen peroxide. It is additionally preferred that the hydrogen peroxide is an aqueous solution of hydrogen peroxide, in which the solution preferably comprises 30 to 50% by weight of hydrogen peroxide in relation to the total amount of water. It is also possible that hydrogen peroxide is formed in situ in the reaction mixture of hydrogen and oxygen in the presence of an appropriate catalyst or catalyst system, for example, in the presence of a titanium-containing zeolite, which in addition contains one or more noble metals, or a zeolite containing titanium and an additional catalyst containing one or more noble metals, for example, supported on a suitable support such as coal or a suitable inorganic oxide or mixture of inorganic oxides.
[068] For the preparation of hydrogen peroxide used in the process of (i), the anthraquinone process can be used. This process is based on the catalytic hydrogenation of an anthraquinone compound to form the corresponding anthrahydroquinone compound, the subsequent reaction of this with oxygen to form hydrogen peroxide and subsequent extraction of the hydrogen peroxide formed. The cycle is completed by rehydrogenation of the anthraquinone compound that was formed again during oxidation. A review of the anthraquinone process is given in the "Ullmann’s Encyclopedia of Industrial Chemistry", 5th edition, volume 13, pages 447 to 456.
[069] Alternatively, it is conceivable to obtain hydrogen peroxide by anodic oxidation of sulfuric acid with simultaneous evolution of hydrogen at the cathode to produce peroxodisulfuric acid. Hydrolysis of peroxodisulfuric acid forms, first, peroxosulfuric acid and then hydrogen peroxide and sulfuric acid, which is therefore recovered.
[070] In an additional alternative, hydrogen peroxide can be prepared directly from the elements hydrogen and oxygen.
[071] In this way, the spent catalyst, comprising a zeolite containing titanium to be subjected to regeneration steps (a) to (d) is obtained by a process for the preparation of an olefin oxide, comprising: (i) providing a mixture comprising an organic solvent, propene, hydrogen peroxide and at least partially dissolved potassium, comprising salt, wherein the organic solvent is selected from the group consisting of methanol and acetonitrile; (ii) subjecting the mixture provided in (i) in a reactor to conditions of epoxidation in the presence of catalyst, obtaining a mixture comprising the organic solvent and propylene oxide and obtaining the catalyst having a potassium salt deposited in it POTASSIUM SALT
[072] Regarding the chemical nature of at least one potassium salt under consideration, there are no specific restrictions. Preferably, the at least one potassium salt is selected from the group consisting of at least one inorganic potassium salt, at least one organic potassium salt and combinations of at least one inorganic potassium salt and at least one organic potassium salt .
[073] Preferred inorganic potassium salts include, but are not restricted to, potassium halides, such as potassium chloride or potassium bromide, potassium nitrate, potassium sulfate, potassium hydrogen sulfate, potassium hydroxide, potassium perchlorate , potassium salts, comprising phosphorus, such as potassium dihydrogen phosphate or dipotassium hydrogen phosphate or potassium phosphate or potassium pyrophosphates, such as monobasic potassium pyrophosphate or dibasic potassium pyrophosphate or potassium pyrophosphate or potassium pyrophosphate or potassium pyrophosphate or potassium pyrophosphate potassium etidronates, such as monobasic potassium etidronate or dibasic potassium etidronate or tribasic potassium etidronate or tetrabasic potassium etidronate, potassium cyanate, potassium oxides, such as potassium oxide (K2O) or superoxide or potassium peroxide (K2O2).
[074] Preferred organic potassium salts include, but are not restricted to, potassium carbonate (K2CO3), potassium hydrogen carbonate, potassium salts of aliphatic saturated carboxylic acids, such as monocarboxylic acids, preferably from 1 to 6, more preferably from 1 to 5, more preferably from 1 to 4, most preferably from 1 to 3 carbon atoms, such as formic acid, acetic acid, propionic acid, dicarboxylic acids, more preferably from 2 to 6, more preferably from 2 to 4 carbon atoms, such as oxalic acid, malonic acid, succinic acid, tartaric acid, tricarboxylic acids, preferably having 6 to 10 carbon atoms, such as isocitric acid, citric acid or propane-1, 2,3-tricarboxylic acid or tetracarboxylic acids. Preferably, the organic potassium salt is selected from the group consisting of potassium salts of saturated aliphatic monocarboxylic acids, preferably having 1, 2, 3, 4, 5 or 6 carbon atoms, potassium carbonate and potassium hydrogen carbonate. More preferably, the organic potassium salt is selected from the group consisting of potassium formate, potassium acetate, potassium propionate, potassium carbonate and potassium hydrogen carbonate. More preferably, the organic potassium salt is selected from the group consisting of potassium formate, potassium acetate, potassium carbonate and potassium hydrogen carbonate.
[075] In this way, potassium comprising salt is selected from the group consisting of at least one inorganic potassium salt selected from the group consisting of potassium hydroxide, potassium halides, potassium nitrate, potassium sulfate, potassium hydrogen, potassium perchlorate, potassium dihydrogen phosphate or dipotassium hydrogen phosphate or potassium phosphate or potassium pyrophosphates such as monobasic potassium pyrophosphate or dibasic potassium pyrophosphate or potassium or potassium pyrophosphate, potassium or phosphate potassium or tribasic potassium such as monobasic potassium etidronate or dibasic potassium etidronate or tribasic potassium etidronate or tetrabasic potassium etidronate, at least one organic potassium salt selected from the group consisting of saturated aliphatic monocarboxylic acid potassium salts, preferably having 1, 2 , 3, 4, 5 or 6 carbon atoms, carbon potassium act and potassium hydrogen carbonate and a combination of at least one of at least one inorganic potassium salt and at least one of at least one organic potassium salt.
[076] More preferably, potassium comprising salt is selected from the group consisting of at least one inorganic potassium salt selected from the group consisting of potassium dihydrogen phosphate or hydrogen diphosphate phosphate or potassium hydroxide, potassium halides, potassium nitrate, potassium sulphate, potassium hydrogen sulphate, potassium perchlorate, at least one organic potassium salt selected from the group consisting of potassium formate, potassium acetate, potassium propinoate, potassium carbonate and potassium hydrogen carbonate , and a combination of at least one of the at least one of the inorganic potassium salts and at least one of the at least one of the organic potassium salts.
[077] Especially preferably, the potassium comprising salt according to (i) is potassium dihydrogen phosphate, dipotassium hydrogen phosphate or potassium formate. Therefore, if according to (i), a single potassium salt is used, the potassium salt comprising is more preferably potassium dihydrogen phosphate, dipotassium hydrogen phosphate or potassium formate. If according to (i), two or more potassiums comprising salts are used, a potassium salt is potassium dihydrogen phosphate, dipotassium hydrogen phosphate or potassium formate.
[078] In this way, the spent catalyst, comprising a zeolite containing titanium to be subjected to regeneration steps (a) to (d) is obtained by a process for the preparation of an olefin oxide, comprising: (i) providing a mixture comprising an organic solvent, propene, hydrogen peroxide, and at least partially dissolved potassium, comprising salt, in which the organic solvent is selected from the group consisting of methanol and acetonitrile and in which the potassium comprising salt is selected from the group consisting of dihydrogen phosphate, dipotassium hydrogen phosphate, potassium formate and a mixture of two or more of these; (ii) subjecting the mixture provided in (i) in a reactor to conditions of epoxidation in the presence of catalyst, obtaining a mixture comprising the organic solvent and propylene oxide and obtaining the catalyst having a potassium salt deposited in it
[079] According to (i), a mixture is provided comprising potassium comprising salt. Regarding the concentration of potassium comprising salt in the liquid supply stream, there is no specific restriction. Preferably, the concentration of potassium comprising salt in the mixture provided in (i) is at least 10%, preferably in the range of from 10 to 100%, preferably from 20 to 100%, more preferably from 30 to 100 %, more preferably from 40 to 100% of the potassium solubility limit comprising salt in the liquid feed stream provided in (i). The term "limit of solubility of at least one potassium salt in the liquid feed stream" as used in the context of the present invention refers to the saturation concentration of potassium comprising salt in the liquid feed stream, where by adding more than potassium comprising salt, the concentration of potassium comprising salt as a solute in the mixture does not increase and potassium comprising salt would begin to precipitate. The limit of solubility of potassium comprising salt in the mixture will depend on the composition of the mixture and conditions, such as the temperature at which, and the pressure under which, the mixture is provided in (i). Determining the potassium solubility limit comprising salt in the mixture is an easy and direct task for the person skilled in the art knowing these conditions and said composition of a certain mixture. A simple procedure to assess whether the amount of potassium comprising salt being added is above the solubility limit is to pass the mixture before subjecting it to epoxidation conditions in (ii) through a filter and to measure the pressure drop through the filter . If the pressure drop across the filter increases over time and the potassium comprising salt is found in the filter when it is taken offline, the amount of potassium comprising salt being added is already above the solubility limit.
[080] Preferably in (i), the molar ratio of potassium comprised in potassium comprising salt in relation to the epoxidation agent, preferably hydrogen peroxide, comprised in the range of 10 x 10-6: 1 to 1500 x 10-6: 1 , preferably from 20 x 10-6: 1 to 1300 x 10- 6: 1, more preferably from 30 x 10-6: 1 to 1000 x 10-6: 1, The molar amount of potassium comprised in the potassium comprising salt refers to if the total molar amount of potassium comprised in all potassium comprising salts used in (i), if two or more potassium comprising salts are used.
[081] Additionally preferably in (i), the molar ratio of potassium to the epoxidation agent, preferably hydrogen peroxide, in the mixture, is in the range of 10 x 10-6: 1 to 1500 x 10-6: 1, preferably from 20 x 10-6: 1 to 1300 x 10-6: 1, more preferably from 30 x 10-6: 1 to 1000 x 10-6: 1,
[082] In this way, the spent catalyst, comprising a zeolite containing titanium to be subjected to regeneration steps (a) to (d) is obtained by a process for the preparation of an olefin oxide, comprising: (i) providing a mixture comprising an organic solvent, propene, hydrogen peroxide, and at least partially dissolved potassium, comprising salt, in which the organic solvent is selected from the group consisting of methanol and acetonitrile and in which the potassium comprising salt is selected from the group consisting of dihydrogen phosphate, dipotassium hydrogen phosphate, potassium formate and a mixture of two or more of these; (ii) subjecting the mixture provided in (i) in a reactor to conditions of epoxidation in the presence of catalyst, obtaining a mixture comprising the organic solvent and propylene oxide and obtaining the catalyst having a potassium salt deposited in it,
[083] wherein the mixture according to (i) contains potassium comprising salt with a molar ratio of potassium comprising potassium comprising salt to hydrogen peroxide in the range of 10x10-6: 1 to 1500x10-6: 1, preferably from 20x10-6: 1 to 1300x10-6: 1, more preferably from 30x10-6: 1 to 1000x10-6: 1.
[084] Preferably, the process for preparing an olefin oxide according to the present invention is a continuous process. In this way, the spent catalyst, comprising a zeolite containing titanium to be subjected to regeneration steps (a) to (d) is obtained by a process for the preparation of a propylene oxide, comprising: (i) providing a supply current liquid comprising an organic solvent, an olefin, an epoxidizing agent and at least partially dissolved potassium, comprising salt; (ii) passing the feed stream provided in (i) in an epoxidation reactor comprising a catalyst comprising a zeolite containing titanium as a catalytically active material and subjecting the feed stream to epoxidation reaction conditions in the epoxidation reactor, obtaining a mixture reaction comprising the organic solvent and the olefin oxide, and obtaining the catalyst having a potassium salt deposited in it.
[085] More preferably, the spent catalyst, comprising a zeolite containing titanium to be subjected to regeneration steps (a) to (d) is preferably obtained by a process for the preparation of a propylene oxide, comprising: (i) providing a liquid feed stream comprising an organic solvent, propene, hydrogen peroxide, and at least partially dissolved potassium, comprising salt, in which the organic solvent is selected from the group consisting of methanol and acetonitrile and in which the potassium comprising salt is selected from the group consisting of dihydrogen phosphate, dipotassium hydrogen phosphate, potassium formate and a mixture of two or more of these; (ii) passing the feed stream provided in (i) in an epoxidation reactor comprising a catalyst comprising a zeolite containing titanium as a catalytically active material and subjecting the feed stream to epoxidation reaction conditions in the epoxidation reactor, obtaining a mixture of reaction comprising the organic solvent and the propylene oxide, and obtain the catalyst having a potassium salt deposited in it.
[086] wherein the mixture according to (i) contains potassium comprising salt with a molar ratio of potassium comprising potassium comprising salt to hydrogen peroxide in the range of 10x10-6: 1 to 1500x10-6: 1, preferably from 20x10-6: 1 to 1300x10-6: 1, more preferably from 30x10-6: 1 to 1000x10-6: 1.
[087] Preferably, the mixture, preferably the liquid feed stream provided in (i), is free of ammonium dihydrogen phosphate More preferably, the mixture, preferably the liquid feed stream provided in (i), is free of phosphate ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate. More preferably, the mixture, preferably the liquid feed stream provided in (i), is free of ammonium carbonate, ammonium hydrogen carbonate, ammonium dihydrogen phosphate, ammonium hydrogen phosphate, ammonium phosphate, hydrogen pyrophosphate ammonium, ammonium pyrophosphate, ammonium chloride, ammonium nitrate and ammonium acetate. Preferably, the mixture, preferably the liquid feed stream provided in (i), is free of an ammonium salt. The term "free of", as used in this context of the present invention, refers to a concentration of a respective compound of a maximum of 2 weight-ppm, preferably a maximum of 1 weight-ppm, based on the total weight of the mixture, preferably the liquid feed stream.
[088] Preferably, the mixture, preferably the liquid feed stream provided in (i), contains sodium in molar ratio of sodium to the epoxidation agent, preferably hydrogen peroxide in the range of 1x10-6: 1 to 250x10-6 : 1, preferably from 5x10-6: 1 to 50x10-6: 1. Preferably, the mixture, preferably the liquid feed stream provided in (i), does not comprise dissolved sodium dihydrogen phosphate (NaH2PO4), more preferably neither dissolved sodium dihydrogen phosphate nor dissolved disodium hydrogen phosphate (Na2HPO4), more preferably neither sodium dihydrogen phosphate dissolved neither disodium hydrogen phosphate nor dissolved sodium phosphate (Na3PO4). LIQUID SUPPLY CHAIN
[089] Generally, the liquid supply stream can be provided in (i) according to any conceivable method. Preferably, the liquid feed stream is provided in (i) by combining at least four individual streams in which a first stream comprises the epoxidizing agent, preferably hydrogen peroxide, a second stream comprises the olefin, preferably propene and optionally propane, a third stream comprises the organic solvent, preferably selected from the group consisting of methanol and acetonitrile and, optionally, water and a fourth stream comprises potassium comprising salt.
[090] These at least four individual streams can be combined in all appropriate orders. Preferably, the stream comprising potassium comprising salt is combined with the stream comprising the epoxidating agent, and the resulting combined stream is combined with a stream resulting from the combination of stream comprising the organic solvent and the stream comprising the olefin. The current obtained in this way is the net current provided in (i).
[091] Preferably, the chain comprising propene also comprises propane in which preferably at least 98% by weight, more preferably at least 99% by weight, more preferably at least 99.5% by weight, more preferably at least 99.9% by weight of current consist of propylene and propane. Preferably, the weight ratio of propene to propane in the chain is at least 7: 3. For example, commercially available propylene can be used, which can be either a polymer-grade propylene or a chemical-grade propene. Typically, polymer grade propene has a propene content in the range of 99 to 99.8% by weight and a propane content in the range of 0.2 to 1% by weight. Chemical grade propene typically has a propene content in the range of 92 to 98% by weight and a propane content in the range of 2 to 8% by weight. Preferably, a chain is employed having a propene content in the range of 99% and 99.8% by weight and a propane content in the range of 0.2% to 1% by weight.
[092] Preferably, the stream comprising olefin and, optionally, propane is free of potassium cations (K +) and free of phosphorus (P) in the form of anions of at least one phosphorus oxy acid. The term "potassium cations (K +) free", as used in this context of the present invention, refers to a chain comprising olefin and, optionally, propane containing potassium (K +) cations in an amount of less than 1 weight- ppm, preferably less than 0.1 weight-ppm, based on the total weight of the chain. The term "phosphorus-free (P) in the form of anions of at least one phosphorus oxy acid", as used in this context of the present invention, refers to a stream comprising the olefin and optionally propane containing phosphorus (P) in the form of anions of at least one phosphorus oxyacid in an amount of less than 1 weight-ppm, preferably less than 0.1 weight-ppm, based on the total weight of the chain.
[093] The stream comprising hydrogen peroxide can be prepared according to any conceivable method. It is conceivable to obtain the current comprising hydrogen peroxide by converting sulfuric acid into peroxodisulfuric acid by anodic oxidation with simultaneous evolution of hydrogen at the cathode. The hydrolysis of peroxodisulfuric acid then leads, by means of peroxomonosulfuric acid, to hydrogen peroxide and sulfuric acid which is thus obtained again. The preparation of hydrogen peroxide from the elements is also possible. Depending on the specific method of preparation, the stream comprising hydrogen peroxide can be, for example, a stream of aqueous / methanolic hydrogen peroxide, preferably a stream of aqueous hydrogen peroxide. If aqueous hydrogen peroxide feed is used, the content of the stream with respect to hydrogen peroxide is, in most cases, in the range of 3 to 85% by weight, preferably 25 to 75% by weight, more preferably 30 to 50% by weight, such as 30 to 40% by weight or 35 to 45% by weight from 40 to 50% by weight. Preferably, at least 25% by weight, more preferably at least 30% by weight, more preferably 35% by weight of the chain comprising hydrogen peroxide consists of water and hydrogen peroxide. Preferred ranges are 30 to 80% by weight or 35 to 75% by weight or 40 to 70% by weight.
[094] According to the present, it is preferable to employ a chain comprising hydrogen peroxide which is obtained as a crude solution of hydrogen peroxide by extracting a mixture that results from a process known as the anthraquinone process, by means of from which practically all the world's production of hydrogen peroxide is produced (see, for example Ullmann's Encyclopedia of Industrial Chemistry, fifth edition [5th edition], volume A 13 (1989) pages 443-466) in which a solution of an anthraquinone is used containing alkyl group preferably having between 2 to 10 carbon atoms, more preferably at least 5 carbon atoms such as 5 carbon atoms or 6 carbon atoms and where the solvent used consists, in most cases, of a mixture of two different solvents. This anthraquinone solution is, in most cases, referred to as the working solution. In this process, the hydrogen peroxide formed in the course of the anthraquinone process is, in most cases, generally separated by means of extraction from the respective working solution after a hydrogenation / reoxidation cycle. This extraction can be carried out preferably with essentially pure water, and the crude aqueous hydrogen peroxide solution is obtained. Although it is generally possible to further purify the crude aqueous hydrogen peroxide solution by distillation, it is preferred, according to the present invention, to use such a crude aqueous hydrogen peroxide solution which has not been subjected to purification by distillation. In addition, it is generally possible to subject the crude aqueous hydrogen peroxide solution to an additional extraction step in which a suitable extraction agent, preferably an organic solvent, is used. Preferably, the organic solvent used in this additional extraction step is the same solvent which is used in the anthraquinone process. Preferably, the extraction is performed using only one of the solvents in the working solution, and more preferably using only the most non-polar solvent in the working solution. If the crude aqueous hydrogen peroxide solution is subjected to such an additional extraction step, a so-called washed crude hydrogen peroxide solution is obtained. According to a preferred embodiment of the present invention, the washed crude hydrogen peroxide solution is used as a feed of hydrogen peroxide. The production of a crude solution is described, for example, in European Patent Application EP 1 122 249 A1. As regards the term "essentially pure water", reference is made to paragraph 10, page 3 of EP 1 122 249 A1, which is incorporated into this document as a reference.
[095] In order to provide sufficient stability of hydrogen peroxide during extraction with water, preferably essentially pure water, suitable stabilizing agents are, in most cases, added to the water, preferably to the essentially pure water used. Strong inorganic acids and / or chelating agents should be specifically mentioned. According to preferred extraction processes, small amounts of nitrates and / or phosphates and pyrophosphates, respectively, are added as stabilizing agents, either as acids or as sodium salts. Such stabilizing agents are added, in most cases, in quantities in such quantities that the aqueous crude hydrogen peroxide solution contains 50 to 400 wt-wt sodium cations, 100 to 700 wt-wt phosphorus calculated as phosphate (PO43-), and from 50 to 400 weight-ppm of nitrate anions, in each case calculated with respect to the hydrogen peroxide contained in the crude aqueous hydrogen peroxide solution. Preferred ranges are, for example, between 50 to 200 weight-ppm or 50 to 100 weight-pmm of sodium cations, 100 to 500 weight-ppm or 100 to 300 weight-pmm of phosphorus, and 50 to 200 weight-ppm or 50 to 100 weight-ppm of nitrate. In addition, it is conceivable that other stabilizing agents, such as stannites, such as, for example, sodium stannite (Na2SnO2) and / or organic phosphonic acids, in particular organic diphosphonic acids such as etidronic acid, are used. Preferably, the aqueous hydrogen peroxide stream comprises sodium with the molar ratio of sodium to hydrogen peroxide in the range between 1x10-6: 1 and 250x10-6: 1, more preferably from 5x10-6: 1 to 50x10-6: 1.
[096] In general, the molar ratio of water to the organic solvent in the liquid feed stream provided in (i) is not subject to any specific restrictions. Preferably, in particular if the organic solvent is acetonitrile, the molar ratio of water to the organic solvent is at most 1: 4, more preferably in the range of 1:50 to 1: 4, preferably from 01:15 to 1 : 4.1, more preferably from 1:10 to 1: 4.2.
[097] In this way, the spent catalyst, comprising a zeolite containing titanium to be subjected to regeneration steps (a) to (d) is obtained by a process for the preparation of an olefin oxide, comprising: (i) providing a liquid feed stream comprising an organic solvent, optionally propene, hydrogen peroxide, water, and at least partially dissolved potassium, comprising salt, in which the organic solvent is selected from the group consisting of methanol and acetonitrile and in which the potassium comprising salt is selected from the group consisting of dihydrogen phosphate, dipotassium hydrogen phosphate, potassium formate and a mixture of two or more of these; (ii) passing the feed stream provided in (i) in an epoxidation reactor comprising a catalyst comprising a zeolite containing titanium as a catalytically active material and subjecting the feed stream to epoxidation reaction conditions in the epoxidation reactor, obtaining a mixture of reaction comprising the organic solvent and the propylene oxide, water, optionally propene, optionally propane, and obtaining the catalyst having a potassium salt deposited itself.
[098] in which the mixture according to (i) contains potassium comprising salt with a molar ratio of potassium comprising potassium comprising salt to hydrogen peroxide in the range of 10x10-6: 1 to 1500x10-6: 1, preferably from 20x10-6: 1 to 1300x10-6: 1, more preferably from 30x10-6: 1 to 1000x10-6: 1.
[099] In the event that acetonitrile is used as a solvent, the mixture provided in (i), preferably the liquid feed stream provided in (i), preferably comprises acetonitrile in an amount of 60% to 75% by weight, preferably of 60% to 65% by weight, based on the total weight of the liquid feed stream; hydrogen peroxide in an amount of 6% to 10% by weight, preferably from 7% to 9% by weight, based on the total weight of the liquid feed stream; water in a molar ratio of water to acetonitrile of a maximum of 1: 4, preferably in the range of 1:50 to 1: 4, preferably of 1:15 to 1: 4.1 more preferably of 1:10 to 1 : 4.2; propene with a molar ratio of propene to hydrogen peroxide comprised in the liquid feed stream in the range of 1: 1 to 1.5: 1, preferably from 1.1: 1 to 1.4: 1; and optionally, propane with a molar ratio of propane to the sum of propene and propane in the range of 0.0001: 1 to 0.15: 1, preferably from 0.001: 1 to 0.05: 1;
[100] Where at least 95% by weight, preferably from 95 to 100% by weight, more preferably from 98 to 100% by weight of the liquid feed stream provided in (i) consists of propene, peroxide hydrogen, acetonitrile, water, potassium comprising salt, and optionally propane. STEP (II)
[101] The mixture provided in (i) is submitted in (ii) in an appropriate reactor to appropriate epoxidation conditions in the presence of the catalyst comprising a titanium containing zeolite as a catalytically active material. CATALYST UNDERSTANDING A ZEOLITE CONTAINING TITANIUM AS CATALYTICALLY ACTIVE MATERIAL
[102] In general, the titanium-containing zeolite used as a catalytically active material may have a type of frame structure according to the following three-letter codes: ABW, ACO, AEI, AEL, AEN, AET, AFG, AFI, AFN , AFO, AFR, AFS, AFT, AFX, AFY, AHT, ANA, APC, APD, AST, ASV, ATN, ATO, ATS, ATT, ATV, AWO, AWW, BCT, BEA, BEC, BIK, BOG, BPH , BRE, CAN, CAS, CDO, CFI, CGF, CGS, CHA, CHI, CLO, CON, CZP, DAC, DDR, DFO, DFT, DOH, DON, EAB, EDI, EMT, EPI, ERI, ESV, ETR , EUO, FAU, FER, FRA, GIS, GIU, GME, GON, GOO, HEU, IFR, ISV, ITE, ITH, ITW, IWR, IWW, JBW, KFI, LAU, LEV, LIO, LOS, LOV, LTA , LTL, LTN, MAR, MAZ, MEI, HONEY, MEP, MER, MMFI, MFS, MON, MOR, MSO, MTF, MTN, MTT, MTW, MWW, NAB, NAT, NEES, NON, NPO, OBW, OFF , OSI, OSO, PAR, PAU, PHI, PON, RHO, RON, RRO, RSN, RTE, RTH, RUT, RWR, RWY, SAO, SAS, SAT, SAV, SBE, SBS, SBT, SFE, SFF, SFG , SFH, SFN SFO, SGT, SOD, SSY, STF, STI, STT, TER, THO, TON, TSC, UEI, UFI, UOZ, USI, UTL, VET, VFI, VNI, VSV, WEI, WEN, YUG, ZON, or a mi structure or two or more of these frame structures. About the three-letter codes and their definitions, reference is made to “Atlas of Zeolite Framework Types”, 5 edition, Elsevier, London, England (2001). "
[103] In addition, it is preferred that the titanium-containing zeolite has an MFI frame structure, a MEL frame structure, a MWW frame structure, a MWW type frame structure, an ITQ frame structure, a BEA frame structure. , a MOR frame structure or a mixed structure of two or more of these frame structures, preferably an MFI frame structure, a MWW frame structure or a MWW type frame structure. Most preferably, the zeolite-containing titanium is a zeolite, known as "TS-1" (titanium silicalite-1) or TiMWW.
[104] Preferably, in particular if the titanium-containing zeolite is TiMWW, the titanium-containing zeolite comprises at least one element selected from the group consisting of Al, B, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Zn, Ga, Ge, In, Sn, Pb, Pd, Pt, Au, preferably from the group consisting of B, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co , Ni, Zn, Ga, Ge, In, Sn, Pb, Pd, Pt, Au, more preferably from the group consisting of Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Zn , Ga, Ge, In, Sn, Pb, Pd, Pt, Au. More preferably, the titanium-containing zeolite further comprises Zn.
[105] The term "MWW frame structure titanium zeolite", as used in the context of the present invention, also called "TiMWW", refers to a MWW frame structure zeolite which contains titanium as an element of isomorphic substitution in the zeolitic frame. Preferably, the zeolitic frame is essentially free of aluminum and consists essentially of silicon, titanium and oxygen. Preferably, at least 99% by weight, more preferably at least 99.5% by weight, more preferably at least 99.9% by weight of the zeolitic frame consists of silicon, titanium and oxygen. Optionally, the MWW frame type titanium zeolite may comprise extra-frame titanium, which should be comprised of any and all titanium species that are not part of the MWW zeolitic frame. The preparation of TiMWW catalysts is described, for example, in US 2007043226 A1, in particular in Examples 3 and 5 of US 2007043226 A1.
[106] The titanium content of MWW-type frame structure titanium zeolite is not subject to any specific restrictions. Preferably, the MWW-type frame structure titanium zeolite comprised in the catalyst in (ii) contains titanium, calculated as elemental titanium, in an amount ranging from 0.1 to 5% by weight, more preferably from 0.2 to 4% by weight, more preferably from 0.5 to 3% by weight, more preferably from 1 to 2% by weight, based on the total weight of the MWW type frame titanium zeolite. Consequently, the present invention relates to the process as described above, wherein the MWW-type frame structure titanium zeolite comprised in the catalyst in (ii) contains titanium, calculated as elementary titanium, in an amount in the range between 0.1 to 5% by weight, preferably between 1 to 2% by weight, silicon, based on the total weight of the titanium zeolite of frame structure type MWW.
[107] In addition to titanium, the MWW-type frame structure titanium zeolite can comprise at least one additional element other than titanium, silicon and oxygen. In general, it is conceivable that this at least one additional element is an isomorphic replacement element that is part of the MWW zeolitic frame structure. Preferably, this at least one additional additional element is not an isomorphic replacement element. Such an additional element that is not a replacement isomorphic element can be applied to the zeolite by, for example, a spraying process, a moisture impregnation process such as incipient moisture process, or any other suitable process. Preferably, the at least one additional element is selected from the group consisting of Al, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Zn, Ga, Ge, In, Sn, Pb, and a combination of two or more, preferably from the group consisting of Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Zn, Ga, Ge, In, Sn, Pb, and a combination of two or more. More preferably, the MWW-type frame structure titanium zeolite contains zinc as an additional element in addition to titanium, silicon and oxygen. More preferably, the MWW-type frame structure titanium zeolite contains zinc as the only additional element in addition to titanium, silicon and oxygen. More preferably, the MWW type frame titanium zeolite contains zinc as the only additional element in addition to titanium, silicon and oxygen in which at least 99% by weight, more preferably at least 99.5% by weight, more preferably at least 99.9 % by weight of the zeolitic frame structure consists of silicon, titanium and oxygen. More preferably, in the case of the MWW-type frame structure titanium zeolite contains zinc as the only additional element, at least 99% by weight, more preferably 99.5% by weight, more preferably 99.9% by weight of the frame structure titanium zeolite type MWW consists of zinc, titanium, silicon and oxygen; this MWW-type frame structure titanium zeolite containing zinc as the only additional element is also called "ZnTiMWW". ZnTiMWW Catalyst
[108] The zinc content of MWW-type frame structure titanium zeolite is not subject to any specific restrictions. Preferably, the MWW frame structure titanium zeolite comprised in the catalyst in (ii) contains zinc, calculated as elemental zinc, in an amount ranging from 0.1 to 5% by weight, more preferably from 0.2 to 4% by weight, more preferably from 0.5 to 3% by weight, more preferably from 1 to 2% by weight, based on the total weight of the MWW type frame titanium zeolite. Consequently, the present invention relates to the process as described above, in which the MWW-type frame structure titanium zeolite comprised in the catalyst in (ii) contains zinc, calculated as elemental zinc, in an amount ranging from 0.1 to 5% by weight, preferably between 1 to 2% by weight, silicon, based on the total weight of the MWW type frame titanium zeolite.
[109] The catalyst according to (ii), comprising the MWW frame structure titanium zeolite, may consist of the MWW frame structure titanium zeolite, preferably consisting of TiMWW or ZnTiMWW, as described. In such cases, the catalyst may be the titanium zeolite of MWW-type frame structure in the form of the zeolitic powder which can be molded, for example, into granules, a microsphere such as microsphere obtained from spray drying or granulation by spraying, a body shaped with, for example, the shape of a pellet, a tablet, a cylinder, a wheel, a star, a sphere and the like.
[110] Preferably, the catalyst according to (ii), comprising the MWW type frame titanium zeolite, preferably the TiMWW or the ZnTiMWW, is prepared as a molding body comprising the type frame structure titanium zeolite MWW, preferably TiMWW or ZnTiMWW, properly mixing the MWW frame structure titanium zeolite with at least one binder and / or with at least one binder precursor, and optionally at least one binder forming agent pores and / or at least one plasticizing agent. The molding bodies can be shaped in every conceivable geometry, such as strands, having, for example, rectangular, triangular, hexagonal, square, oval or circular cross sections, in the shape of a star, tablets, spheres, hollow cylinders and the like. Examples of such binders are metal oxides such as, for example, SiO2, Al2O3, TiO2, ZrO2 or MgO or clays or mixtures of two or more of these oxides or mixed oxides of at least two among Si, Al, Ti, Zr, and Mg , with SiO2 being preferred. Pore forming agents, such as mesoporous forming agents include polymeric vinyl compounds, such as polyalkylene oxides, such as polyethylene oxides, polystyrene, polyacrylates, polymethacrylates, polyolefins, polyamides and polyesters. Sizing agents include organic polymers, in particular hydrophilic, such as carbohydrates, such as cellulose, cellulose derivatives, such as methyl cellulose and starch, such as potato starch, wallpaper plaster, polyacrylates, polymethacrylates, polyvinyl alcohol, polyvinylpyrrolidone , polyisobutene or polytetrahydrofuran. The use of water, alcohols, glycols or mixtures thereof, such as mixtures of water and alcohol, or water and glycol, such as water and methanol, or water and ethanol, or water and propanol, or water and propyleglycol, as collage can be mentioned. Preferably, the catalyst according to (ii) is employed as a molding body that is shaped like an extrudate, preferably extrudates having a length preferably 1 to 10 millimeters, more preferably 1 to 7 millimeters, more preferably from 1 to 5 mm, and a diameter preferably from 0.1 to 5 mm, more preferably from 0.2 to 4 mm, more preferably from 0.5 to 2 mm. Specifically, with regard to the preferred catalyst according to (ii) comprising ZnTiMWW, it is preferable to employ this catalyst in the form of a micropowder or in the form of a molding body, in which the molding body preferably contains said micropowder.
[111] Said catalyst according to step (ii) of the present invention in the form of a micropowder, comprising ZnTiMWW, is preferably characterized by the following attributes and modalities, including combinations of modalities according to the given dependencies: 1. A micropowder, whose particles have a Dv10 value of at least 2 micrometers, said micropowder comprising mesopores with average pore diameter (4V / A) in the range of 2 to 50 nm as determined by Hg porosimetry according to DIN 66133, and comprising, based on the weight of the micropowder, at least 95% by weight of a MWW structure-type microporous aluminum zeolitic material containing titanium and zinc (ZnTiMWW). The Dv10 value is understood to be determined according to Reference Example 5.1 of the present invention. 2. The micropowder of modality 1, with a Dv10 value in the range between 2 and 5.5 micrometers, preferably 3 to 5.5 micrometers. 3. The micropowder of modalities 1 or 2, with a Dv50 value in the range between 7 and 25 micrometer and optionally a Dv90 value in the range between 26 and 85 micrometers. The Dv50 and Dv90 values are understood to be determined in accordance with Reference Example 5.1 of the present invention. 4. The micropowder of any of the modalities 1 to 3, in which the mesopores have an average pore diameter (4V / A) in the range between 10 to 50 nm, preferably from 15 to 40 nm, more preferably from 20 to 30 nm such as determined by Hg porosimetry according to DIN 66133. 5. The micropowder of any of the modalities 1 to 4, additionally comprising macropores with average pore diameter (4V / A) in the interval between more than 50 nm, said macropores, preferably having an average pore diameter in the range between 0.05 and 3 micrometers, as determined by Hg porosimetry according to DIN 66133. 6. The micropowder of any of the modalities 1 to 5, in which the microporous of the ZnTiMWW have an average diameter of pore in the range between 1.0 and 1.2 nanometers, as determined by nitrogen adsorption according to DIN 66135. 7. The micropowder of any of the modalities 1 to 6, comprising, based on the micropowder weight, at least 99% by weight , preferably at least 9 9.7% by weight of ZnTiMWW. 8. The micropowder of any of the modalities from 1 to 7, in which the ZnTiMWW contains zinc in an amount of 1.0% to 2.0% by weight, preferably from 1.2% to 1.9% by weight, calculated as Zn and based on the weight of the ZnTiMWW. 9. The micro-powder of any of the modalities from 1 to 8, in which ZnTiMWW contains titanium in an amount of 1.0% to 2.0% by weight, preferably from 1.2% to 1.8% in weight, calculated as Ti and based on the weight of the ZnTiMWW. 10. The micropowder of any of the modalities 1 to 9, presenting a crystallinity, as determined by X-ray diffraction analysis (XRD), of at least (80 +/- 10)%, preferably of at least (85+ / - 10)%. Crystallinity is understood to be determined according to Reference Example 5.7 of the present invention. 11. The micropowder of any of the modalities 1 to 10, comprising, based on the total weight of the micropowder and calculated as an element, less than 0.001% by weight, preferably less than 0.0001% by weight of a noble metal, preferably selected from among group consisting of gold, metal, platinum, palladium, iridium, ruthenium, osmium and a mixture of two or more of the same, most preferably selected from the group consisting of gold, platinum, gold and a mixture of two or more of the same . 12. The micropowder of any of the modalities 1 to 11, comprising, based on the total weight of the micropowder and calculated as an element, less than 0.1% by weight, preferably less than 0.01% by weight of boron. 13. The micropowder of any of the modalities 1 to 12, with apparent density in the range between 80 and 100 g / ml. 14. The micropowder of any of the modalities 1 to 13, being a spray powder, preferably capable of being obtained or obtained by spray drying.
[112] Furthermore, said catalyst according to step (ii) of the present invention in the form of a molding body, comprising the ZnTiMWW, is preferably characterized by the following attributes and modalities, including combinations of modalities according to the given dependencies: 1. A molding body, comprising MWW-free microporous aluminum zeolitic material containing titanium and zinc (ZnTiMWW), the said molding body preferably comprising a micropowder comprising, based on the weight of the micropowder , at least 95% of a MWW-free microporous aluminum zeolitic material containing titanium and zinc (ZnTiMWW), the said molding body comprising, even more preferably, the micropowder according to any of the modalities 1 to 14 described above, the molding body additionally preferably comprising at least one binder, preferably a silica binder. 2. The molding body of modality 1, comprising mesopores having an average pore diameter between 4 and 40 nm, preferably between 20 to 30 nm, as determined by Hg porosimetry according to DIN 66133. 3. The molding body of modality 1 or 2, with crystallinity, as determined by XRD analysis, of at least (55 +/- 10)%, preferably in the range of ((55 to75) +/- 10)%. Crystallinity is understood to be determined according to Reference Example 5.7 of the present invention. 4. The molding body of any one of modalities 1 to 3, comprising the micropowder in an amount in the range between 70 and 80% by weight and the silica binder in an amount between 30 to 20% by weight, the micropowder being together with the silica binder they make up at least 99% by weight of the molding body, where the molding body has a concentration of silanol groups with respect to the total number of Si atoms of a maximum of 6%, preferably a maximum of 3% , as determined according to 29SiMAS NMR. The concentration of the silanol groups is understood to be determined according to Reference Example 5.2 of the present invention. 5. The molding body of any of the modalities 1 to 4, being a filament with circular cross section and a diameter in the range between 1.5 to 1.7 mm and presenting a crushing force of at least 5 N, preferably in the range between 5 and 20 N, more preferably in the range between 12 and 20 N, the crushing force being determined by the crushing force testing machine Z2.5 / TS1S according to the method as described in Reference Example 5.3 of the present invention. 6. The molding body of any of modalities 1 to 5, the 29Si-NMR spectrum of said molding body comprising six peaks in the following position: peak 1 at -98 +/- x ppm, peak 2 at -104 + / - x ppm, peak 3 at -110 +/- x ppm, peak 4 at -113 +/- x ppm, peak 5 at -115 +/- x ppm, peak 6 at -118 +/- x ppm, with x at any of the peaks being 1.5, preferably 1.0, more preferably 0.5. where Q is defined as: Q = 100 * {[a1 + a2] / [a4 + a5 + a6]} / a3
[113] It is a maximum of 2.5, preferably a maximum of 1.6, preferably a maximum of 1.4, with [a1 + a2] being the sum of the peak areas of peaks 1 and 2, and [a4 + a5 + a6] being the sum of the areas of peak of peaks 4, 5, and 6, and a3 being the peak area of peak 3. Such 29Si-NMR characteristics are understood to be determined in accordance with Reference Example 5.4 of the present invention. 7. The molding body of any of the modalities 1 to 6, presenting water capture in the range between 3 to 8% by weight, preferably between 4 and 7% by weight. Water uptake is understood to be determined according to Reference Example 5.5 of the present invention. 8. The molding body of any one of the modalities 1 to 7, the infrared spectrum of said molding body comprising a strip in the region of (3700 - 3750) +/- 20 cm-1 and a strip in the region of ( 3670 - 3690) +/- 20 cm-1, where the ratio of the band's intensity in the region of (3700 - 3750) +/- 20 cm-1 with respect to the band in the region of (3670 - 3690) +/- 20 cm-1 is a maximum of 1.5, preferably a maximum of 1.4. Such IR characteristics are understood to be determined in accordance with Reference Example 5.6 of the present invention.
[114] Furthermore, a preferred process for the preparation of said catalyst according to (ii) in the form of a micropowder and / or molding body, comprising ZnTiMWW, is preferably characterized by the following attributes and modalities, including combinations of modalities according to the given dependencies: 1. A process that comprises (a) the provision of a suspension containing MWW-free microporous aluminum zeolitic material with titanium and zinc (ZnTiMWW) structure; (b) subjecting the suspension provided in (a) to spray drying in order to obtain a micropowder; (c) optional calcination of the micropowder obtained in (b), wherein the micropowder obtained in (b) or (c), preferably in (c), is preferably the micropowder according to any one of said modalities of microwell 1 to 14 as described above. 2. The method of mode 1, in which the suspension provided in (a) has a solids content in the range of 5 to 25% by weight, preferably between 10 and 20% by weight, the suspension being preferably an aqueous suspension. 3. The modality 1 or 2 process, in which the ZnTiMWW according to (a) contains zinc in an amount of between 1.0 to 2.0% by weight, preferably from 1.2% to 1.9% by weight, calculated as Zn, and titanium in quantities between 1.0 and 2.0% by weight, preferably between 1.2 and 1.8% by weight, calculated as Ti and based on the weight of ZnTiMWW. 4. The process of any of the modalities 1 to 3, in which (b) a spray apparatus, preferably a spray tower, is used to spray dry the suspension, said apparatus having at least one spray nozzle, preferably at least one bicomponent nozzle, said nozzle having a diameter in the range between 3.5 and 4.5. 5. The process of any of the modalities 1 to 4, in which in (b), a spraying apparatus, preferably a spraying tower, is used for drying the spray suspension, said apparatus being operated with a spray nozzle. gas having a temperature in the range between 20 to 50 ° C, preferably from 20 to 30 ° C and a drying gas having a temperature in the range between 250 and 350 ° C, preferably between 275 and 325 ° C, said nozzle gas being one inert gas, preferably technical nitrogen, and said drying gas being an inert gas, more preferably technical nitrogen. 6. The process of any of the modalities 1 to 5, in which (c) the micropowder is calcined at a temperature in the range between 600 and 700 ° C for a duration in the range between 0.5 to 6 h. 7. The process, according to any of modalities 1 to 6, further comprising (d) molding the micropowder obtained in (b) or (c) so as to obtain a molding body; (e) optional drying and / or calcining of the impression body obtained in (d). 8. The modality 7 process, in which the molding according to (d) comprises (aa) mixing the micropowder with a binder or binder precursor, preferably silica binder or silica binder precursor, in which the ratio of weight of the ZnTiMWW contained in the micropowder with respect to the silica contained in or resulting from the silica binder is in the range between 3: 7 and 1: 4, in order to obtain the mixture; (bb) the molding of the mixture obtained in (aa) to obtain the molding body, said molding comprising submitting the mixture obtained in (aa) to the extrusion from which, preferably, filaments are obtained, preferably having a diameter in the interval between 1.0 and 2.0 mm, more preferably from 1.5 to 1.7 mm. 9. The process of modality 8, in which (aa), a carbohydrate and / or water are added as bonding agents. 10. The 8 or 9 modality process, in which the mixture in (aa) is performed for a duration ranging from 15 to 60 min, preferably from 30 to 55 min, more preferably from 40 to 50 min. 11. The process of any of the modalities 7 to 10, in which (d), no mesoporous forming agent selected from the group consisting of polyalkylene oxides such as polyethylene oxides, polystyrene, polyacrylates, polymethacrylates, polyolefins , polyamides and polyesters is added. 12. The process of any of the modalities 7 to 11, in which in (e), the molding body is dried at a temperature in the range between 100 and 150 ° C for a duration in the range between 10 and 20 h and calcined to a temperature in the range between 500 and 600 ° C for a duration in the range between 0.5 and 2 h. 13. The process of any of modalities 7 to 12 further comprising (f) subjecting the impression body obtained in (d) or (e), preferably in (e), to a water treatment; (g) optional drying and / or calcining of the water-treated impression body, wherein the impression body obtained in (f) or (g), preferably in (g), is preferably the impression body according to any one of said molding body modalities 1 to 8, as described above. 14. The 13-mode process, in which (f), the water treatment comprises the treatment of the molding body with liquid water in an autoclave under autogenous pressure at a temperature between 100 and 200 ° C, preferably between 125 and 175 ° C, more preferably between 140 and 150 ° C for a period of 2 to 24 hours, preferably between 6 to 10 hours. 15. The 13 or 14 modality process, in which (f) the weight ratio of the molding body with respect to water is between 0.02 and 0.08, preferably between 0.03 and 0.07, more preferably between 0.04 and 0.06. 16. The process of any of the modalities 13 to 15, in which in (g), the molded body treated with water is dried at a temperature in the range between 100 and 150 ° C for a duration in the range between 10 and 20 h calcined at a temperature in the range between 400 and 500 ° C for a duration in the range between 1 and 3 h. 17. The process of any of the modalities 7 to 16, in which the molding body is not subjected to steam.
[115 With respect to said preferred process for preparing said catalyst according to (b) in the form of a micropowder and / or a molding body, comprising ZnTiMWW, described above by modalities 1 to 17, the ZnTiMWW based on which the suspension in mode 1. (a) is provided can be prepared according to any conceivable method. For example, it is possible to prepare a microporous aluminum-free zeolitic material of a MWW-type structure containing titanium (TiMWW) and subject the TiMWW to an appropriate treatment to obtain the ZnTiMWW. In addition, it is possible to prepare a microporous aluminum-free zeolitic of MWW-type structure (MWW) and subject the MWW to an appropriate treatment in order to obtain the ZnTiMWW in which, for example, both Zn and Ti are properly incorporated into the MWW. Furthermore, it is conceivable to prepare microporous aluminum-free zeolitic material of MWW-type structure in which, during the synthesis of the MWW-type frame, Ti is introduced and the resulting material is subjected to a suitable treatment to incorporate Zn, or Zn is introduced and the The resulting material is subjected to a suitable treatment to incorporate Ti, or both Zn and Ti are introduced. As conceivable methods for the preparation of TiMWW, the processes as described, for example, in US 6,114,551, or in Wu et al., “Hydrothermal Synthesis of a novel Titanosílicate with MWW Topology”, Chemistry Letters (2000), can be mentioned. pp. 774-775. Preferably, an aluminum-free microporous zeolitic material of MWW-type structure containing Ti (TiMWW) is prepared in a first stage, and in a second stage, TiMWW is subjected to an appropriate treatment to obtain ZnTiMWW. More preferably, ZnTiMWW is prepared according to a process which comprises (I) preparing an aluminum-free zeolitic material of a MWW-type structure containing boron (B-MWW); (II) removal of boron from the B-MWW in order to obtain a microporous aluminum-free zeolitic material of MWW type structure (MWW); (III) incorporation of titanium (Ti) in the MWW in order to obtain a zeolitic aluminum-free material of MWW type structure containing Ti (TiMWW); (IV) preferably, the treatment with TiMWW acid; (V) submission of TiMWW to zinc (Zn) impregnation in order to obtain ZnTiMWW.
[116] Preferably, in step (I), the B-MWW is prepared by a process whose preferred stages and conditions are defined by the following modalities 1 to 28 and the respective dependencies, as indicated: 1. A process for the preparation of a zeolitic material containing free aluminum boron comprising the MWW frame structure (B-MWW), comprising (a) the hydrothermal synthesis of a BMWW precursor from a synthesis mixture containing water, a source of silicon, a source of boron, and a MWW model compound obtaining the precursor of B-MWW in its mother liquor, with the mother liquor pH above 9; (b) adjusting the pH of the mother liquor, which was obtained in (a) and containing the precursor of B-MWW, to a value in the range between 6 and 9; (c) separating the B-MWW precursor from the adjusted pH mother liquor obtained in (b) by filtration in a filtration device. 2. The method of mode 1, wherein in (a) at least 95% by weight, preferably at least 99% by weight, more preferably at least 99.9% by weight of the synthesis mixture consists of water, the source of silicon , the boron source, and the model compound. 3. The modality 1 or 2 process, in which (a), the silicon source is selected from the group consisting of smoked silica, colloidal silica, and a mixture of them, the silicon source preferably being colloidal silica, more preferably ammonia stabilized silica, the boron source is selected from the group consisting of boric acid, borates, boron oxide, and a mixture of two or more of them, the boron source preferably being boric acid, and the compound model MWW selected from the group consisting of piperidine, hexamethylene imine, Ion N, N, N, N ', N', N'-hexamethyl-1,5-pentanediamonium, 1,4-bis (N-methylpyrrolidinium) butane , octyltrimethylammonium hydroxide, heptyltrimethylammonium hydroxide, hexyltrimethylammonium hydroxide, N, N, N-trimethyl-1-adamantyl ammonium hydroxide, and a mixture of two or more of them, the MWW structural director compound preferably being piperidine. 4. The process of any of the modalities 1 to 3 in which in (a), the synthesis mixture contains the source of boron, which was calculated as elemental boron, in relation to the source of silicon, which was calculated as elemental silicon, in a molar ratio in the range from 0.4: 1 to 2.0: 1, preferably from 0.6: 1 to 1.9: 1, more preferably from 0.9: 1 to 1 , 4: 1, water with respect to the silicon source, which was calculated as elemental silicon, in a molar ratio in the range from 1: 1 to 30: 1, preferably from 3: 1 to 25: 1, more preferably from 6: 1 to 20: 1; and the MWW model compound with respect to the silicon source, which was calculated as elemental silicon, in a molar ratio in the range from 0.4: 1 to 2.0: 1, preferably from 0.6: 1 to 1.9: 1, more preferably from 0.9: 1 to 1.4: 1, 5. The process, of any of the modalities 1 to 4, in which in (a), the hydrothermal synthesis is carried out at a temperature in the range from 160 to less than 180 ° C, preferably from 170 to 175 ° C, for a period of time in the range from 1 to 72 h, preferably from 6 to 60 h, more preferably from 12 to 50 h. 6. The process of any one of modalities 1 to 5, in which in (a), the hydrothermal synthesis is carried out at least partially under agitation. 7. Process, according to any one of modalities 1 to 6, in which in (a), the synthesis mixture additionally contains a seeding material, preferably a zeolitic material comprising the MWW framework structure, more preferably a boron-containing zeolitic material understanding the MWW framework structure. 8. The process, according to modality 7, in which the synthesis mixture contains the seeding material, with respect to the silicon source, in a weight ratio in the range from 0.01: 1 to 1 : 1, preferably from 0.02: 1 to 0.5: 1, more preferably from 0.03: 1 to 0.1: 1, which was calculated as the amount of seeding material in kg with respect to silicon contained in the silicon source that was calculated as silicon dioxide in kg. 9. The process, according to any of modalities 1 to 8, in which the pH of the mother liquor obtained from (a) is above 10, preferably in the range from 10.5 to 12, more preferably from 11 to 11.5. 10. The process, according to any of modalities 1 to 9, in which in (b), the pH of the mother liquor obtained in (a) is adjusted to a value in the range from 6.5 to 8.5, preferably at from 7 to 8. 11. The process, according to any of modalities 1 to 10, in which in (b), the pH is adjusted by a method comprising (aa) adding an acid to the mother liquor obtained from (a) containing the precursor BMWW, wherein the addition is preferably carried out at least partially with stirring. 12. The process, according to modality 11, in which (aa), the addition is carried out at a temperature in the range from 20 to 70 ° C, preferably between 30 and 65 ° C, more preferably between 40 and 60 ° C. 13. The process, according to modality 11 or 12, in which (aa), the acid is an inorganic acid, preferably an aqueous solution containing the inorganic acid. 14. The process, according to modality 13, in which the inorganic acid is selected from the group consisting of phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, and a mixture of two or more of them, the inorganic acid preferably nitric acid. 15. The process, according to any of modalities 11 to 14, the method additionally comprising (bb) the stirring of the mother liquor to which the acid has been added according to (i), in which during (ii), no acid is added to the mother liquor. 16. The process, according to modality 15, in which (bb), the stirring is carried out at a temperature in the range from 20 to 70 ° C, preferably between 25 and 65 ° C, more preferably between 30 and 60 ° C. 17. The process of any of the modalities 1 to 16, in which in (b), the size of the particles contained in the mother liquor, expressed by the respective values Dv10, Dv50, and Dv90, is increased is increased to at least 2%, preferably at least 3%, more preferably at least 4.5% with respect to Dv10, at least 2%, preferably at least 3%, more preferably at least 4.5% with respect to Dv50, and at least 5%, preferably at least 6%, more preferably at least 7% with respect to Dv90, 18. Process, according to any of the modalities 1 to 17, in which the pH adjusted mother liquor obtained from (b) has a solids content in the range from 1 to 10% by weight, preferably from 4 to 9% by weight, more preferably from 7 to 8% by weight, based on the total weight of the pH adjusted mother liquor obtained from (B). 19. Process of any of the modalities 1 to 18 in which the pH-adjusted mother liquor obtained from (b) has a resistance to filtration in the range from 10 to 50 mPa * s / m2, preferably from 15 to 45 mPa * s / m2, more preferably from 20 to 40 mPa * s / m2. 20. The process of any of modalities 1 to 19, additionally comprising (d) washing the precursor of B-MWW obtained from (c), preferably the filter cake obtained from (c) ), where washing is preferably performed using water as the washing agent. 21. The process of modality 20 in which in (d), the filter cake obtained from (c) is has a resistance to washing in the range of from 10 to 50 mPa * s / m2, more preferably from 15 to 45 mPa * s / m2, more preferably from 20 to 40 mPa * s / m2. 22. The 20 or 21 modality process, in which washing is carried out until the conductivity of the filtrate is a maximum of 300 microSiemens / cm, preferably a maximum of 250 microSiemens / cm, more preferably a maximum of 200 microSiemens / cm. 23. The process of any of modalities 1 to 22, additionally comprising (e) drying the precursor of B-MWW obtained from (c), preferably from (d), at a temperature in the range of from 20 to 50 ° C, preferably from 20 to 40 ° C, preferably from 20 to 30 ° C, where drying is preferably carried out by subjecting the precursor of B-MWW to a current of gas, preferably a stream of nitrogen. 24. The process of any of the modalities 1 to 23, in which the residual moisture of the precursor of B-MWW obtained from (c), preferably from (d), more preferably from (e) , is in the range of from 80 to 90% by weight, preferably from 80 to 85% by weight. 25. The process of any one of modalities 1 to 24, additionally comprising (f) the preparation of a suspension, preferably an aqueous suspension, containing the precursor of B-MWW obtained from (c), preferably from (d), optionally from (e), and having a solids content in the range of from 10 to 20% by weight, preferably from 12 to 18% by weight, more preferably from 14 to 16 % by weight; (g) spray drying the suspension obtained from (f) containing the precursor of B-MWW, obtaining a spray powder; (h) calcination of the spray powder obtained from (g) containing the precursor of B-MWW, preferably at a temperature in the range between 500 and 700 ° C, more preferably 550 and 650 ° C, more preferably 575 and 625 ° C for a period of time in the range of 1 to 24 h, preferably from 2 to 18 h, more preferably from 6 to 12 h, obtaining a spray powder of which at least 99% by weight, more preferably at least 99.5 % by weight consists of B-MWW. 26. The process, according to modality 25, in which (h), the calcination is performed in a continuous mode, preferably in a rotary calciner, preferably at a transfer rate in the range from 0.5 to 20 kg sprinkling powder per h. 27. The process of claims 25 or 26, wherein the degree of crystallinity of B-MWW contained in the spray powder obtained from (h) is at least (75 ± 5)%, preferably at least (80 ± 5)%, as determined by means of XRD. 28. The process of any of the modalities 25 to 27 in which the BET specific surface area of B-MWW contained in the spray powder obtained from (h) is at least 300 m2 / g, preferably in the interval from 300 to 500 m2 / g, as determined according to DIN 66131.
[117] Preferably, step (II) is performed by a process whose preferred steps are defined by the following modalities 1 to 7 and the respective dependencies, as indicated: 1. A process for the preparation of a zeolitic material, comprising (a) ) the provision of the zeolitic material containing boron of the MWW type structure (B-MWW) obtained according to step (I); (b) removal of boron from B-MWW by treating B-MWW with a liquid solvent system, thus obtaining B-MWW without boron (MWW); in which the liquid solvent system is selected from a group consisting of water, monohydric alcohols, polyhydric alcohols and mixtures of two or more of them, and in which said liquid solvent system contains neither organic nor inorganic acid nor a salt of the same, being the acid selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, propionic acid, oxalic acid and tartaric acid. 2. The modality 1 process, in which the liquid solvent system does not contain organic or inorganic acid, or salt thereof. 3. The modalities 1 or 2 process, in which the liquid solvent system is selected from the group consisting of water, methanol, ethanol, propanol, ethane-1,2-diol, propane-1,2-diol, propane -1,3-diol, propane-1,2,3-triol and mixtures of two or more of them, preferably water. 4. The process of any of the modalities 1 to 3, in which the treatment according to (b) is carried out at a temperature in the range of 50 to 125 ° C. 5. The process of any one of modalities 1 to 4, in which the treatment according to (b) is performed for a time interval between 6 and 20 h. 6. The process of any one of modalities 1 to 5, in which the treatment according to (b) is performed in at least 2 separate stages, in which between at least 2 treatment stages, the MWW is dried, preferably in a temperature in the range between 100 and 150 ° C. 7. The process, according to any of modalities 1 to 6, additionally comprising (c) post-treatment of MMW obtained from (b) by a process comprising (c.1) the separation of MWW from the solvent system liquid; (c.2) drying, preferably, the separated MWW, preferably by means of spray drying; (c.3) optional calcination of the MWW obtained from (c.1) or (c.2), preferably the temperature in the range between 500 700 ° C.
[118] Regarding step (III), preferably a suitable starting mixture, preferably an aqueous mixture, containing the MWW and a precursor containing Ti, and preferably containing at least one suitable microporous forming agent, is subjected to crystallization hydrothermal under autogenous pressure. It may be conceivable to use at least one suitable seeding material. As a suitable Ti-containing precursor, tetraalkylortothyanates such as tetrabutyl orthotitanate can be mentioned by way of example. As a suitable microporous forming agent, piperidine, hexamethylene imine or mixtures of piperidine and hexamethylene imine can be mentioned by way of example. Preferably, the crystallization time is in the range between 4 and 8 days, more preferably between 4 and 6 days. During hydrothermal synthesis, the crystallization mixture can be stirred. The temperatures applied during crystallization are preferably in the range between 160 and 200 ° C, more preferably 160 to 180 ° C. After hydrothermal synthesis, the TiMWW crystalline zeolitic material obtained is preferably separated from the mother liquor. All methods of separating TiMWW from its mother liquor are conceivable. These methods include, for example, filtration, ultrafiltration, diafiltration and centrifugation methods or, for example, spray drying processes and spray granulation processes. A combination of two or more of these methods can be applied. According to the present invention, TiMWW is preferably separated from its mother liquor by filtration in order to obtain a filter cake which is preferably subjected to washing, preferably with water. Subsequently, the filter cake, optionally further processed to obtain a suitable suspension, is subjected to spray drying or ultrafiltration. Before separating TiMWW from its mother liquor, it is possible to increase the TiMWW content of the mother liquor by concentrating the suspension. If washing is applied, it is preferable to continue the washing process until the washing water has a conductivity of less than 1,000 microSiemens / cm, more preferably less than 900 microSiemens / cm, more preferably less than 800 microSiemens / cm, more preferably less than 700 microSiemens / cm. After separating the TiMWW from its mother liquor, preferably carried out by means of filtration, and after washing, the washed filter cake containing the TiMWW is preferably subjected to pre-drying, for example by submitting the filter cake to a appropriate gas stream, preferably a nitrogen stream, for a period of time preferably in the range between 4 to 10 h, more preferably 5 to 8 h. Subsequently, the pre-dried filter cake is preferably dried at temperatures in the range between 100 and 300 ° C, more preferably 150 and 275 ° C, more preferably 200 and 250 ° C in a suitable atmosphere such as technical nitrogen, air or air poor, preferably air or poor air. Such drying can be carried out, for example, by spray drying. After drying, TiMWW can be subjected to calcination at temperatures in the range of 500 to 700 ° C, more preferably between 550 and 675 ° C, more preferably between 600 and 675 ° C in a suitable atmosphere such as technical nitrogen, air or poor air, preferably in air or poor air. Preferably, no calcination is performed according to (III).
[119] Preferably, steps (III) and (IV) are performed by a process whose preferred steps are defined by the following modalities 1 to 27 and the respective dependencies, as indicated: [1] A process for the preparation of a material zeolitic containing titanium having a MWW frame structure, comprising (a) providing a boron-free crystalline zeolitic material MWW obtained according to step (II); (b) incorporation of titanium into the zeolitic material provided in (a) comprising (b.1) preparation of an aqueous synthesis mixture containing the zeolitic material provided in (i), a MWW model compound and a titanium source, in which the molar ratio of the MWW model compound to Si, calculated as SiO2 and contained in the zeolitic material provided in (a), is in the range between 0.5: 1 to 1.4: 1; (b.2) hydrothermal synthesis of a zeolitic material containing titanium having a MWW framework structure from the aqueous synthesis mixture prepared in (b.1), obtaining a mother liquor comprising the zeolitic material containing titanium having a frame structure MWW; (c) spray drying of the mother liquor obtained from (b.2) comprising the zeolitic material containing titanium having a MWW frame structure. [2] The process of modality 1, in which (b.1) the model MWW compound is selected from the group consisting of piperidine, hexamethylene imine, N, N, N, N ', N', N'-hexamethyl -1,5-pantanediammonium ion, 1,4-bis (N-methylpyrrolidine) butane, octyltrimethylammonium hydroxide, heptyltrimethylammonium hydroxide, hexyltrimethylammonium hydroxide, and a mixture of two or more of them, the MWW model compound preferably being piperidine . [3] The modality 1 or 2 process, in which (b.1), the source of titanium is selected from the group consisting of tetrabutyl orthotitanate, tetraisopropyl orthotitanthin, tetraethyl orthotitanate, titanium dioxide , titanium tetrachloride, titanium tert-butoxide and a mixture of two or more of them, the titanium source being preferably tetrabutyl orthotitanat. [4] The process of any of claims 1 to 3 wherein the mixture of aqueous synthesis in (b.1), the molar ratio of Ti, calculated as TiO2 and contained in the titanium source, in relation to Si, calculated as SiO2 and contained in the zeolitic material having a B2O3: SiO2 molar ratio, of at most 0.02: 1, is in the range between 0.005: 1 and 0.1: 1, preferably between 0.01: 1 to 0.08: 1, more preferably between 0.02: 1 to 0.06: 1. [5] The process of any of claims 1 to 4 wherein the aqueous synthesis mixture in (b.1), the molar ratio H2O to Si, calculated as SiO2 and contained in the zeolitic material with a B2O3: SiO2 molar ratio of at most 0.02: 1, is in the range between 8: 1 to 20: 1, preferably between 10: 1 and 18: 1, more preferably from from 12: 1 to 16: 1. [6] The process of any of claims 1 to 5 wherein the aqueous synthesis mixture in (b.1), the molar ratio of the MWW model compound to Si, calculated as SiO2 and contid o in the zeolitic material provided in (i), it is in the range between 0.5: 1 and 1.7: 1, preferably between 0.8: 1 to 1.5: 1, more preferably from 1.0: 1 to 1 , 3: 1. [7] The process of any of modalities 1 to 6 in which in (b.2), hydrothermal synthesis is carried out at a temperature in the range between 80 and 250 ° C, preferably between 120 and 200 ° C, more preferably between 160 and 180 ° C. [8] The process of any of the modalities 1 to 7 in which in (b.2), the hydrothermal synthesis is carried out for a period in the interval between 10 and 100 h, more preferably between 20 and 80 ° C, more preferably between 40 and 60 h. [9] The process of any of modalities 1 to 8, in which (b.2), hydrothermal synthesis is performed in a closed system under autogenous pressure. [10] The process of any of modalities 1 to 9, in which neither during (b.2), nor after (b.2) and before (c), the titanium-containing zeolitic material having a MWW frame structure is separated from its mother liquor. [11] Process of any of claims 1 to 10 wherein the mother liquor subjected to (c) comprising the zeolitic material containing titanium having a MWW frame structure has a solids content, optionally after concentration or dilution, in the range between 5 and 25% by weight, more preferably between 10 and 20% by weight, based on the total weight of the mother liquor comprising the zeolitic material containing titanium. [12] The process of any of modalities 1 to 11 in which, during spray drying in (c), the inlet temperature of the drying gas is in the range between 200 and 350 ° C and the outlet temperature of the gas drying range is between 70 and 190 ° C. [13] The process of any of modalities 1 to 12 in which the zeolitic material with MWW frame structure obtained from (c) has Si content in the range between 30 to 40% by weight, calculated as elementary Si, a total organic carbon content (TOC) in the range between 0 to 14% by weight, and a Ti content between 2.1 to 2.8% by weight, calculated as elementary titanium, in each case based on the total weight of the zeolitic material. [14] The process of any one of modalities 1 to 13, further comprising (d) the treatment of the zeolitic material containing titanium having a MWW frame structure obtained from (iii) with an aqueous solution having a pH of at most 5 [15] The modality process 14, where after (c) and before (d), the zeolitic material containing titanium having a spray-dried MWW frame structure obtained from (c) is not subjected to calcination . [16] The process of modality 14 or 15, in which (d) the weight ratio of the aqueous solution to the zeolitic material containing titanium having a MWW frame structure is in the range between 10: 1 and 30: 1, preferably between 15: 1 and 25: 1, more preferably between 18: 1 and 22: 1. [17] The process of any of the modalities 14 to 16 wherein in (d) the aqueous solution preferably comprises an inorganic acid , preferably selected from the group consisting of phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, and a mixture of two or more of them, the aqueous solution preferably comprising nitric acid. [18] The process of any of the modalities 14 to 17 where in (d), the aqueous solution has a pH in the range between 0 and 5, preferably between 0 and 3, more preferably between 0 and 2. [19] Process any of the modalities 14 to 18, in which (d), the zeolitic material containing titanium having MWW frame structure is treated with aqueous solution at a temperature in the range between 50 and 175 C, preferably between 70 and 125 C, more preferably between 95 and 105 C. [20] The process of any of the modalities 14 to 19, in which (d), the zeolitic material containing titanium having MWW frame structure is treated with aqueous solution for an interval of time between 0.1 to 6 h , preferably between 0.3 to 2 h, more preferably between 0.5 and 1.5 h. [21] The process of any of the modalities 14 to 20, in which the treatment according to (d) is performed in a closed system under autogenous pressure. [22] The process of any of the modalities 14 to 21, additionally comprising (e) the separation of the zeolitic material containing titanium which has a MWW frame structure obtained from (d) the aqueous solution, optionally followed by washing of the material titanium-containing zeolitic having a separate MWW frame structure. [23] Process of modality 22, in which (e) comprises the drying of the zeolitic material containing titanium having a separate and optionally washed MWW frame structure. [24] The process of any of modalities 14 to 23, further comprising (f) preparing a suspension, preferably an aqueous suspension containing zeolitic material containing titanium with MMW frame structure obtained from (d), preferably from (e), said suspension having a solids content preferably in the range between 5 and 25% by weight, more preferably between 10 and 20% by weight, based on the total weight of the suspension, and subjecting the suspension to spray drying . [25] The 24-mode process where, during spray drying, the inlet temperature of the drying gas is in the range between 200 and 330 ° C and the outlet temperature of the drying gas is in the range between 120 and 180 ° C. [26] The process of any of the modalities 14 to 25, additionally comprising (g) calcining the zeolitic material containing titanium having a MWW frame structure obtained from (d), preferably from (e), more preferably from from (f), where the calcination is preferably carried out at a temperature in the range between 400 and 800 ° C, more preferably between 600 and 700 ° C. [27] The modality 26 process, in which (vii), the calcination is performed in a continuous mode, preferably with a rate in the range between 0.2 and 2.0 kg of zeolitic material per hour, more preferably from 0.5 to 1.5 kg of zeolitic material per hour.
[120] According to step (V), TiMWW preferably obtained according to step (IV) is subjected to an appropriate treatment with Zn to obtain the ZnTiMWW used in preparing the suspension according to (a). Generally, with respect to (V), no specific restrictions exist, as long as the preferred ZZnTiMWW defined above can be obtained with the preferred Zn and Ti contents. More preferably, step (V) comprises at least one suitable impregnation step, more preferably at least one wet impregnation step. Regarding this impregnation step, it is preferable to contact TiMWW, preferably as obtained according to (IV), with at least one precursor containing suitable Zn in at least one suitable solvent (wet impregnation), more preferably Water. As a suitable precursor containing Zn, water-soluble Zn salts are especially preferred, with zinc acetate dihydrate being especially preferred. It is also preferable to prepare a precursor solution containing Zn, preferably an aqueous solution, and suspend TiMWW in this solution. Even more preferably, the impregnation is performed at elevated temperatures in relation to the ambient temperature, preferably in the range between 75 and 125 ° C, more preferably between 85 and 115 ° C, for a period of time preferably in the range between 3.5 and 5 h, more preferably between 3 and 6 h. Shaking the suspension during impregnation is preferred. After impregnation, the ZnTiMWW obtained is preferably properly separated from the suspension. All methods of separating the ZnTiMWW from the suspension are conceivable. Especially preferably, the separation is carried out by means of filtration, ultrafiltration, difiltration or centrifuge methods. A combination of two or more of these methods can be applied. According to the present invention, the ZnTiMWW is preferably separated from the suspension by filtration, in order to obtain a filter cake which is preferably subjected to washing, preferably with water. If washing is applied, it may be preferable to continue the washing process until the washing water has a conductivity of less than 1,000 microSiemens / cm, more preferably less than 900 microSiemens / cm, more preferably less than 800 microSiemens / cm, more preferably less at 700 microSiemens / cm. Subsequently, the preferably washed filter cake is subjected to pre-drying, for example, by subjecting the filter cake to an appropriate gas stream, preferably a nitrogen stream, for a period of time between 5 and 15 h, plus preferably 8 to 12.
[121] If TiMWW or ZnTiMWW is used as a catalytically active material according to the present invention, it is preferable that the organic solvent comprises, preferably consists essentially of acetonitrile.
[122] Therefore, the present invention preferably relates to a process of regeneration of a catalyst, comprising a zeolite containing titanium having a MWW frame structure optionally composed of zinc, as a catalytically active material, said catalyst, having been used in a process for preparing an olefin oxide comprising (i) providing a mixture comprising an olefin, an epoxidating agent and at least partially dissolved potassium, comprising salt; (j)) subjecting the mixture provided in (i) in a reactor to conditions of epoxidation in the presence of catalyst, obtaining a mixture comprising acetonitrile and the olefin oxide and obtaining the catalyst having a potassium salt deposited in said process for the regeneration comprising (k) separating the mixture obtained from (ii) the catalyst; (l) washing the catalyst obtained from (a) with an aqueous liquid system; (m) optionally drying the catalyst obtained from (b) in a gas stream comprising an inert gas, at a temperature of less than 300 ° c; (n) calcining the catalyst obtained from (b) or (c) in a gas stream comprising oxygen, at a temperature of at least 300 ° C.
[123] Therefore, the present invention is preferably related to a process of regeneration of a catalyst, comprising a zeolite containing titanium having a MWW frame structure optionally composed of zinc, as a catalytically active material, said catalyst, having been used in a continuous process for the preparation of a propylene oxide comprising (i) providing a mixture comprising acetonitrile, propene, hydrogen peroxide, water, optionally, propene and at least partially dissolved potassium, comprising salt, in which a potassium comprising salt is selected from the group consisting of dihydrogen phosphate Dipotassium hydrogen phosphate, potassium formate and a mixture of two or more of these; (j)) subjecting the mixture provided in (i) in a reactor to conditions of epoxidation in the presence of catalyst, obtaining a mixture comprising acetonitrile and propylene oxide, water, optionally propene, optionally propane, and obtaining the catalyst having a salt of potassium deposited itself in which the mixture according to (i) contains potassium comprising salt with a molar ratio of potassium comprised in potassium comprising salt to hydrogen peroxide in the range of 10 x 10 - 6: 1 to 1500 x 10-6: 1, preferably from 20 x 10-6: 1 to 1300 x 10-6: 1, more preferably from 30 x 10-6: 1 to 1000 x 10-6: 1, said process for regeneration comprising ( k) separating the mixture obtained from (ii) the catalyst; (l) washing the catalyst obtained from (a) with an aqueous liquid system containing at least 99.9% by weight of water more preferably at least 99.99% by weight, more preferably at least 99.999% by weight water of, based on the total weight of the liquid aqueous system, at a pressure in the range of 0.8 to 1.5 bar, preferably from 1.0 to 1.4 bar and a temperature in the range of 40 to 90 ° C, preferably from 60 to 80 ° C; (m) optionally drying the catalyst obtained from (b) in a gas stream comprising an inert gas, at a temperature in the range of 25 to 100 ° C, preferably from 30 to 50 ° C (n) Calcining the obtained catalyst from (b) or (c), preferably (c), in a gas stream comprising oxygen used in (d) contains oxygen in the range of 3 to 40% by volume, preferably from 5 to 50% by volume based in the total volume of the gas stream at a temperature of a temperature in the range of 375 to 525 ° C, preferably 400-500 ° C. CATALYST TS-1
[124] According to the present invention, a siliconite-1 titanium catalyst, preferably a fixed-bed titanium silicalite-1 catalyst, can be employed as a catalyst. Titanium silicalite-1 is a microporous zeolite of the MFI structure type that contains no aluminum and in which the Si (IV) in the silicate structure is partially replaced by titanium such as Ti (IV). The term "micropores" as used in the context of the present invention refers to pores, having a pore size of less than 2 nm, determined in accordance with DIN 66134.
[125] The catalyst titanium silicite-1 zeolite can in principle be prepared by any conceivable method. Typically, the synthesis of the zeolite of at least one titanium according to the present invention is carried out in hydrothermal systems involving the combination of an active source of silicon oxide and a source of titanium, such as titanium oxide, with at least one compound structural driver capable of forming the desired titanium zeolite in an aqueous suspension, for example in a basic suspension. Typically, organic structural drivers are employed. Preferably, the synthesis is carried out at elevated temperatures, for example, temperatures in the range of 150 to 200 ° C, preferably from 160 to 180 ° C.
[126] In principle, any suitable compound can be used as a source of silicon oxide. Typical sources of silicon oxide (SiO2) include silicates, silica hydrogel, silicic acid, colloidal silica, pyrogenic silica, tetraalkoxysilanes, silicon hydroxides, precipitated silica and clays. Both so-called "wet process" silicon dioxide and so-called "dry process" silicon dioxide can be employed. In such cases, silicon dioxide is particularly preferably amorphous, in which the size of the silicon dioxide particles is, for example, in the range of 5 to 100 nm and the surface area of the silicon dioxide particles is, for example, in the range of 50 to 500 m2 / g. Colloidal silicon dioxide is, inter alia, commercially available as Ludox ®, Syton ®, Nalco ® or Snowtex ®. "Wet process" silicon dioxide is commercially available, in particular, as Hi-Sil ®, Ultrasil ®, Vulcasil ®, Santocel ®, Valron-Estersil ®, Tokusil ® or Nipsil ®. "Dry process" silicon dioxide is commercially available, namely as Aerosil ®, Reolosil ®, Cab-O-Sil ®, Fransil ® or ArcSílica ®. It is also within the scope of the present invention to use a precursor compound of silicon dioxide as a source of silicon oxide. For example, tetraalkoxysilanes, such as, for example, tetraethoxysilane or tetrapropoxysilane, can be mentioned as a precursor compound.
[127] As a structural driver, any appropriate structural driver to provide the desired zeolitic structure MFI can be used. In particular, tetrapropylammonium hydroxide, more preferably tetra-n-propylammonium hydroxide is employed. In a preferred embodiment of the process according to the invention, at least one of the pore-forming agents is removed in a later step by calcination, as described below.
[128] Normally, the synthesis of silica-1 titanium is carried out according to the batch in an autoclave so that the reaction suspension is subjected to autogenous pressure for a number of hours or a few days until the silicaite-1 zeolite of titanium is obtained. According to a preferred embodiment of the present invention, the synthesis generally proceeds at elevated temperatures, where the temperatures during the hydrothermal crystallization step are typically in the range of 150 to 200 ° C, preferably in the range of 160 to 180 ° C. , the reaction is carried out for a time ranging from a few hours to several days, preferably for a time in the range of 12 h to 48 h, more preferably 20 to 30 h. Additionally, it is conceivable to add seed crystals to the synthesis batches.
[129] According to an embodiment of the present invention, the crystalline titanium silicalite-1 obtained is separated out of the reaction suspension, that is, from the mother liquor, optionally, washed and dried.
[130] All methods known for separating crystalline titanium silica-1 from the suspension can be employed. In particular, the methods of filtration, ultrafiltration, diafiltration and centrifugation must be mentioned.
[131] In the event that the crystalline titanium silicalite-1 obtained is washed, said washing step can be carried out using any suitable washing substance, such as, for example, water, alcohols, such as, for example, methanol, ethanol or methanol and propanol, or ethanol and propanol, or methanol and ethanol and propanol or mixtures of water and at least one alcohol, such as, for example, water and ethanol or water and methanol, or water and ethanol, or water and propanol , or water and methanol and ethanol, or water and methanol and propanol, or water and ethanol and propanol or water and ethanol and methanol and propanol. Water or a mixture of water and at least one alcohol, preferably water and ethanol, are used as a washing substance.
[132] Drying of crystalline titanium silicalite-1 is carried out at temperatures, in general, in the range of 80 to 160 ° C, preferably from 90 to 145 ° C, particularly preferably from 100 to 130 ° C.
[133] Instead of the aforementioned separation methods, such as, inter alia, filtration, ultrafiltration, diafiltration and centrifugation methods, the suspension can, according to an alternative embodiment, also be subjected to spraying methods, such as granulation spray and spray drying.
[134] If the separation of silicite-1 crystalline titanium is carried out using a spray method, the separation and drying step can be combined in a single step. In this case, either the reaction suspension as such or a concentrated reaction suspension can be employed. In addition, it is possible to add a suitable additive, such as at least one suitable binder and / or at least one pore forming agent to the suspension - in the reaction suspension as such or to the concentrated suspension - prior to spray drying or spray granulation. Suitable binders are described in detail below. As a pore forming agent, all of the pore forming agents described above can be used. If the suspension is spray dried, the pore-forming agent - if added - can be added in two ways. First, the pore forming agent can be added to the reaction mixture before spray drying. However, it is also possible to add a portion of the pore forming agent to the reaction mixture prior to spray drying, with the remainder of the pore forming agent being added to the spray dried material.
[135] In the event that the suspension is concentrated first to improve the content of titanium silicite-1 in the suspension, concentration can be achieved, for example, by evaporation, such as evaporation under reduced pressure, or by cross-flow filtration. Likewise, the suspension can be concentrated by separating said suspension into two fractions, in which the solid contained in one of the two fractions is separated by filtration, diafiltration, ultrafiltration or centrifugation methods and is suspended after an optional washing step and / or drying step in the suspension fraction. The concentrated suspension obtained in this way, then, can be subjected to spraying methods, such as spray granulation and spray drying.
[136] According to an alternative embodiment, concentration is achieved by separating at least one titanium zeolite from the suspension, and re-suspending the titanium zeolite, optionally, together with at least one appropriate additive as already described above, in that titanium zeolite can be subjected to at least one washing step and / or at least one drying step before resuspension. The resuspended titanium zeolite can then be used for spraying methods, preferably spray drying.
[137] Spray drying is a direct method of drying sludge, suspensions or solutions, by providing a well-dispersed liquid-slurry, suspension or solution, often additionally containing a binder, an atomiser and then partially drying in an air stream. hot. The atomizer mentioned above can be of several different types. Most common is wheel atomization which uses high-speed rotation of a wheel or disc to finish the sludge in the droplets that spin out of the wheel in a chamber and are flash dried before reaching the chamber walls. Atomization can also be performed by single fluid nozzles which depend on hydrostatic pressure to force the sludge through a small nozzle. Multi-fluid nozzles are also used, in which gas pressure is used to force the mud through the nozzle. The pulverized material obtained by using spray drying and spray granulation methods, such as fluidized bed drying, can contain solid and / or hollow spheres and substantially can consist of such spheres, which have, for example, a diameter in the range from 5 to 500 μm or 5 to 300 μm. Single component or multiple component nozzles can be used. The use of a rotating sprinkler is also conceivable. Possible inlet temperatures for the carrier gas used are, for example, in the range of 200 to 600 ° C, preferably in the range of 300 to 500 ° C. The outlet temperature of the carrier gas is, for example, in the range of 50 to 200 ° C. Air, poor air or oxygen-nitrogen mixtures with an oxygen content of up to 10% by volume, preferably up to 5% by volume, more preferably less than 5% by volume, such as up to 2% by volume can be referred to as carrier gases. The spraying methods can be carried out in countercurrent or parallel current flow.
[138] Preferably, titanium silicalite-1 is separated from the reaction suspension by conventional filtration or centrifugation, optionally dried and / or calcined and resuspended, preferably in a mixture, preferably an aqueous mixture of at least one binder material and / or a pore forming agent. The resulting suspension is then preferably subjected to spray drying or spray granulation. The sprayed material obtained can be subjected to an additional washing step, said washing step, being carried out as described above. The pulverized material, optionally washed, is then dried and calcined, and drying and calcination is preferably carried out as described above.
[139] According to an alternative embodiment, crystallization of siliconite-1 from titanium is carried out not before the suspension described above has been spray dried. Therefore, first a suspension is formed comprising the source of silicon oxide, preferably, silicon dioxide, the source of titanium oxide and the structural targeting compound capable of forming the titanium silicalite-1. The suspension is then spray dried, where an additional pore-forming agent is subsequently added to the spray dried titanium silicalite-1.
[140] The spray dried titanium silicalite-1 obtained according to the processes mentioned above can optionally be subjected to at least one washing process. If at least one washing process is carried out, preferably at least one drying step and / or at least one calcining step follows.
[141] Titanium-1 silicalite, optionally obtained by spraying methods, can additionally be subjected to at least one calcination step, which is carried out according to a preferred embodiment of the invention after the drying step, or instead of drying step. At least one calcination step is carried out at temperatures in the general range of 350-750 ° C, preferably 400-700 ° C, particularly preferably 450-650 ° C.
[142] Calcination of titanium silicalite-1 can be carried out under any appropriate gas atmosphere, where air and / or poor air is preferred. In addition, calcination is preferably carried out in a muffle furnace, rotary cone and / or a belt calcination furnace, where calcination is generally carried out for an hour or more, for example, for a time in the range 1 to 24 , or 4 to 12 hours. It is possible in the process according to the present invention, for example, to calcine titanium silicalite-1 once, twice or more times ppr, in each case, at least one hour, for example, in each case from 4 to 12 h, preferably from 4 to 8 h, in which it is possible to maintain temperatures during the constant calcination step or to change temperatures continuously or discontinuously. If the calcination is carried out twice, or more frequently, the calcination temperatures in the individual steps can be identical or different.
[143] Thus, a preferred embodiment of the present invention relates to a process as described above, in which the titanium silicalite-1 separated from the suspension, for example, by filtration or spray drying, is washed with a washing substance and subsequently subjected to at least one drying step. Drying is carried out at high temperatures, in general, in the range of 80 to 160 ° C, preferably from 90 to 145 ° C, particularly preferably from 100 to 130 ° C. More preferably, after drying, a calcination step is carried out. At least one step is carried out at temperatures generally in the range 350-750 ° C, preferably 400-700 ° C, particularly preferably 450-650 ° C.
[144] Titanium-1 silicalite, prepared as described above, can generally be used directly as a catalyst in stages (i) and (iii). However, it is especially preferred to use a fixed bed catalyst in stages (i) and (iii), that is, to employ not the crystalline zeolitic material itself as a catalyst, but the crystalline material processed to give a molding body comprising the titanium silicalite-1. Thus, according to a preferred embodiment, a molding body that includes titanium silicalite-1, as described above, is employed as a catalyst.
[145] In general, in the event that a molding body is used as a catalyst, said catalyst can comprise all conceivable additional compounds in addition to titanium silicalite-1 according to the invention, for example, inter alia, at least one binder and / or at least one of the pore-forming agents. In addition, the catalyst may comprise at least one sizing agent instead of at least one binder and / or at least one pore forming agent or in addition, at least one binder and / or at least one pore forming agent .
[146] As a binder all compounds are suitable, which provide adhesion and / or cohesion between the siliconite-1 titanium to be molded that goes beyond the physiosorption that can be present without a binder. Examples of such binders are metal oxides, such as, for example, SiO2, Al2O3, TiO2, ZrO2 or MgO or clays or mixtures of two or more of these compounds. Clay minerals and naturally occurring aluminas or synthetic production, such as, for example alpha, beta, gamma, delta, eta, kappa, chi or teta-alumina and the inorganic and / or organometallic precursor compounds thereof, such as gibbsite , bayerite, boehmite, pseudoboehmite or trialcoxialuminates, such as aluminum triisopropylate, are particularly preferred as Al2O3 binders. Additional preferred binders are amphiphilic compounds, having a polar and an apolar and graphite fraction. More binders are, for example, clays, such as, for example, mont-morillonites, kaolin, metakaolin, hectorite, bentonites, halloysites, dickitas, nacritas or anaxitas.
[147] These binders can be used as such. It is also within the scope of the present invention to use compounds from which the binder is formed in at least one additional step in the production of the molding bodies. Examples of such binder precursors, tetraalkoxysilanes, tetraalkoxytitanates, tetraalkoxy zirconates or a mixture of two or more different tetraalkoxysilanes or a mixture of two or more different tetraalkoxy zitanates or a mixture of two or more different tetraalkoxy zirconates or a mixture of at least one tetraalkoxy zirconates or a mixture of at least one tetraalkoxy zircones at least one tetraalkoxytitanate or at least one tetraalkoxysilane and at least one tetraalkoxy zirconate or at least one tetraalkoxytitanate and at least one tetraalkoxy zirconate or a mixture of at least one tetraalkoxysilane and at least one tetraalkoxytitanate and at least one tetraalkoxytitanate.
[148] In the context of the present invention, ligands that completely or partially make up SiO2, or that are a precursor to SiO2, of which SiO2 is formed in at least one additional step, are very particularly preferred. In this context, colloidal silica and so-called "wet process" silica and so-called "dry process" silica can be used. Particularly preferably, this silica is amorphous silica, in which the size of the silica particles is, for example, in the range of 5 to 100 nm and the surface area of the silica particles is, for example, in the range of 50 to 500 m2 / g.
[149] Colloidal silica, preferably as an alkaline and / or ammoniacal solution, more preferably as an ammoniacal solution, is commercially available, namely, for example as Ludox ®, Syton ®, Nalco ® or Snowtex ®. "Wet process" silica is commercially available, namely, for example, as Hi-Sil ®, Ultrasil ®, Vulcasil ®, Santocel ®, Valron-Estersil ®, Tokusil ® or Nipsil ®. "Dry process" silica is commercially available, namely, for example, as Aerosil ®, Reolosil ®, Cab-O-Sil ®, Fransil ® or ArcSílica ®. Namely, an ammoniacal solution of colloidal silica is preferred in the present invention. Accordingly, the present invention also describes a catalyst containing a molding body, as described above, said molding body comprising titanium silicalite-1, as described above and additionally SiO2 as a binder material in which the binder used according to ( I) is a linker comprising or forming SiO2. Generally, titanium zeolite can also be shaped without using a binder.
[150] Thus, the present invention is also related to a process, in which in stages (i) and (iii), the titanium silicalite-1 catalyst is obtained by molding the titanium silicalite-1, to give a body molding material comprising titanium silicalite-1 and preferably at least one binder, in particular a silica binder.
[151] If desired, at least pore-forming agents can be added to the mixture of silicalite-1 titanium and at least one binder or at least binder-precursor, for further processing and for forming the catalyst-shaped body to be used as a fixed bed catalyst. Pore forming agents that can be used are all compounds that, with regard to the molding body produced, provide a specific pore size and / or a specific pore size distribution and / or certain pore volumes. In particular, pore forming agents which provide, with respect to the molding body produced, micropores and / or micropores, in particular mesopores and micropores.
[152] Thus, the present invention is also related to a process, in which in stages (i) and (iii), the titanium silicalite-1 catalyst is obtained by molding the titanium silicalite-1, to give a body molding material comprising titanium silicalite-1 and preferably at least one binder, in particular a silica binder, the molding body in particular having micropores and mesopores.
[153] With regard to examples for pore forming agents that can be used, reference is made to the pore forming agents already mentioned above. Preferably, the pore-forming agents used in the modeling process of the invention are polymers that are dispersible, suspendable or emulsifiable in water or mixtures of aqueous solvents. Especially preferred polymers are polymeric vinyl compounds, such as, for example, polyalkylene oxides, such as polyethylene oxides, polystyrene, polyacrylates, polymethacrylates, polyolefins, polyamides and polyesters, carbohydrates, such as, for example, cellulose or cellulose derivatives , such as, for example, methyl cellulose, or sugars or natural fibers. Suitable additional pore forming agents are, for example, pulp or graphite.
[154] If desired, in order for pore size distribution to be achieved, a mixture of two or more pore forming agents can be used. In a particularly preferred embodiment of the process according to the invention, as described below, the pore-forming agents are removed by calcination to give the body a porous catalyst shape. Preferably, pore forming agents that provide mesopores and / or micropores, particularly preferably mesopores, are added to the mixture of at least one binder and titanium silicalite-1 to mold titanium silicalite-1. Generally, titanium silicalite-1 can also be shaped to obtain a catalyst-shaped body, without the use of a pore-forming agent.
[155] In addition to the binder and, optionally, pore forming agent, it is also possible to add additional components, for example to glue at least one agent, to the mixture that is shaped to obtain the catalyst shaped body.
[156] If at least one sizing agent is used in the process of the invention, said sizing agent is used instead of or in addition to at least one pore forming agent. In particular, compounds that also act as pore-forming agents can be used as a sizing agent. Sizing agents that can be used are all compounds known to be suitable for this purpose. These are preferably organic, namely hydrophilic polymers, such as, for example, cellulose, cellulose derivatives, such as, for example, methyl cellulose and starch, such as, for example, potato starch, wallpaper plaster, polyacrylates, polymethacrylates, polyvinyl alcohol, polyvinylpyrrolidone, polyisobutene or polytetrahydrofuran. The use of water, alcohols, glycols or mixtures thereof, such as mixtures of water and alcohol, or water and glycol, such as water and methanol, or water and ethanol, or water and propanol, or water and propylene glycol, as collage can be mentioned. Preferably, cellulose, cellulose derivatives, water and mixtures of two or more of these compounds, such as water and cellulose or water and cellulose derivatives are used as a sizing agent. In a particularly preferred embodiment of the process according to the invention, the at least one sizing agent is removed by calcination, as further described below, to give the impression body.
[157] According to another embodiment of the present invention, at least one acid additive can be added to the mixture that is shaped to obtain the molding body. If an acid additive is used, compounds of organic acids that can be removed by calcination are preferred. In the present context, carboxylic acids, such as, for example, formic acid, oxalic acid and / or citric acid, can be mentioned. It is also possible to use two or more of these acid compounds.
[158] The order of addition of the components to the mixture that is shaped to obtain the molding body is not a critical element. If, for example, a combination of a binder, a pore forming agent, a sizing agent and, optionally, at least one acidic compound is employed, it is possible to first add at least one binder, then at least one pore forming agent, the at least one acidic compound and, finally, the at least one bonding agent and changing the sequence with respect to at least one binder, the at least one of the pore forming agents, the hair at least one acidic compound and at least one sizing agent.
[159] After adding at least one binder and / or at least one sizing agent and / or at least one pore-forming agent and / or at least one acid additive to the mixture comprising titanium silicalite-1, the mixture is normally homogenized for 10 to 180 minutes. In particular, kneaders, edge mills or extruders are particularly used, preferably for homogenization. The mixture is preferably kneaded. On an industrial scale, grinding in a stone mill is preferred for homogenization. Homogenization is, as a general rule, carried out at temperatures in the range of about 10 ° C to the boiling point of the bonding agent and atmospheric pressure or slightly super-atmospheric pressure. Optionally, at least one of the compounds described above can be added. The mixture obtained in this way is homogenized, preferably kneaded, until an extrudable plastic material is formed.
[160] The homogenized mixture is then molded to obtain a molding body. All known suitable molding methods, such as extrusion, spray drying, spray granulation, briquetting, that is, mechanical compression with or without the addition of additional binder or granulation, ie compacting by circular and / or rotating movements, can be employed.
[161] Preferred modeling methods are those in which conventional extruders are used to mold the mixture comprising titanium silicalite-1. Thus, for example extrudates having a diameter of 1 to 10 mm and preferably 2 to 5 mm are obtained. In addition to the use of an extruder, an extrusion press can also be used for the preparation of the molding bodies. The shape of the molding bodies produced according to the invention can be chosen as desired. In particular, in particular, spheres, oval shapes, cylinders or tablets are possible. Likewise, hollow structures, for example, hollow cylinders or structures formed in honeycomb or also star-shaped geometries can be mentioned.
[162] Modeling can be done at ambient pressure, or at a pressure higher than ambient pressure, for example, in a pressure range of 1 bar to several hundred bars. In addition, compression can occur at room temperature or above room temperature, for example, in a temperature range of 20 to 300 oC. If drying and / or calcination are part of the modeling step, temperatures up to 600 oC are conceivable. Finally, compression can be done in an ambient atmosphere or in a controlled atmosphere. Controlled atmospheres are, for example, inert gas atmospheres, reducing atmospheres and / or oxidizing atmospheres.
[163] The modeling step is preferably followed by at least one drying step. At least one drying step is carried out at temperatures in the general range of 80 to 160 oC, preferably from 90 to 145 oC and particularly preferably from 100 to 130 oC, generally for 6 h or more, for example, in the range of 6 to 24 h. However, depending on the moisture content of the material to be dried, shorter drying times, such as, for example, about 1, 2, 3, 4 or 5 h are also possible.
[164] Before and / or after the drying step, the preferred extrudate obtained can, for example, be comminuted. Preferably granules or chips having a particle diameter of 0.1 to 5 mm, in particular, 0.5 to 2 mm, are obtained in this way.
[165] According to a preferred embodiment of the present invention, the drying of the mold bodies, respectively, is preferably followed by at least one calcination step. Calcination is carried out at temperatures generally in the range 350-750 ° C, preferably 400-700 ° C, particularly preferably 450- 650 ° C. Calcination can be carried out under any appropriate gas atmosphere, where air and / or poor air is preferred. In addition, the calcination is preferably carried out in a muffle furnace, a rotary kiln and / or a belt calcination furnace, in which the calcination duration in general is equal to or greater than 1 h, for example, in the range of 1 at 24 h or in the range of 3 to 12 h. In the process according to the present invention, it is suitably possible, for example, to calcine the catalyst-shaped body once, twice or more times in each case for at least 1 hour, for example, in each case in the range of 3 to 12 h, in which it is possible to keep the temperatures during the calcination step constant or to change the temperatures continuously or discontinuously. If the calcination is carried out twice, or more frequently, the calcination temperatures in the individual steps can be identical or different.
[166] According to a particularly preferred modality, the catalyst-shaped body is subjected to a hydrothermal treatment. Hydrothermal treatment can be carried out by using any suitable method, known to those skilled in the art. Thus, the catalyst or catalyst, generally in shape, comes into contact with water or water vapor. Usually, said hydrothermal treatment is carried out by loading the catalyst or according to the invention together with water in an autoclave, heating the mud to a temperature in the range of 100 to 200 ° C, preferably in the range of 120 to 150 ° C to a pressure in the range of 1.5 to 5 bar, preferably in the range of 2 to 3 bar, for a period in the range of 1 to 48 hours, preferably in the range of 24 to 48 hours. Usually, at least one washing step, preferably with water as the washing substance, follows. After treatment with water, the catalyst is preferably being dried and / or calcined, in which drying and calcination is carried out as already described above. According to a preferred modality, hydrothermal treatment is carried out by shaking the body in the form of a catalyst in an autoclave, in which the shaking rate is adjusted to a shaking rate such as to avoid friction as far as possible. The catalyst is used in the form of cylindrical extrudates, however, some friction is desired to achieve cylindrical extrudates with rounded corners. With such extrudates having rounded edges, a higher bulk density can be achieved, for example for the use of the extrudates as a fixed bed catalyst in a tube reactor R1 and / or in a rod reactor R2. In addition, the dust formation of said catalysts in the epoxidation process in phases (i) and (iii) is reduced.
[167] Furthermore, in the epoxidation process of the present invention, a titanium silicalite-1 catalyst as described above is employed, having micropores and mesopores, comprising from 49.5 to 80%, preferably 69.5 to 80% in weight of titanium silicalite-1, based on the total weight of the catalyst and from 19.5 to 50%, preferably from 19.5 to 30% by weight of at least one binder, preferably a silica binder, based on the weight total catalyst-shaped body.
[168] If TS-1 is used as a catalytically active material according to the present invention, it is preferable that the organic solvent comprises, preferably consists essentially of methanol.
[169] Therefore, the present invention preferably relates to a process of regeneration of a catalyst, comprising a TS-1 as a catalytically active material, said catalyst, having been used in a process for the preparation of an olefin oxide comprising (i ) providing a mixture comprising methanol, an epoxidizing agent and at least partially dissolved potassium, comprising salt; (j)) subjecting the mixture provided in (i) in a reactor to conditions of epoxidation in the presence of catalyst, obtaining a mixture comprising methanol and olefin oxide and obtaining the catalyst having a potassium salt deposited in said process for regeneration comprising (k) separating the mixture obtained from (ii) the catalyst; (l) washing the catalyst obtained from (a) with an aqueous liquid system; (m) optionally drying the catalyst obtained from (b) in a gas stream comprising an inert gas, at a temperature of less than 300 ° c; (n) calcining the catalyst obtained from (b) or (c) in a gas stream comprising oxygen, at a temperature of at least 300 ° C.
[170] Specifically preferably, the present invention relates to a process of regeneration of a catalyst, comprising a TS-1 as a catalytically active material, said catalyst, having been used in a continuous process for the preparation of a propylene oxide comprising ( i) providing a mixture comprising methanol, propene, hydrogen peroxide, water, optionally, propene and a potassium at least partially dissolved, comprising salt, in which a potassium comprising salt is selected from the group consisting of dihydrogen phosphate, dipotassium hydrogen phosphate, potassium formate and a mixture of two or more of these; (j)) subjecting the mixture provided in (i) in a reactor to conditions of epoxidation in the presence of catalyst, obtaining a mixture comprising methanol and propylene oxide, water, optionally propene, optionally propane, and obtaining the catalyst having a salt of potassium deposited itself in which the mixture according to (i) contains potassium comprising salt with a molar ratio of potassium comprised in potassium comprising salt to hydrogen peroxide in the range of 10 x 10 - 6: 1 to 1500 x 10-6: 1, preferably from 20 x 10-6: 1 to 1300 x 10-6: 1, more preferably from 30 x 10-6: 1 to 1000 x 10-6: 1, said process for regeneration comprising ( k) separating the mixture obtained from (ii) the catalyst; (l) washing the catalyst obtained from (a) with an aqueous liquid system containing at least 99.9% by weight of water more preferably at least 99.99% by weight, more preferably at least 99.999% by weight water of, based on the total weight of the liquid aqueous system, at a pressure in the range of 0.8 to 1.5 bar, preferably from 1.0 to 1.4 bar and a temperature in the range of 40 to 90 ° C, preferably from 60 to 80 ° C; (m) optionally drying the catalyst obtained from (b) in a gas stream comprising an inert gas, at a temperature in the range of 25 to 100 ° C, preferably from 30 to 50 ° C (n) Calcining the obtained catalyst from (b) or (c), preferably (c), in a gas stream comprising oxygen used in (d) contains oxygen in the range of 3 to 40% by volume, preferably from 5 to 50% by volume based in the total volume of the gas stream at a temperature of a temperature in the range of 375 to 525 ° C, preferably 400-500 ° C. THE EPOXIDATION REACTION
[171] The reaction can be carried out in batch mode or in a continuous mode, where continuous mode is preferred. Conveniently, the reactor comprises the heterogeneous catalyst disposed therein and is equipped with means of controlling the reaction temperature, such as a cooling jacket.
[172] Conveniently, the rate of educt conversion can be controlled by adjusting the temperature, pressure, WHSV of the educts and the like. For example, the reaction temperature can be adjusted so that at least 90% of the epoxidating agent is converted. The amounts of educt present in the reaction mixture before and after the epoxidation reaction can be analyzed by any suitable technique, for example, chromatography.
[173] As will be explained in more detail below, a gradual decrease in catalyst activity comprising a zeolite containing titanium as a catalytically active material can be compensated for a certain period of time by increasing the reaction temperature. The reaction temperature (II) is typically in the range of 20 to 50 ° C, depending on the momentary activity of the catalyst used.
[174] In general, the continuous epoxidation reaction in (a) can be carried out in any suitable way. Preferably, the reaction in (ii) is carried out in at least one reactor continuously operated, such as a tube reactor or a tube bundle reactor which preferably contains at least one cooling jacket around the at least one tube. If the reaction in (ii) is carried out in such a reactor containing at least one cooling jacket, the term "reaction temperature" as used in this document refers to the temperature of the cooling medium when inserted into the cooling jacket.
[175] The catalyst comprising the MWW type frame titanium zeolite can be used in all conceivable ways described above, including powder, micropowder, preferably a spray powder, as a mold body comprising a powder, or as a body of molding comprising micropowder, preferably a spray powder. Preferably, the catalyst comprising the titanium zeolite of structure is used as a mold body comprising a powder or micropowder, preferably a spray powder, more preferably as a mold body comprising a micropowder, preferably a spray powder.
[176] The catalyst used in step (ii) of the present invention can be arranged in the reactor in any conceivable manner. Preferably, the catalyst is arranged as a fluidized bed or as a fixed bed, more preferably as a fixed bed.
[177] As mentioned above, the liquid supply stream provided in (i) is passed inside the reactor in (i) containing the catalyst preferably present as a fixed bed. During the epoxidation reaction, the catalyst load is preferably in the range of 0.05 to 1.25 h-1, preferably from 0.1 to 1 h-1, more preferably from 0.2 to 0.7 h-1 , in which the catalyst load is defined as the ratio between the mass flow rate in kg / h of the epoxidation agent, preferably hydrogen peroxide contained in the liquid feed stream provided in (i) divided by the quantity in kg of catalyst comprising a titanium zeolite comprised in the epoxidation reactor in (ii). The term "epoxidation conditions comprise" as used in this context of the present invention refers to an epoxidation reaction in step (ii) in which at least 90%, preferably at least 95% of the catalyst bed in the reactor and for at least 90% preferably at least 95% of the total reaction time, the catalyst charge is in the ranges described above.
[178] During the epoxidation reaction in (ii), the temperature of the reaction mixture in the reactor is preferably controlled, more preferably maintained at preferred intervals. In order to control the temperature of the reaction mixture, external / internal temperature control means can be used. The term "internal temperature control means" as used in this context of the present invention refers to means which are arranged in the reactor. The term "external temperature control means" as used in this context of the present invention refers to means which are arranged outside the reactor. Preferably, the temperature of the reaction mixture is controlled by external temperature control means, more preferably by means of a heat transfer medium which is preferably passed through a suitable jacket, which preferably involves the reactor. If a tube bundle reactor is used as a reactor, the jacket preferably involves all tubes in the tube bundle.
[179] Preferably, during the epoxidation reaction in (ii), the reaction temperature is in the range between 20 and 100 ° C, more preferably between 25 and 90 ° C, more preferably between 30 and 80 ° C, more preferably between 35 and 70 ° C, more preferably between 40 and 60 ° C. The term "reaction temperature" as used in this context of the present invention refers to the temperature of the heat transfer medium prior to controlling the temperature of the reaction mixture, preferably to the temperature of the heat transfer medium at the inlet of the jacket. epoxidation reactor, through which the heat transfer medium is passed through the jacket. Therefore, the present invention relates to the process as described above, in which (ii), the epoxidation conditions comprise, preferably consist of an epoxidation reaction temperature in the range of 20 to 100 ° C, preferably from 30 to 80 ° C, more preferably from 40 to 60 ° C, where the epoxidation reaction temperature is defined as the temperature of the heat transfer medium before controlling the temperature of the reaction mixture, preferably as the temperature of the heat transfer medium at the entrance of the epoxidation reactor jacket. The term "epoxidation conditions comprise" as used in this context of the present invention refers to an epoxidation reaction in step (ii) in which at least 98%, preferably at least 99%, more preferably 99.9% of the time of the reaction, the reaction temperature is within the ranges described above. The term "total reaction time" as used in this context of the present invention refers to the reaction time during which a given catalyst bed is used before it is either discarded or subjected to regeneration. Specifically at the beginning of an epoxidation reaction in (ii) when the catalyst is fresh, that is, at the beginning of the epoxidation reaction in (ii), the reaction temperature may be outside the ranges mentioned above for a brief period of time. Preferably, the luxury rate of the heat transfer medium is chosen so that the temperature difference between the inlet temperature and its outlet temperature is at most 3 K, more preferably at most 2 K, most preferably at most 1 K .
[180] Preferably, during the epoxidation reaction in (ii), the epoxidation reaction pressure is in the range between 14 to 100 bar, more preferably between 14.5 and 50 bar, more preferably between 15 and 32 bar, more preferably between 15 and 25 bar. The term "epoxidation reaction pressure" as used in this context of the present invention refers to the pressure at the outlet of the epoxidation reactor where the effluent is removed from the reactor according to (iii). Consequently, the present invention relates to the process as described above, in which (ii) the epoxidation conditions comprise, preferably consist of an epoxidation reaction pressure between 14 and 100 bar, preferably 15 to 32 bar, more preferably 15 to 25 bar. The term "epoxidation conditions comprise" as used in this context of the present invention refers to an epoxidation reaction in step (ii) in which at least 98%, preferably at least 99%, more preferably 99.9% of the time of the reaction, the reaction temperature is within the ranges described above. The term "total reaction time" as used in this context of the present invention refers to the reaction time during which a given catalyst bed is used before it is either discarded or subjected to regeneration.
[181] Preferably, the epoxidation reaction according to step (ii) of the present invention is performed in an essentially constant epoxidation agent conversion, preferably hydrogen peroxide conversion. Preferably, in order to determine the conversion of the epoxidation agent, preferably the conversion of hydrogen peroxide, the molar flow rate of the epoxidation agent, preferably, hydrogen peroxide in the effluent stream removed in (iii), referred to in this document , in contrast, is compared with the molar flow rate of the epoxidation agent, preferably hydrogen peroxide in the liquid feed stream provided in (i), referred to in this document as min, and in which the conversion of the epoxidation agent, preferably peroxide hydrogen is defined as 100 x (1-mph / min). Preferably, the inlet temperature of the heat transfer medium described above is adjusted to the preferred ranges mentioned above in order to maintain the conversion of epoxidizing agent, preferably hydrogen peroxide essentially constant in the range of 80 to 100%, more preferably from 90 to 100%, more preferably from 95 to 100%, more preferably from 99 to 100%, more preferably from 99.5 to 100%, more preferably from 99.9 to 100%. The term "epoxidation conditions comprise" as used in this context of the present invention refers to an epoxidation reaction in step (ii) in which at least 98%, preferably at least 99%, more preferably 99.9% of the time total reaction, conversion of epoxidation agent, preferably conversion of hydrogen peroxide are within the intervals defined above. The term "total reaction time" as used in this context of the present invention refers to the reaction time during which a given catalyst bed is used before it is either discarded or subjected to regeneration. Specifically at the beginning of an epoxidation reaction in (ii) when the catalyst is fresh, that is, at the beginning of the epoxidation reaction in (ii), the conversion of the epoxidation agent, preferably conversion of hydrogen peroxide can be found out of the intervals mentioned above for a brief period of time. Preferably, the reaction temperature is not kept constant during the reaction but is adjusted continuously or in a stepwise manner to allow conversion of constant epoxidizing agent. Generally, due to the deactivation of a certain catalyst, the reaction temperature is continuously or gradually increased. Preferably, the reaction temperature is continuously or gradually increased by 1 ° K / d (Kelvin / day) at most, more preferably, by less than 1 ° K / d.
[182] Preferably, the reaction mixture which is present in the reactor in (ii) is liquid under epoxidation conditions. Preferably, the reaction mixture consists of a single liquid phase, two phases or three or more liquid phases. Preferably, the reaction mixture in the reactor in (ii) consists of a single liquid phase or two liquid phases more preferably of a single liquid phase.
[183] Generally, the reactor used in step (ii) of the present invention can be arranged horizontally or vertically. Preferably, the reactor is arranged vertically. In the preferably vertically arranged reactor, the liquid supply stream provided in (i) can be passed in an upflow or downflow mode, with the upflow mode being preferred. Preferably, in comparison with the flow direction of the liquid feed stream, the heat transfer medium is passed through the jacket in concurrent mode.
[184] In general, the epoxidation reaction in (ii) can be performed in one or more reactors in which such reactors can be arranged in parallel or in series. Preferably, the reaction in (ii) is carried out in a reactor or at least two reactors, preferably two reactors, which are arranged in series where between two reactors arranged in series, a suitable intermediate treatment can be performed. If the reaction is carried out in two reactors arranged in series, it is preferable that the first reactor is operated as described above, that is, as an isothermal reactor, and the second reactor, that is, the downstream reactor, is operated as an adiabatic reactor. or essentially adiabatic. The term "reactor", as used in this document, also encompasses two or more reactors arranged in parallel in which a passed supply current is divided into two or more sub-currents, each sub-current is passed into a reactor and the effluent streams removed from the reactors are combined in order to obtain the general effluent stream. Consequently, the epoxidation reaction can be performed in at least one first reactor such as two or more first reactors, for example, 2, 3, 4 first reactors, which are arranged in parallel and are preferably isothermal reactors, and in at least one second reactor such as two or more second reactors, for example, 2, 3, 4 second reactors, which are arranged in parallel and are preferably adiabatic or essentially adiabatic reactors.
[185] If the epoxidation reaction according to (ii) is carried out in two reactors arranged in series, it is preferable that in the first reactor, which is preferably an isothermal reactor, the conversion of the epoxidation agent, preferably conversion of hydrogen peroxide is kept essentially constant in a range of 80 to 99%, preferably from 85 to 98%, more preferably from 90% to 97% and in a second reactor, which is preferably designed as an adiabatic or essentially adiabatic reactor, conversion of epoxidation agent, preferably conversion of general hydrogen peroxide, that is, conversion of epoxidation agent, preferably conversion of hydrogen peroxide taking into account the conversion in the first and second reactor, is carried out at a higher value to 99%, preferably at least 99.5%, more preferably at least 99.9%. THE SPEND CATALYST
[186] Normally, after a prolonged period of time using a freshly produced catalyst comprising a zeolite containing titanium in a process for preparing an olefin oxide, a decrease in its catalytic activity is observed compared to the freshly prepared catalyst . Such a gradual decrease in catalytic activity can be compensated to some extent by increasing the reaction temperature. The catalytic activity can be followed by determining the conversion rate of at least one educt during the reaction at a given temperature. In the event that a drop in the conversion rate is observed during the process, the reaction temperature will be increased. In this sense, the catalyst, comprising a zeolite containing titanium, can be subjected to regeneration when the reaction temperature has reached an upper temperature limit, above which the process becomes economically and environmentally inefficient. For example, the catalyst, comprising a zeolite containing titanium, can be subjected to regeneration when the reaction temperature in (ii) necessary to maintain a conversion rate for one of the above educts, for example, 90%, is 70 ° C or higher, preferably 60 ° C or higher, more preferably 50 ° C or higher.
[187] Alternatively, a catalyst comprising a zeolite containing titanium having potassium deposited in it following steps (i) and (ii), can be submitted for regeneration according to steps (a) to (d), when its selectivity departs by more than a certain percentage in relation to the selectivity of the fresh catalyst, comprising a zeolite containing titanium. Here, the selectivity of the catalyst comprising a zeolite-containing titanium is defined by the total conversion of an educt divided by the conversion of said educt to the desired product. For example, a catalyst, comprising a zeolite containing titanium, can undergo regeneration following steps (i) and (ii), when its selectivity of the catalyst in relation to the olefin oxide determined in (ii) differs by 2% or more from respective selectivity of the fresh catalyst, comprising a zeolite containing titanium under otherwise reaction identical conditions.
[188] According to the present invention, it has been found that a catalyst, comprising a zeolite containing titanium intended for regeneration that has met one of the criteria described above following steps (i) and (ii) normally has a potassium content of above 0.5% by weight, preferably in the range of 0.6 to 1.3 by weight. Furthermore, it was found that, after a sequence of steps (a) to (d) according to the present invention, the regenerated catalyst, comprising a zeolite containing titanium obtained from (d), has a potassium content of at most 0 , 5% by weight, preferably at most 0.4% by weight, more preferably at most 0.3% by weight, based on the total weight of the catalyst and determined by elementary analysis.
[189] The regenerated catalyst obtained according to the process of the present invention can be used for each use. Preferably, the catalyst comprising a titanium-containing zeolite obtained from (d) is employed in a process for the preparation of an olefin oxide, preferably in an olefin epoxidation process comprising (i '), providing a mixture comprising an organic solvent, an olefin, an epoxidating agent and a phosphate-containing compound; (ii ') subjecting the mixture provided in (i') in a reactor to conditions of epoxidation in the presence of catalyst obtained from (d), obtaining a mixture comprising the organic solvent and the olefin oxide.
[190] The preferred modalities of steps (i ') and (ii') are carried out as described in detail for steps (i) and (ii) above.
[191] The present invention additionally relates to a catalyst, comprising a zeolite containing titanium as a catalytically active material, obtained or obtainable by the regeneration process of the present invention.
[192] It is preferable that the regenerated catalyst according to the present invention exhibits, in the process for preparing an olefin oxide, a differential conversion temperature of a maximum of 5 K, where the differential conversion temperature is defined as the absolute difference between (A1) the temperature at which a predetermined conversion of the epoxidation agent is achieved in said process for the preparation of an olefin oxide in which the regenerated catalyst is used as a catalyst and (B1) the temperature at which it dictates predetermined conversion of the epoxidation agent is achieved in said process for the preparation of an olefin oxide in which the respective fresh catalyst is used as a catalyst under identical epoxidation reaction conditions.
[193] It has already been indicated that after a certain period of operation a decrease in catalytic activity of a catalyst, comprising a zeolite containing titanium as a catalytically active material is observed in an epoxidation reaction. The reduced catalytic activity is directly related to a reduced conversion rate for at least one of the educts, that is, the olefin and / or the epoxidation agent, in which the reduced conversion rate can be compensated by the increase in the overall reaction temperature . This implies that, with the continued operation of the catalyst, a gradual increase in the reaction temperature is necessary in relation to the initial temperature, making the epoxidation process increasingly ineffective.
[194] However, by subjecting a catalyst comprising a zeolite containing titanium passed in an epoxidation reaction to the regeneration process of the present invention, its initial catalytic activity can be restored. Initial catalytic activity refers here to the catalytic activity of freshly prepared catalyst. Since the catalytic activity is conveniently directly related to the reaction temperature under identical reaction conditions, the efficiency of regeneration of the spent catalyst can be deduced from the reaction temperature required to maintain a set conversion rate. In the present case, the regenerated catalyst according to the present invention has a conversion temperature favorably in the process for the preparation of an olefin oxide deviating by a maximum of 5 K from the conversion temperature of fresh catalyst under identical epoxidation conditions , Besides that.
[195] It is additionally preferred that the regenerated catalyst, according to the process of the present invention, exhibits, in the process for the preparation of an olefin oxide, a differential selectivity of a maximum of 2, where the differential selectivity is defined as the difference absolute in% between (A2) the selectivity based on the epoxidation agent in said process for the preparation of an olefin oxide in which the regenerated catalyst is used as catalyst and (B2), the selectivity based on the epoxidation agent in said process for the preparation of an olefin oxide in which the respective fresh catalyst is used as a catalyst under identical epoxidation reaction conditions. where selectivity based on the epoxidation agent is defined as moles of epoxide produced divided by moles of epoxidation agent consumed x 100.
[196] The quality of the catalyst comprising a regenerated titanium-containing zeolite according to the process of the present invention can also be quantified by comparing the selectivity of the regenerated catalyst with the selectivity of the fresh catalyst under identical epoxidation conditions. Usually, after a prolonged use, a decrease in the selectivity of the catalyst is also observed. Favorably, in the present case, after having undergone the regeneration process of the present invention, a catalyst, comprising a zeolite containing titanium, has a selectivity that deviates by a maximum of 2 percentage points from the selectivity of the fresh catalyst under identical epoxidation reaction conditions, Besides that. DESCRIPTION OF THE FIGURES
[197] Figure 1 shows the amount of potassium and phosphorus deposited in the spent catalyst in relation to the total silicon content. Fraction 1 is an example taken from the first meter at the bottom of a reactor tube, fraction 2 is a sample taken 1 to 2 meters away from the bottom of a reactor tube and fraction 3 is a sample taken from 2 to 3 meters away from the bottom of a reactor tube.
[198] Figure 2 shows the amount of carbon and nitrogen deposited in the spent catalyst in relation to the total silicon content. Fraction 1 is an example taken from the first meter at the bottom of a reactor tube, fraction 2 is a sample taken 1 to 2 meters away from the bottom of a reactor tube and fraction 3 is a sample taken from 2 to 3 meters away from the bottom of a reactor tube.
[199] Figure 3 shows the catalytic performance of spent catalyst regenerated according to a prior art method compared to the catalytic performance of fresh catalyst under identical epoxidation conditions, other than that. The conversion rate based on hydrogen peroxide, the normalized selectivities based on hydrogen peroxide and propene spent catalyst and fresh catalyst are indicated and further the reaction temperature (° C) of spent catalyst, as well as the catalyst fresh.
[200] Figure 4 shows a fresh catalyst FT-IR spectrum. The x-axis shows the wave number (wn) in cm-1, the y-axis shows the absorbance (A).
[201] Figure 5 shows a spent catalyst FT-IR spectrum to follow after the regeneration of cycles, each cycle, comprising steps (a) to (b) according to the invention. The x-axis shows the wave number (wn) in cm-1, the y-axis shows the absorbance (A).
[202] Figure 6 shows the catalytic performance of spent catalyst, having been subjected to five regeneration cycles comprising steps (a) to (b) according to the invention in comparison to the catalytic performance of fresh catalyst under identical epoxidation conditions. . The conversion rate to hydrogen peroxide, the normalized selectivities based on hydrogen peroxide and propene based on the regenerated catalyst and the fresh catalyst are indicated, plus the reaction temperature (° C) applied when using the regenerated catalyst, and the fresh catalyst.
[203] The present invention is further illustrated by the following reference examples, examples and reference examples. EXAMPLES REFERENCE EXAMPLE 1: PREPARATION OF A CATALYST, UNDERSTANDING A ZEOLITE CONTAINING TITANIUM (ZNTIMWW); 1.1 Preparation of MWW containing boron
[204] 470.4 kg of deionized water were provided in a container. Under agitation at 70 rpm (revolutions per minute), 162.5 kg of boric acid were suspended in water. The suspension was stirred for another 3 h. Subsequently, 272.5 kg of piperidine were added and the mixture was stirred for an additional hour. 392.0 g of Ludox® AS-40 was added to the resulting solution, and the resulting mixture was stirred at 70 rpm for an additional hour. The finally obtained mixture was transferred to a crystallization vessel and heated to 170 ° C, within 5 h under autogenous pressure and under stirring (50 rpm). The temperature of 170 ° C was kept essentially constant for 120 h; during those 120 h, the mixture was stirred at 50 rpm. Thereafter, the mixture was cooled to a temperature of 50 ° C to 60 ° C within 5 h. The aqueous suspension containing B-MWW had a pH of 11.3 as determined by measurements with a pH electrode. From this suspension, the B-MWW was separated by filtration. the filter cake was then washed with deionized water until the wash water had a conductivity of less than 700 microSiemens / cm. The filter cake obtained in this way was subjected to spray drying in a spray tower using technical nitrogen as the drying gas. The spray-dried material was then subjected to calcination at 650 ° C for 2 h. The calcined material had a boron (B) content of 1.9% by weight, a silicon (Si) content of 41% by weight and a total organic carbon (TOC) content of 0.18% by weight. 1.2 PREPARATION OF DEBORONED MWW
[205] Based on the spray dried material obtained according to section 1.1 above, 4 MWW lots of debored zeolite were prepared. In each of the first 3 batches, 35 kg of spray-dried material obtained in accordance with section 1.1 and 525 kg of water were used. In the fourth batch, 32 kg of spray-dried material obtained in accordance with section 1.1 and 480 kg of water were used. In total, 137 kg of spray dried material obtained according to section 1.1 and 2025 kg of water were used. For each batch, the respective amount of water was passed to a container equipped with a reflux condenser. Under stirring at 40 rpm, the given amount of the spray-dried material was suspended in water. Subsequently, the container was closed and the reflux condenser was put into operation. The agitation rate was increased to 70 rpm. Under stirring at 70 rpm, the contents of the vessel were heated to 100 ° C within 10 h and maintained at this temperature for 10 h. Then, the contents of the container were cooled to a temperature below 50 ° C. The de-forested zeolitic material resulting from the MWW structure type was separated from the suspension by filtration under a nitrogen pressure of 2.5 bar and washed four times with deionized water. After filtration, the filter cake was dried in a nitrogen stream for 6 h. The debored zeolitic material obtained in 4 batches (dry filter cake with nitrogen of 625.1 kg in total) had a residual moisture content of 79%, as determined using an IR (infrared) scale at 160 ° C. From the nitrogen dried filter cake having a residual moisture content of 79% obtained above, an aqueous suspension was prepared with deionized water, the suspension having a solids content of 15% by weight. The suspension was subjected to spray drying in a spray tower using technical nitrogen as the drying gas. The spray-dried MWW material obtained had a B content of 0.08% by weight, a Si content of 42% by weight and a TOC content of 0.23% by weight. 1.3 TIMWW PREPARATION
[206] Based on the deforested MWW material obtained according to section 1.2 above, a zeolitic material of MWW type structure containing titanium (Ti) was prepared, referred to below as TiMWW. 54.16 kg of the deforested zeolitic material of MWW type structure were transferred to a first container A. In a second container B, 200.00 kg of deionized water were transferred and stirred at 80 rpm. 118.00 kg of piperidine was added with stirring, and during the addition, the temperature of the mixture increased to about 15 ° C. Subsequently, 10.90 kg of tetrabutylortotitanate and 20.00 kg of deionized water were added. Then, stirring was continued for 60 min. The mixture from container B was then transferred to container A, and stirring was started in container A (70 rpm). 24.00 kg of deionized water were filled into container A and transferred to container B. The mixture in container B was then stirred for 60 minutes at 70 rpm. At the start of stirring, the pH of the mixture in vessel B was 12.6, as determined with a pH electrode. After said stirring at 70 rpm, the frequency was decreased to 50 rpm, and the mixture in vessel B was heated to a temperature of 170 ° C within 5 h. At a constant stirring rate of 50 rpm, the temperature of the mixture in vessel B was maintained at an essentially constant temperature of 170 ° C for 120 h under autogenous pressure. During this crystallization of TiMWW, a pressure increase of up to 10.6 bar was observed. Thereafter, the suspension obtained containing TiMWW having a pH of 12.6 was cooled within 5 hours. The cooled suspension was subjected to filtration and the separated mother liquor was transferred to discharge residual water. The filter cake was washed 4 times with deionized water under a nitrogen pressure of 2.5 bar. After the last washing step, the filter cake was dried in a nitrogen stream for 6 h. From 246 kg of said filter cake, an aqueous suspension was prepared with deionized water, the suspension having a solids content of 15% by weight. The suspension was subjected to spray drying in a spray tower using technical nitrogen as the drying gas. The spray dried TiMWW material obtained from the first experiment had a Si content of 37% by weight, a Ti content of 2.4% by weight and a TOC of 7.5% by weight. 1.4 TIMWW ACID TREATMENT
[207] The spray dried TiMWW material obtained in section 1.3 above was subjected to acid treatment, followed by spray drying and calcination, as described below. A container was filled with 670.0 kg of deionized water. 900 kg of nitric acid was added and 53.0 kg of spray dried TiMWW were added under agitation at 50 rpm. The resulting mixture was stirred for another 15 minutes. Thereafter, the agitation rate was increased to 70 rpm. Within 1 h, the mixture in the vessel was heated to 100 ° C and maintained at this temperature and under autogenous pressure for 20 h with stirring. The mixture thus obtained was then cooled within 2 hours to a temperature below 50 ° C. The cooled mixture was subjected to filtration and the filter cake was washed six times with deionized water under a pressure of nitrogen of 2.5 bar. After the last washing step, the filter cake was dried in a nitrogen stream for 10 h. The wash water after the sixth wash step had a pH of about 2.7. 225.8 kg of dry filter cake were obtained. From the filter cake obtained, an aqueous suspension was prepared with deionized water, the suspension having a solids content of 15% by weight. The suspension was subjected to spray drying in a spray tower using technical nitrogen as the drying gas. The spray dried acid treated TiMWW material had a Si content of 42% by weight, a Ti content of 1.6% by weight and a TOC content of 1.7% by weight. The spray-dried material was then subjected to calcination at 650 ° C in a rotary kiln for 2 h. The calcined material had a Si content of 42.5% by weight, a Ti content of 1.6% by weight and a TOC content of 0.15% by weight. Langmuir's surface area is determined by nitrogen adsorption at 77 K, according to DIN 66131 it was 612 m 2 / g, the specific multipoint BET surface area, determined by nitrogen adsorption at 77 K, according to DIN 66131 was 442 m 2 / g. The total intrusion volume determined according to Hg porosimetry according to DIN 66133 was 4.9 ml / g (gram / milliliter), the respective total pore area 104.6 m 2 / g. The degree of crystallization, determined by XRD was 80%, average mineral grain size 31 nm. 1.5 TIMWW IMPREGNATION WITH ZN
[208] The spray-treated and calcined acid-treated material, as obtained according to 1.4, was then subjected to an impregnation stage. Impregnation was carried out in 3 batches a) to c) as follows: a) In a container equipped with a reflux condenser a solution of 840 kg of deionized water and 5.13 kg of dehydrated zinc acetate was prepared within 30 minutes. Under agitation (40 rpm), 28 kg of the calcined Ti-MWW material obtained according to 1.4 were suspended. Subsequently, the container was closed and the reflux condenser was put into operation. The agitation rate was increased to 70 rpm. b) In a container equipped with a reflux condenser, a solution of 840 kg of deionized water and 5.13 kg of dehydrated zinc acetate was prepared within 30 minutes. Under agitation (40 rpm), 28 kg of the calcined Ti-MWW material obtained according to 1.4 were suspended. Subsequently, the container was closed and the reflux condenser was put into operation. The agitation rate was increased to 70 rpm. c) In a container equipped with a reflux condenser, a solution of 930 kg of deionized water and 5.67 kg of dehydrated zinc acetate was prepared within 30 minutes. Under agitation (40 rpm), 31 kg of the calcined Ti-MWW material obtained according to 1.4 were suspended. Subsequently, the container was closed and the reflux condenser was put into operation. The agitation rate was increased to 70 rpm. In all batches a) to c), the mixture in the vessel was heated to 100 ° C within 1 hour and held at reflux for 4 hours at a stirring rate of 70 rpm. Then, the mixture was cooled within 2 hours to a temperature below 50 ° C. For each batch a) to c), the cooled suspension was subjected to filtration and the mother liquor was transferred to discharge residual water. The filter cake was washed five times with deionized water under a nitrogen pressure of 2.5 bar. After the last washing step, the filter cake was dried in a nitrogen stream for 10 h. For batch a), 106.5 kg of dry nitrogen filter cake were finally obtained. For batch b), 107.0 kg of dry nitrogen filter cake were finally obtained. For batch c), 133.6 kg of dry nitrogen filter cake were finally obtained. The TiMWW material impregnated with Zn dried in this way (ZnTiMWW), for each batch, had a Si content of 42% by weight, a Ti content of 1.6% by weight, a Zn content of 1.4% by weight and a TOC content of 1.4% by weight. 1.6 PREPARING A MOLDING BODY
[209] Starting from the calcined spray dried ZnTiMWW material, a molding body was prepared, dried and calcined. Therefore, 22 batches were prepared, each from 3.4 kg of calcined spray-dried ZnTiMWW material obtained in Example 1, 0.220 kg of Walocel ™ (Walocel MW 15000 GB, Wolff Cellulosics GmbH & Co. KG, Germany) , 2.125 kg of Ludox® AS-40 and 6.6 l of deionized water, as follows: 3.4 kg of ZnTiMWW and 0.220 kg of Walocel were kneaded in a stone mill for 5 minutes. Then, in addition to kneading, 2,125 kg of Ludox were continuously added. After another 10 minutes, the addition of 6 l of deionized water started. After another 30 minutes, 0.6 l of additional deionized water was added. After a total time of 50 min, the kneaded dough was able to be extruded. After that, the kneaded dough was extruded under 65 bar at 80 bar, in which the extruder was cooled with water during the extrusion process. Per batch, the extrusion was in the range of 15 to 20 minutes. The energy consumption per batch during extrusion was 2.4 A. A tint head was used to produce cylindrical filaments having a diameter of 1.7 mm. In the hue head outside the outlet, the filaments were not cut to length. The filaments thus obtained were dried for 16 h at 120 ° C in an air drying chamber. In total (sum of the 22 lots), 97.1 kg of white filaments with a diameter of 1.7 mm were obtained. 65.5 kg of dry filaments were subjected to calcination in a rotary kiln at 550 ° C for 1 hour under air, yielding 62.2 kg of calcined filaments. After that, the filaments were sieved (1.5 mm mesh size), and the yield, after sieving, was 57.7 kg. CHARACTERIZATION OF THE FILAMENTS OBTAINED:
[210] The modeling bodies obtained in this way exhibited a density of 322 g / l (gram per liter) and
[211] had a Zn content of 1.2% by weight, a Ti content of 1.4% by weight, a Si content of 43% by weight and a C content of 0.13% by weight. The sodium (Na) content was 0.07% by weight. The micropore mesopores had an average pore diameter (4V / A) of 20.1 nm, as determined by Hg porosimetry according to DIN 66133. The micropore macropores had an average pore diameter (4V / A) of 46, 8 nm, as determined by Hg porosimetry according to DIN 66133. The degree of crystallization, determined by XRD was 74 +/-%, average mineral grain size 38.0 nm +/- 10% The Langmuir surface area is determined by of nitrogen adsorption at 77 K, according to DIN 66131 was 499 m 2 / g, the specific multipoint BET surface area, determined by nitrogen adsorption at 77 K, according to DIN 66131 was 361 m 2 / g. The total intrusion volume determined according to Hg porosimetry according to DIN 66133 was 1.2 ml / g (gram / milliliter), the respective total pore area 92.2 m 2 / g. 1.7 POST-TREATMENT OF THE MOLDING BODY
[212] Starting from the calcined filaments obtained according to section 1.6, a post-treatment stage was carried out as follows: a container was filled with 590 kg of deionized water. Then, 29.5 kg of the calcined molding bodies obtained according to example 2 were added. The container was closed (pressure-proof) and the mixture obtained was heated to a temperature of 145 ° C within 1.5 he is maintained at this temperature under autogenous pressure (about 3 bar) for 8 h. Then, the mixture was cooled for 2 h. The water-treated filaments were subjected to filtration and washed with deionized water. The obtained filaments were heated in an air drying chamber within 1 h at a temperature of 120 ° C and maintained at this temperature for 16 h. Subsequently, the dry material was heated in air to a temperature of 450 ° C within 5.5 hours and maintained at this temperature for 2 h. After that, the filaments were sieved (1.5 mm mesh size) and the yield, after sieving, was 27.5 kg. CHARACTERIZATION OF THE FILAMENTS OBTAINED:
[213] The water-treated molds obtained in this way exhibited an apparent density of 340 g / l (gram per liter) and had a Zn content of 1.3% by weight, a Ti content of 1.4% by weight, a Si content of 43% by weight and a C content of 0.10% by weight. The micropowder mesopores had an average pore diameter (4V / A) of 20.2 nm, as determined by Hg porosimetry according to DIN 66133. Thus, the inventive water treatment has virtually no influence on the body's mesoporous characteristics. modeling (cf. the modeling body as described above, having a respective mean pore diameter of 20.1 nm). The micropore macropores had an average pore diameter (4V / A) of 45.9 nm, as determined by Hg porosimetry according to DIN 66133. Thus, the inventive water treatment has virtually no influence on the macropore characteristics of the modeling body (cf. the modeling body as described above, having a mean pore diameter of 46.8 nm). The degree of crystallization, determined by XRD was 64 +/- 10%, average mineral grain size 39.4 nm +/- 10%. Langmuir's surface area is determined by nitrogen adsorption at 77 K, according to DIN 66131 was 418.1 m 2 / g, the specific multipoint BET surface area, determined by nitrogen adsorption at 77 K, according to DIN 66131 was 299.8 m 2 / g. The total intrusion volume determined according to Hg porosimetry according to DIN 66133 was 1.1332 ml / g (gram / milliliter), the respective total pore area 92.703 m 2 / g. REFERENCE EXAMPLE2: LARGE-SCALE PROPYLENE OXIDE PRODUCTION USING THE ZNTIMWW CATALYST
[214] An epoxidation of propene to propylene oxide using the ZnTiMWW catalyst obtained as described in reference example 1 was carried out as described in reference example 3. The aqueous hydrogen peroxide feed was mixed with 390 micromol of K2PO4 additive for 1 mol of H2O2 in the stream (3). The reaction was additionally carried out on the condition that the conversion rate of hydrogen peroxide was at least 91% at all times, which required that the reaction temperature be gradually increased.
[215] Here, to compensate for the loss of activity of the ZnTiMWW catalyst, the initial water cooling temperature, ie the reaction temperature, from 30 ° C was gradually increased to 55 ° C, while the reaction is carried out. Epoxidation was carried out for 2100 hours in total.
[216] After 2100 hours the ZnTiMWW catalyst was removed from the reactor tubes and 12 samples were taken for elementary analysis. A sample of the catalyst located in each meter of the reactor was taken.
[217] Samples 1 to 12 were analyzed using the inductively coupled Plasma (ICP) technique. Figure 1 shows the amounts of potassium and phosphorus deposited in the spent catalyst plotted as molar ratios relative to the silicon content, the latter essentially not changing during the reaction. This corresponds to about 0.5 to 2% by weight of potassium and about 0.5 to 2% by weight of phosphorus in relation to the total amount of catalyst. Figure 2 shows the amounts of carbon and nitrogen deposited in the spent catalyst plotted as molar ratios relative to the silicon content. REFERENCE EXAMPLE 3: EPOXIDATION REACTION INSTALLATION (LARGE SCALE)
[218] According to a large-scale installation, the epoxidation reaction was carried out as follows: a) Epoxidation in a Main Epoxidation Reactor (epoxidation unit A)
[219] Main reactor A was a 5-tube vertically mounted tube reactor (tube length: 12 m, tube inner diameter: 38 mm), each tube being equipped with an axially placed multi-point thermocouple with 10 equally spaced measuring points wrapped in a suitable capsule with a diameter of 18 mm. Each tube was loaded with 17.5 kg of the ZnTiMWW impression body catalyst as prepared according to Reference Example 1, section 1.7 (post-treated impression bodies). Any remaining free space was filled with steatite spheres (3 mm diameter). The reaction heat was removed by circulating a thermostated heat transfer medium (water / glycol mixture) on the co-current side of the feed. The flow rate of the heat transfer medium was adjusted so that the temperature difference between the inlet and the outlet did not exceed 1 ° C. The reaction temperature referred to below in this document was defined as the temperature of the heat transfer medium entering the reactor housing. At the outlet of the reactor, the pressure was controlled by a pressure regulator and kept constant at 20 bar.
[220] The reactor was fed from below with a single-phase liquid flow (1). Stream 1 was prepared by mixing three streams (2), (3) and (4). The current temperature (1) was not actively controlled, but was generally in the range of 20 ° C to 40 ° C: - Current (2) having a flow rate of 85 kg / h. At least 99.5% by weight of chain (2) consisted of acetonitrile, propene and water. This stream (2) came from the bottom of the acetonitrile recycling distillation unit (J). - Stream (3) having a flow of 15 kg / h was an aqueous solution of hydrogen peroxide having a hydrogen peroxide concentration of 40% by weight ("crude / washed" grade from Solvay with a TOC in the range of 100 to 400 mg / kg The aqueous solution of hydrogen peroxide was supplied from a storage tank, allowing continuous feeding and fed using a suitable metering pump. - Chain (4) was a pure acetonitrile elaboration chain ( chemical grade, from Ineos, purity about 99.9%, containing between 70 to 180 ppm by weight of propanonitrile, 5 to 20 ppm by weight of acetamide and less than 100 ppm by weight of water as impurities). Sufficient fresh water was added to compensate for losses in the process. Under normal conditions, an average of 100 to 150 g / h of acetonitrile elaboration was added.
[221] the output current leaving epoxidation unit A was sampled every 20 minutes in order to determine the concentration of hydrogen peroxide using the titanyl sulfate method and calculate the conversion of hydrogen peroxide. The conversion of hydrogen peroxide was defined as 100 x (1-m / m / m) where m-m is the molar flow rate of H2O2 in the reactor supply and mfora is the molar flow rate of H2O2 at the reactor outlet. Based on the hydrogen peroxide conversion values respectively obtained, the temperature input of the heat transfer medium was adjusted in order to keep the hydrogen peroxide conversion essentially constant in the range of 90% to 92%. The inlet temperature of the heat transfer medium was adjusted to 30 ° C at the beginning of a given run with a fresh batch of the epoxidation catalyst and was increased, if necessary, to maintain the conversion of hydrogen peroxide in the mentioned range. The required temperature rise was generally less than 1 ° C / d. b) Intermediate Propylene Oxide Removal (Distillation Unit B)
[222] After releasing pressure, the effluent from epoxidation unit A (stream (5)) was sent to an intermediate propylene oxide removal column (distillation unit B) operated at about 1.1 bar. The column was 6 m high, had a diameter of 200 mm and was equipped with 30 trays with bubblers, an evaporator and a condenser. The column feed entered above the tray with bubblers 25 (counted from the top). The suspended flow leaving the column at about 50 ° C, mainly contained propylene oxide, unconverted propene and small amounts of oxygen formed as a by-product. This current was partially condensed (T = 15-25 ° C), and the condensed liquid served as an internal reflux current, considering that the gaseous part (current (6)) was sent to the light separation column (light unit). distillation D).
[223] The bottom temperature of the intermediate propylene oxide removal column was about 80 ° C. The bottom stream (stream (7)) was almost free of propylene oxide (<300 ppm by weight) and was a mixture of acetonitrile (about 78% to 80% by weight), water (about 18% to 20% % by weight), unconverted hydrogen epoxide and heavy boilers having a normal boiling point above 100 ° C, the main heavy boiler being propylene glycol. This bottom flow (7) was subsequently cooled to 35 ° C and pumped to the finishing reactor (epoxidation unit C; see section c) below) using a suitable metering pump. c) Epoxidation in a Finishing Reactor (Epoxidation Unit C)
[224] The total supply current of the finishing reactor C was obtained by mixing the current (7) obtained according to section b) above with a current (8) of polymer grade liquid propylene containing propane (purity> about 99.5%, feed rate: 0.9 kg / h, at room temperature). Both streams (7) and (8) were mixed using a static mixer and fed to the bottom of the finishing reactor C.
[225] The finishing reactor C was a fixed bed reactor adiabatically operated. In this context, the term "adiabatic" refers to a mode of operation, according to which no active cooling is carried out and according to which the finishing reactor is substantially isolated, in order to minimize heat losses) . The finishing reactor C had a length of 4 m and a diameter of 100 mm. The reactor was filled with 9 kg of the same epoxidation catalyst that was used in the main epoxidation reactor A. Free space was filled with stealite spheres (3 mm diameter). The operating pressure of the finishing reactor C was 10 bar, which was kept constant by a suitable pressure regulator at the reactor outlet. The output of the finishing reactor C was sampled every 20 minutes in order to determine the concentration of hydrogen peroxide using the titanyl sulfate method.
[226] The effluent from the finishing reactor C, flow (9), was depressurized in an evaporation drum, and both the liquid and the gas in this drum were fed to a light boiler separation column (distillation unit D).
[227] The stream (6), obtained from the top of the intermediate propylene oxide removal column (distillation unit B), and the stream (9), obtained as effluent from the finishing reactor C (epoxidation unit C ) together constitute the effluent stream of the epoxidation reaction REFERENCE EXAMPLE 4: EPOXIDATION REACTION INSTALLATION (MICRO-PLANT)
[228] A tubular reactor (length: 1.4 m, internal diameter: 7 mm) equipped with a thermostat jacket was loaded with 15 g of the desired catalyst in the form of filaments, with a diameter of 1.5 mm, as described in the examples below. The remaining volume of the reactor was filled with inert material (steatite spheres, 2 mm in diameter, for a height of about 5 cm at the lower end of the reactor and the remainder at the upper end of the reactor). The reactor was thermostated by flowing a heat transfer medium (a mixture of water and ethylene glycol) through the jacket. The heat transfer medium is fed to the bottom end of the jacket so that it flows in currents parallel to the reactor contents. The temperature of the heat transfer medium at the jacket entrance is defined as the reaction temperature. The flow rate of the heat transfer medium is adjusted so that the difference between the inlet and outlet temperature is not more than 1 ° C. Pressure in the reactor is controlled by a suitable pressure control valve and kept constant at 20 ° C. bar (abs).
[229] The reactor feed stream is combined from three separate feed streams that are measured when using separate metering pumps: The first stream consists of acetonitrile (flow rate: 68 g / h). The second stream consists of liquefied polymer quality propylene (flow rate: 11 g / h) and the third stream consists of an aqueous hydrogen peroxide solution with a concentration of 40% by weight (flow rate: 17 g / h) H). The potassium salt additive used in the experiments was dissolved in the hydrogen peroxide solution. The three feed streams were premixed before being fed at room temperature to the bottom of the tubular reactor. Under the conditions used, the feed is liquid and only one liquid phase is present.
[230] The experiments were carried out on a continuous basis. At the beginning of the test (t = 0 elimination is defined, in which the H2O2 metering pump is started) the reaction temperature was set at 30 ° C. With a fresh catalyst this initially results in a conversion of 100% hydrogen peroxide. After a certain period of time (usually within 100 hours in the stream), the conversion of hydrogen peroxide begins to drop. The temperature is then adjusted (usually once to twice a day is sufficient) in order to keep the hydrogen peroxide conversion between 85 and 95%. Most of the time in current, the conversion remains between 88 and 92%. The reactor effluent after the pressure control valve was collected, weighed and analyzed.
[231] Organic components (with the exception of hydroperoxypropanols) and O2 were analyzed on two separate gas chromatographs. Hydrogen peroxide was determined colorimetrically using the titanyl sulfate method. The content of hydroperoxypropanols (a mixture of 1-hydroperoxypropanol-2 and 2-hydroperoxypropanol-1) was determined by measuring the total peroxide content (idiometrically) and then subtracting the hydrogen peroxide content. In addition, the hydroperoxypropanol concentration can also be crossed and checked by determining the amount of propylene glycol before and after reduction with an excess of triphenylphosphane. The difference between the two values gives the amount of hydroperoxypropanols present in the unreduced sample.
[232] The selectivity for propylene oxide given is relative to H2O2 and was calculated as 100 times the ratio of moles of propylene oxide in the reactor effluent, divided by the sum of moles of propylene oxide plus propylene glycol, twice more the moles of hydroperoxypropanols and twice the moles of O2 (factor two reflects the stoichiometry of the reactions leading to these products: 2 H2O2 ^ 2 H2O + O2 and Propylene + 2 H2O2 ^ hydroperoxypropanol + H2O). COMPARATIVE EXAMPLE1 CONVENTIONAL CATALYST REGENERATION ZNTiMWW
[233] Zn TiMWW catalyst spent from fractions 1 to 3 of Reference Example 2 has been regenerated by undergoing a heat treatment. Specifically, 30 g of spent catalyst was transferred into an oven. The ZnTiMWW catalyst was contacted with nitrogen at a temperature of 120 ° C to remove volatile reaction compounds after which the ZnTiMWW catalyst was calcined in an air oven at 450 ° C for 5 hours. COMPARATIVE EXAMPLE 2 CATALYTIC PERFORMANCE OF CONVENTIONAL REGENERATED ZNTIMWW CATALYST
[234] After multiple regeneration according to Comparative Example 1, the catalytic performance of the regenerating ZnTiMWW catalyst was compared to the catalytic performance of the fresh ZnTiMWW catalyst.
[235] Two separate epoxidation reactions were performed according to the installation as described in reference example 3 using 15 g of fresh ZnTiMWW catalyst and with 15 g of conventionally regenerated ZnTiMMW catalyst, respectively, under identical reaction conditions.
[236] Epoxidation using fresh ZnTiMWW catalyst was terminated after 405 hours, whereas epoxidation using conventionally regenerated ZnTiMWW catalyst was terminated after 500 hours. The reaction temperatures (ie, cooling water temperatures), were adjusted in each experiment, so that at all times, the conversion rate of hydrogen peroxide is at least 91%.
[237] In figure 3, selectivity based on hydrogen peroxide, selectivity based on propene (C3), the conversion rate based on hydrogen peroxide and the reaction temperature required to maintain a conversion rate to peroxide hydrogen content of at least 91% of fresh ZnTiMWW catalyst and conventionally regenerated ZnTiMWW catalyst were compared. The quantities of the products obtained and the amount of educt converted were determined by gas chromatography.
[238] For the fresh ZnTiMWW catalyst, the reaction temperature could be maintained at 35 ° C for most of the reaction time to maintain a conversion rate based on hydrogen peroxide of at least 91%. In addition, selectivities based on hydrogen peroxide and propene remained above 98% during the period of time when epoxidation was performed with fresh ZnTiMWW catalyst.
[239] The conventionally regenerated ZnTiMWW catalyst, as described in Comparative Example 1, required a significant increase in reaction temperature of up to 64 ° C to maintain a conversion rate based on hydrogen peroxide of at least 91%. While propylene-based selectivity also remained above 98% similar to the fresh ZnTiMWW catalyst, hydrogen peroxide-based selectivity dropped to 94% after 400 hours when using the regenerated ZnTiMWW catalyst just by heating. EXAMPLE 1: UNIQUE ZNTIMWW CATALYST REGENERATION ACCORDING TO THE INVENTION
[240] Two separate regenerations according to the invention were carried out at two different washing temperatures. A regeneration was carried out by washing the catalyst at 50 ° C and another regeneration was performed by washing the catalyst at 70 ° C. For each experiment, 40 g of spent ZnTiMWW catalyst from fractions 1 to 3 of example 1 were used.
[241] The washing of the ZnTiMWW catalyst was carried out in both experiments using a glass tube with double water-cooled cover as a reactor with a length of 1 m and an internal diameter of 20 mm. The water temperatures were controlled by a thermostat to keep the temperature constant during the respective washing procedure. The water was introduced to the reactor cover through a pump with a flow rate of 4 ml / min (corresponding to a WHSV of 7 h-1) in increasing flow.
[242] At 50 ° C, the wash was performed for 420 min. At 70 ° C, the wash was carried out 410 min. In both experiments, washing was carried out until the conductivity of the washing water, leaving the reactor at the top was determined to be approximately 200 microSiemens / cm. Conductivity was determined using a conductometer (WTW, LF320) with a standard conductivity measurement cell (Tetra Con 325).
[243] After washing, the ZnTiMWW catalyst was dried in both experiments in the double-coated glass reactor in a stream of nitrogen gas of 100 l / h at 40 ° C for 16 hours, after which the ZnTiMWW catalyst was removed from the reactor and calcined in an oven at 450 ° C in the air for 5 hours.
[244] After regenerating the ZnTiMWW catalyst at 50 ° C and 70 ° C, the individual compositions were determined by elementary analysis. The elementary analysis was performed as indicated in reference example 2 and the results obtained are summarized in table 1 below. TABLE 1 EXAMPLE 1 RESULTS


[245] In row number 1, the amounts in g of compounds K, P, Si, Ti and Zn in the total amount of 40 g of catalyst ZnTiMWW before regeneration are given. In rows numbers 2 to 4, the total quantities, in g, of the compounds K, P, Si, Ti and Zn are indicated in the washing water collected in different periods of time (row number 2: 0 to 180 min; row number. 3: 181 to 300 min; row number. 4: 301 to 420 min). It is believed that the small losses of Si, Ti and Zn observed during washing are attributed to the formation of small tiny fragments. In row number 5, the total g amounts of these compounds in the waste water removed from the glass tube reactor after finished washing are given. In row number 6, the total quantities, in g of compounds in said ZnTiMWW catalyst after complete regeneration, ie washing, drying and calcination, are indicated.
[246] Consequently, after approximately 7 hours of washing, followed by drying and calcination, the total amounts of K and P were both reduced favorably by approximately 60% by washing at 50 ° C and even more favorably by approximately 82% and 67%, respectively, by washing at 70 ° C.
[247] At both temperatures, deposit removal is satisfactory. However, it is evident that by washing at 70 ° C potassium and phosphorus deposited on the ZnTiMWW catalyst can be removed faster and more deeply. EXAMPLE 2: REPEAT ZNTIMWW CATALYST REGENERATION PERFORMED ACCORDING TO THE INVENTION
[248] 34.3 g ZnTiMWW spent from fractions 1 to 3 of reference example 2 were subjected to 5 subsequent regenerations, as described in example 1.
[249] The wash was performed each time at 70 ° C. After each cycle the exact composition of the ZnTiMWW catalyst and additional properties were determined, specifically, its surface, pore volume, and crushing strength. In addition, a propylene oxide (PO) test was carried out, which is an indicator of the catalytic activity of the ZnTiMWW catalyst.
[250] The total amounts of K, P, Ti, Zn and Si of the ZnTiMWW catalyst were determined as described in example 1 by elementary analysis.
[251] Langmuir's surface area was determined by nitrogen adsorption at 77 K according to DIN 66131. The pore volume was determined according to Hg porosimetry according to DIN 66133.
[252] The crush strength as referred to in the context of the present invention is to be understood as determined by means of a crush resistance testing machine Z2.5 / TS1S, supplier Zwick GmbH & Co., D-89079 Ulm, Germany. As for the fundamentals of this machine and its operation, reference is made to the respective manual of "Register 1: Betriebsanleitung / Sicherheitshandbuch für die Material-Prüfmaschine Z2.5 / TS1S", version 1.5, December 2001 by Zwick GmbH & Co. Technische Dokumentation, August-Nagel-Strasse 11, D-89079 Ulm, Germany. The title page of the instruction manual is shown in Figure 9. With this machine, a ZnTiMWW catalyst pellet is subjected to an increasing force by means of a piston having a diameter of 3 mm until the filament is crushed. The force at which the filament is crushed is referred to as the resistance to crushing the filament. The machine is equipped with a fixed horizontal table on which the filament is positioned. A plunger that is freely movable in the vertical direction drives the filament against the fixed table. The apparatus was operated with a preliminary force of 0.5 N, a shear rate under preliminary force of 10 mm / min and a subsequent test rate of 1.6 mm / min. The vertically mobile plunger was connected to a load cell for accumulation of force and, during the measurement, it moved towards the fixed turntable in which the molding body (filament) to be investigated is positioned, thus, activating the filament against the table. The plunger was applied to the filaments perpendicularly to their longitudinal axis. Control of the experiment was carried out by means of a computer that recorded and evaluated the results of the measurements. The values obtained are the average value of the measurements for 10 filaments in each case.
[253] In a PO d test (propylene oxide test), the ZnTiMWW catalyst regenerated according to the process of the present invention is tested in a mini autoclave by reacting the propene with an aqueous hydrogen peroxide solution (30% by weight) to produce propylene oxide. In particular, 0.63 g of the ZnTiMWW catalyst is introduced along with 79.2 g of acetonitrile and 12.4 g of propene at room temperature, and 22.1 g of hydrogen peroxide (30% by weight in water) in a steel autoclave. After a reaction time of 4 hours at 40 ° C, the mixture was cooled under pressure and the liquid phase was analyzed by gas chromatography in relation to its propylene oxide content. The propylene oxide content of the liquid phase (in% by weight) is the result of the PO test.
[254] The results are summarized in Table 2 below. TABLE 2 RESULTS OF EXAMPLE 2


na * - not determined
[255] The results in table 2 show that the amounts of potassium and phosphorus deposits can be reduced even further by performing the regeneration process of the present invention several times later.
[256] From table 2, it is also evident that the Zn, Ti and Si contents of the ZnTiMWW catalyst have not changed over a process comprising five regeneration cycles compared to the fresh ZnTiMWW catalyst. The slight variations determined are considered within the measurement error.
[257] In addition, Table 2 also shows that the Langmuir surface, pore volume and crushing strength of the ZnTiMWW catalyst did not change during the repeated regeneration process compared to the fresh ZnTiMWW catalyst. Likewise, the observed variations for the determined values are considered within the measurement error.
[258] The PO test also showed that the yield of the repeatedly regenerated ZnTiMWW catalyst did not change significantly after five regeneration cycles.
[259] In addition, a fresh ZnTiMWW catalyst IR spectrum shown in Figure 4 can be compared to the IR spectrum recorded with the five times regenerated ZnTiMWW catalyst in Figure 5. The spectra are largely identical, except for the band visible at approximately 3500 cm-1 in the spectrum of the regenerated ZnTiMWW catalyst. This is an indicator for a decrease in internal silanol nests after regeneration. However, such a change does not have an impact on the activity of a Zeolitic catalyst as confirmed by the results summarized in Table 2.
[260] In summary, these results consistently indicate that the present process of regenerating a catalyst, comprising a titanium zeolite as an active material, is sufficiently effective, so that the original activity of catalytic activity is restored, without even following several cycles of regeneration, the catalyst is not structurally altered significantly. EXAMPLE 3: CATALYTIC PERFORMANCE OF THE REGENERATED CATALYST MULTIPLE TIMES ACCORDING TO THE INVENTION
[261] After multiple regeneration according to example 2, the catalytic performance of the regenerating ZnTiMWW catalyst was compared to the catalytic performance of the fresh ZnTiMWW catalyst.
[262] Two separate epoxidation reactions were performed in a micro-plant with 15 g of fresh ZnTiMWW catalyst and with 15 g of regenerated ZnTiMMW catalyst multiple times, respectively, under identical reaction conditions, other than that.
[263] The micro-plant comprised 1.4m long water-cooled reactor tubes and an internal diameter of 7mm. The feeds introduced in increasing flow were in each case 68 g / h ACN, 16 g / h H2O2 (40% by weight in water), 10.8 g / h propene and a concentration of 130 micromol KH2PO4 per 1 mol of H2O2 was used . Epoxidation using fresh ZnTiMWW catalyst was terminated after 500 hours, whereas epoxidation using the regenerated ZnTiMWW catalyst multiple times was terminated after 310 hours. The reaction temperatures (ie cooling water temperatures) are adjusted in each experiment, so that at all times, the conversion rate of hydrogen peroxide is at least 91%.
[264] In figure 6, selectivity based on hydrogen peroxide, selectivity based on propene, conversion rate based on hydrogen peroxide and the reaction temperatures (ie cooling water temperature) required to maintaining a conversion rate of at least 91% obtained with fresh and regenerated catalyst multiple times, respectively, are compared. Selectivities and conversion rates were determined as shown in comparative example 2 by gas chromatography.
[265] It is immediately evident that the reaction temperatures necessary to keep the hydrogen peroxide conversion rate above 91% are favorably essentially identical when comparing the fresh ZnTiMWW catalyst and the five times regenerated ZnTiMWW catalyst. In both cases, the conversion rate of approximately 45 ° C remained well above 91%, with the exception of an isolated case just below 90 ° C, after approximately 255 h observed for the regenerated ZnTiMWW catalyst multiple times.
[266] Also, selectivities based on hydrogen peroxide and propene remained essentially unchanged, exhibiting a high favorable value of around 99% during the epoxidation reaction when comparing the regenerated ZnTiMWW catalyst five times according to invention with the fresh ZnTiMWW catalyst. EXAMPLE 4: IN SITU REGENERATION OF CATALYST ZNTIMWW EXPENSES ACCORDING TO THE INVENTION
[267] A regeneration according to the present invention was carried out on the ZnTiMWW catalyst inside the reactor used for epoxidation in reference example 2.
[268] The spent ZnTiMWW catalyst was washed in 12 m reactor tubes with water at a flow rate of 130 l / h at 60 ° C for 17.7 hours, followed by a water wash at a flow rate of 130 l / h at 75 ° C for 4.5 hours. The water was introduced in a downward flow at the top of the reactor tubes.
[269] Subsequently, the ZnTiMWW catalyst was dried in the reactor in a stream of nitrogen gas also introduced at the bottom of the reactor tubes. Nitrogen was introduced at a flow rate of 12 m3 / h at a temperature of 60 ° C for 96 hours, followed by an introduction of nitrogen at a flow rate of 14 m3 / h at 65 ° C for 1 h, additionally followed by an introduction of nitrogen at a flow rate of 13 m3 / h at 70 ° C for 354.5 h. At the end of the drying step, the nitrogen moisture leaving the reactor as determined using a humidity sensor (GE, HygroPro) was 243 ppmV, which corresponds to the moisture of the nitrogen gas before its introduction into the reactor.
[270] After the complete drying step, the catalyst was calcined in the reactor for 6.5 hours at 450 ° C, where the calcination temperature was gradually increased, at a rate of 0.5 ° C / minute.
[271] The properties of the catalyst following regeneration when reused in an epoxidation procedure were similar to the results obtained in examples 1 and 3. REFERENCE EXAMPLE 5: CATALYST CHARACTERIZATION REFERENCE EXAMPLE 5.1: DV10, DV50 AND DV90 VALUE DETERMINATION
[272] 1.0 g of the micro powder is suspended in 100 g of deionized water and stirred for 1 min. The sample was subjected to measurement in a device using the following parameters: Mastersizer S long bed version 2.15, ser. No. 33544-325; supplier: Malvern Instruments GmbH, Herrenberg, Germany: focal length 300RF mm; beam length 10.00 mm; MS17 module; shading of 16.9%; dispersion model 3 $$ D; polydispersed correction of analysis model: none. REFERENCE EXAMPLE 5.2: DETERMINATION OF THE SILANOL CONCENTRATION OF THE MOLDING BODIES OF THE PRESENT INVENTION
[273] For the determination of silanol concentration, the 29Si MAS NMR experiments were performed at room temperature on a VARIAN Infinityplus-400 spectrometer using 5.0 mm ZrO2 rotors. The 29Si MAS NMR spectra were collected at 79.5 MHz using a 1.9 μs π / 4 pulse (pi / 4 microseconds) with a 10 s recycling delay and 4000 scans. All spectra of Si 29 were recorded in samples rotated at 6 kHz, and chemical changes were referred to as sodium sulfonate 4,4-dimethyl-4-silapentane (DSS). For the determination of the silanol group concentration, a certain spectrum of Si29MAS NMR is developed by the appropriate Gaussian-Lorentzian line formats. The concentration of silanol groups in relation to the total number of Si atoms is obtained by integrating the developed 29Si MAS NMR spectra. REFERENCE EXAMPLE 5.3: DETERMINATION OF RESISTANCE TO CRUSHING MOLDING BODIES
[274] Crush resistance as referred to in the context of the present invention is to be understood as determined by means of a Z2.5 / TS1S crush resistance testing machine, supplier Zwick GmbH & Co., D-89079 Ulm, Germany. As for the fundamentals of this machine and its operation, reference is made to the respective manual of "Register 1: Betriebsanleitung / Sicherheitshandbuch für die Material-Prüfmaschine Z2.5 / TS1S", version 1.5, December 2001 by Zwick GmbH & Co. Technische Dokumentation, August-Nagel-Strasse 11, D-89079 Ulm, Germany. With said machine, a given filament is subjected to an increasing force by means of a piston having a diameter of 3 mm until the filament is crushed. The force at which the filament is crushed is referred to as the resistance to crushing the filament. The machine is equipped with a fixed horizontal table on which the filament is positioned. A plunger that is freely movable in the vertical direction drives the filament against the fixed table. The apparatus was operated with a preliminary force of 0.5 N, a shear rate under preliminary force of 10 mm / min and a subsequent test rate of 1.6 mm / min. The vertically mobile plunger was connected to a load cell for accumulation of force and, during the measurement, it moved towards the fixed turntable in which the molding body (filament) to be investigated is positioned, thus, activating the filament against the table. The plunger was applied to the filaments perpendicularly to their longitudinal axis. Control of the experiment was carried out by means of a computer that recorded and evaluated the results of the measurements. The values obtained are the average value of the measurements for 10 filaments in each case. REFERENCE EXAMPLE 5.4: 29SI NMR SOLID-STATE SPECTRUMS WITH RESPECT TO Q3 AND Q4 STRUCTURES
[275] The effect of the inventive water treatment on the mold related to Q3 and Q4 structures in the material was characterized by comparing the changes in the Si29 Solid State NMR Spectrum under comparable conditions. All 29Si solid state NMR experiments were performed using a Bruker Advance spectrometer with a 300 MHz frequency of Larmor 1H (Bruker Biospin, Germany). Samples were packed in 7 mm ZrO2 rotors and measured under 5 kHz Magic Angle Rotation at room temperature. Direct polarization spectra of 29Si were obtained using pulse excitation (pi / 2) with a pulse width of 5 microseconds, a carrier frequency of 29Si corresponding to - 65 ppm in the spectrum and a scan recycling delay of 120 s. The signal was acquired for 25 ms under dissociation of 45 kHz high-power protons and accumulated for 10 to 17 hours. Spectra were processed using Bruker Topspin with a 30 Hz exponential line, expanding manual phasing and manual baseline correction over the full spectrum width. Spectra were referenced with the polymer Q8M8 as an external secondary standard, defining the resonance of the trimethylsilyl M group at 12.5 ppm. The spectra were then assembled with a set of Gaussian line formats, according to the number of discernible resonances. Regarding the currently evaluated spectra, a total of 6 lines were used, being responsible for the five distinct peak maximums (at approximately -118, -115, -113, -110 and -104 ppm) plus a clearly visible projection at -98 ppm . Assembly was performed using DMFit (Massiot et al., Magnetic Resonance in Chemistry, 40 (2002), pp. 70-76). Peaks were defined manually at the maximum visible peak or on the ledge. Both the peak position and the line width were then left free, that is, mounting spikes were not fixed in a certain position. The assembly result was numerically stable, that is, distortions in the initial assembly configuration, as described above, led to similar results. The peak areas assembled were additionally used normalized as done by DMFit. After the water treatment of the invention, a decrease in signal intensity was observed on the left side of the spectrum, a region that includes Q3 silanol structures (here especially: around and above-104 ppm, that is, "left" from - 104 ppm). In addition, a signal increase on the right side of the spectrum (here: below -110 ppm, that is, "right" of -110 ppm) was observed, whose region comprises Q4 structures exclusively. For the quantification of spectrum changes, a proportion was calculated that reflects the changes in the peak areas "left hand" and "right hand", as follows. The six peaks were labeled with 1, 2, 3, 4, 5 and 6 and the Q ratio was calculated with the formula 100 * {[a1 + a2] / [a4 + a5 + a6]} / a3. In this formula, ai, i = 1..6 represents the area of the mounted peak to which this number has been assigned. REFERENCE EXAMPLE 5.5: ADSORPTION / DESORPTION WATER ABSORPTION - WATER
[276] Isothermal measurements of water adsorption / desorption were performed on a VTI SA instrument from TA Instruments, following an isothermal step program. The experiment consisted of one run or a series of runs performed on a sample material that was placed in the microbalance pan inside the instrument. Before measurements were started, residual sample moisture was removed by heating the sample to 100 ° C (heating ramp 5 ° C / min) and keeping it for 6 h under a flow of N2. After the drying program, the temperature in the cell was lowered to 25 ° C and kept isothermal during the measurements. The microbalance was calibrated, and the weight of the dry sample was balanced (maximum mass deviation of 0.01% by weight). Water uptake by the sample was measured as the increase in weight over the dry sample. First, an adsorption curve was measured by increasing the relative humidity (RH) (expressed as% by weight of water in the atmosphere inside the cell) to which the samples were exposed and by measuring the water uptake by the equilibrated sample. The RH was increased with a step of 10% by weight. from 5% to 85%, and at each stage the system controlled the HR and monitored the weight of the sample until reaching the conditions of balance and recording of the weight capture. The total amount of water adsorbed by the sample was removed after the sample was exposed to RH of 85% by weight. During the desorption measurement, the RH was decreased from 85% by weight to 5% by weight with a 10% step and the change in the sample weight (water absorption) was monitored and recorded. REFERENCE EXAMPLE 5.6: FT-IR MEASUREMENTS
[277] FT-IR (Fourier-Infrared Transform) measurements were performed on a Nicolet 6700 spectrometer. The impression body was powdered and was then pressed onto a self-supporting pellet without the use of any additives. The pellet was introduced into a high vacuum (VH) cell placed inside the FT-IR instrument. Before measurement, the sample was pre-treated in high vacuum (10-5 mbar) for 3 hours at 300 ° C. The spectra were collected after cooling the cell to 50 ° C. The spectra were recorded in the range of 4000 to 800 cm -1 at a resolution of 2 cm-1. The obtained spectra are represented in a graph with the wave number (cm-1) on the x axis and the absorbance on the y axis (arbitrary units, a.u.). For the quantitative determination of peak heights and the proportion between these peaks, a baseline correction was performed. Changes in the region from 3000 to 3900 cm-1 were analyzed and for comparison of several samples, as a reference, the band was considered in 1880 ± 5 cm-1. REFERENCE EXAMPLE 5.7: DETERMINATION OF CRYSTALLINITY THROUGH DEXRD
[278] The particle size and crystallinity of the zeolitic materials according to the present invention were determined by XRD analysis. Data were collected using a standard Bragg-Brentano Diffractometer with an X-Cu-source and an energy dispersion point detector. The angular range of 2 ° to 70 ° (theta 2) was digitized with a step size of 0.02 °, while the variable divergence slit was defined for a constant illuminated sample size of 20 mm.
[279] The data were then analyzed using the TOPAS V4 software, in which the acute diffraction peaks were modeled using a Pawley fit containing a unit cell with the following starting parameters: a = 14.4 Angstrom (1 Angstrom = 10 -10 m) and c = 25.2 Angstrom in the space group P6 / mmm. These have been refined to fit the data. Independent peaks were inserted in the following positions. 8.4 °, 22.4 °, 28.2 ° and 43 °. These were used to describe the amorphous content. The crystalline content describes the intensity of the crystalline signal for the total dispersed intensity. The model also included a linear background, Lorentz corrections and polarization, mesh parameters, crystallite size and space group. Cited Literature
[280] WO-A 98/55229
[281] WO-A 2011/064191
[282] EP-A 0 934 116
[283] EP-A 0 790 07
[284] EP-A 1 371 414
[285] EP-A 1 221 442
[286] WO-A 2005/000827
[287] WO-A 2007/013739
[288] EP-A 1 122 249
[289] US 2003/0187284 A1
[290] US 2012/142950 A1
[291] WO 2011/115234 A1
[292] US 2004/058798 A1
[293] US 5 916 835 A

权利要求:
Claims (19)
[0001]
1. PROCESS FOR THE REGENERATION OF A CATALYST, characterized by comprising a zeolite containing titanium as a catalytically active material, said catalyst being used in a process for the preparation of an olefin oxide comprising (i) providing a mixture comprising an organic solvent, a olefin, an epoxidation agent and at least partially dissolved potassium, comprising salt; (ii) subjecting the mixture provided in (i) in a reactor to conditions of epoxidation in the presence of catalyst, obtaining a mixture comprising the organic solvent and the olefin oxide and obtaining the catalyst having a potassium salt deposited in itself; said process for regeneration comprising: (a) separating the mixture obtained from (ii) the catalyst; (b) washing the catalyst obtained from (a) with a liquid aqueous system comprising less than 0.1% by weight of compounds with a pKa value of 8 or less; and contain at least 75% by weight of water, based on the total weight of the liquid aqueous system; (c) optionally drying the catalyst obtained from (b) in a gas stream comprising an inert gas, at a temperature of less than 300 ° C; (d) calcining the catalyst obtained from (b) or (c) in a gas flow comprising oxygen, at a temperature of at least 300 ° C.
[0002]
2. PROCESS according to claim 1, characterized in that the liquid aqueous system used in (b) contains at least 90% by weight, preferably at least 95% by weight, more preferably at least 99% by weight, more preferably at least 99.9% by weight of water, based on the total weight of the liquid aqueous system.
[0003]
PROCESS according to any one of claims 1 to 2, characterized in that the washing in (b) is carried out at a pressure in the range of 0.8 to 1.5 bar, preferably from 1.0 to 1.4 bar and a temperature at 40 to 90 ° C, preferably 60 to 80 ° C.
[0004]
4. PROCESS according to any one of claims 1 to 3, characterized in that the washing in (b) is carried out until the potassium content of the liquid aqueous system after having come into contact with the catalyst is at most at 1000 weight-ppm, preferably at most 250 weight-ppm, more preferably at most 25 weight-ppm.
[0005]
PROCESS according to any one of claims 1 to 3, characterized in that the washing in (b) is carried out until the potassium content of the liquid aqueous system, after having contacted the catalyst in relation to the potassium content of the aqueous system liquid before having contact with the catalyst, be at most 333: 1, preferably at most 100: 1, most preferably at most 10: 1.
[0006]
PROCESS according to any one of claims 1 to 5, characterized in that at least 90% by volume, preferably at least 95% by volume, more preferably at least 99% by volume of the gas stream comprises an inert gas , according to (c) consist of at least one inert gas, selected from the group consisting of nitrogen, helium and argon, preferably nitrogen.
[0007]
PROCESS according to any one of claims 1 to 6, characterized in that the drying in (c) is carried out until the water content of the gas stream comprising an inert gas after having come in contact with the catalyst in relation to the content of water from the gas stream comprising an inert gas before contacting the catalyst is at most 1.10: 1, preferably at most 1.08: 1, more preferably at most 1.05: 1, more preferably at most 1.03: 1.
[0008]
PROCESS according to any one of claims 1 to 7, characterized in that after (c), the dry catalyst is heated to the calcination temperature, according to (d) with a rate in the range of 0.5 to 5 K / min, preferably 1 to 4 K / min, more preferably 2 to 3 K / min.
[0009]
PROCESS according to any one of claims 1 to 8, characterized in that the catalyst obtained from (d) has a potassium content of a maximum of 0.5% by weight, preferably a maximum of 0.4% by weight, plus preferably not more than 0.3% by weight, based on the total weight of the catalyst and determined by elementary analysis.
[0010]
PROCESS according to any one of claims 1 to 9, characterized in that the mixture provided in (i) has a potassium content with a molar range of potassium in relation to the epoxidizing agent included in the mixture in the range of 10 x 10- 6: 1 to 1500 x 10-6: 1, preferably 20 x 10-6: 1 to 1300 x 10-6: 1, more preferably from 30 x 10-6: 1 to 1000 x 10 -6: 1.
[0011]
PROCESS according to any one of claims 1 to 10, characterized in that the at least partially dissolved potassium comprising salt according to (i), is selected from the group consisting of at least one inorganic potassium salt, at least one organic potassium salt and combinations of at least one inorganic potassium salt and at least one organic potassium salt, wherein preferably at least one of the at least one potassium salt is an organic potassium salt.
[0012]
PROCESS according to any one of claims 1 to 11, characterized in that the at least partially dissolved potassium comprising salt according to (i) is preferably selected from the group consisting of at least one inorganic potassium salt selected from of the group consisting of potassium hydroxide, potassium halides, potassium nitrate, potassium sulphate, potassium hydrogen sulphate, potassium perchlorate, potassium dihydrogen phosphate or potassium phosphate or potassium phosphate or potassium pyrophosphates such as pyrophosphate monobasic or dibasic potassium pyrophosphate or tribasic potassium pyrophosphate or tetrabasic potassium pyrophosphate, or potassium etidronates, such as monobasic potassium etidronate or dibasic potassium etidronate or a less potassium or potassium potassium etidronate organic selected from the group consisting of potassium salts of saturated aliphatic monocarboxylic acids, preferably having 1, 2, 3, 4, 5 or 6 carbon atoms, potassium carbonate and potassium hydrogen carbonate and a combination of at least one of the at least one inorganic potassium salt and at least one of the at least one organic potassium salt.
[0013]
13. PROCESS according to any one of claims 1 to 12, characterized in that the titanium-containing zeolite has an MFI frame structure, a MEL frame structure, a MWW frame structure, a MWW frame structure, a structure ITQ frame structure, a BEA frame structure, a MOR frame structure or a mixed structure of two or more of these frame structures, preferably an MFI frame structure, a MWW frame structure or a MWW type frame structure.
[0014]
14. PROCESS according to any one of claims 1 to 13, characterized in that the zeolite containing titanium comprises at least one of Al, B, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni , Zn, Ga, Ge, In, Sn, Pb, Pd, Pt, Au, preferably at least one among B, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Zn , Ga, Ge, In, Sn, Pb, Pd, Pt, Au, or more preferably Zn.
[0015]
15. PROCESS, according to any one of claims 1 to 14, characterized in that zeolite containing titanium is a zeolitic material free of aluminum of MWW frame structure or of the MWW type, containing titanium, preferably in an amount of 0.5 to 5% by weight, more preferably 1 to 2% by weight, calculated as elemental titanium and based on the total weight of the zeolite containing titanium and containing zinc, preferably in an amount of 0.5 to 5% by weight, of preferably 1 to 2% by weight, calculated as elemental zinc and based on the total weight of the titanium-containing zeolite.
[0016]
16. PROCESS according to any one of claims 1 to 15, characterized in that the catalyst comprising a titanium-containing zeolite is a micropowder containing the titanium-containing zeolite, preferably a spray powder containing the zeolite-containing titanium, or a mold containing the zeolite containing titanium, preferably a mold containing a micropowder containing the titanium-containing zeolite, more preferably a mold containing a spray powder containing the titanium-containing zeolite.
[0017]
17. PROCESS according to any one of claims 1 to 16, characterized in that the mold containing the zeolite containing titanium comprises at least one binder, preferably a silica binder, preferably in an amount in the range of 5 to 50% by weight , more preferably 10 to 40% by weight, more preferably 20 to 30% by weight, based on the total weight of the mold.
[0018]
18. PROCESS, according to any one of claims 1 to 17, characterized in that the regeneration process is carried out in the reactor in which the mixture provided in (i) is subjected to epoxidation conditions according to (ii).
[0019]
19. PROCESS according to any one of claims 1 to 18, characterized in that it further comprises employing the catalyst obtained from (d) in a process for the preparation of an olefin oxide, preferably in an olefin epoxidation process comprising ( i ') providing a mixture comprising an organic solvent, an olefin, an epoxidizing agent and at least partially dissolved potassium, comprising salt; (ii ') subjecting the mixture provided in (i') in a reactor to conditions of epoxidation in the presence of catalyst obtained from (d), obtaining a mixture comprising the organic solvent and the olefin oxide.

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RU2702349C2|2019-10-08|Method of regenerating catalyst based on titanium-containing zeolite for epoxidation of propylene

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US11180467B2|2021-11-23|Propene recovery by scrubbing with a solvent/water mixture

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RU2766954C2|2022-03-16|Extraction of propene by cleaning in scrubber with solvent/water mixture

同族专利:

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公开号 | 公开日

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EP3024581A1|2016-06-01|

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MX2016001031A|2016-11-10|

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US9943838B2|2018-04-17|

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RU2016105804A|2017-08-28|

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SG10201803792UA|2018-06-28|

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JP2016525446A|2016-08-25|

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RU2673798C2|2018-11-30|

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KR20160039223A|2016-04-08|

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CN105579138B|2019-07-05|

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SG11201600536WA|2016-02-26|

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KR102254371B1|2021-05-24|

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US20160332152A1|2016-11-17|

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JP6581577B2|2019-09-25|

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RU2016105804A3|2018-05-08|

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WO2015010994A1|2015-01-29|

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RU2673798C9|2019-04-08|

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BR112016001518A2|2019-12-17|

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CN105579138A|2016-05-11|

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法律状态:
2018-11-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2020-02-04| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-06-30| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|

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2020-11-03| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-12-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 16/07/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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EP13177916|2013-07-24|

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EP13177916.7|2013-07-24|

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PCT/EP2014/065256|WO2015010994A1|2013-07-24|2014-07-16|Regeneration of a titanium containing zeolite|

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