• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a method of isomerizing dehydration of a feedstock comprising primary alcohol substituted in the 2-position by an alkyl group in which the feed is heated to the reaction temperature by indirect heat exchange and then vaporization by mixing with an effluent diluent, said diluted and vaporized charge being dehydrated in at least one dehydration reactor operating in the gas phase at an inlet temperature of between 250 and 375 ° C, at a pressure of between 0.2 MPa and 1 MPa and at a PPH included between 1 and 18 h -1, in the presence of a catalyst comprising a zeolite comprising at least one series of channels whose opening is defined by an 8-atom oxygen ring (8MR) and a binder, said catalyst being previously coked in-situ or ex-situ, so as to produce a dewatering effluent, the latter being treated and separated into a diluent effluent, an alkenes effluent and a hydro effluent heavy carbides.
    公开号:FR3026406A1
    申请号:FR1459113
    申请日:2014-09-26
    公开日:2016-04-01
    发明作者:Tom Vivien；Sylvie Maury；Vincent Coupard；Delphine Bazer-Bachi；Nikolai Nesterenko；Nadiya Danilina
    申请人:Total Research and Technology Feluy SA；IFP Energies Nouvelles IFPEN；
    IPC主号:
    专利说明:

    [0001] TECHNICAL FIELD OF THE INVENTION The present invention relates to an improved process for producing alkenes from a feedstock comprising a primary monoalcohol substituted in the 2-position by an alkyl group.
    [0002] This charge can be obtained by chemical processes or by fermentative processes. This process uses a zeolite-shaped shaped catalyst comprising at least one series of channels whose opening is defined by an 8-atom oxygen ring (8MR) and pre-coked.
    [0003] The alkenes obtained, in particular isobutene, butene-1 and butenes-2, are of great interest in the field of the petrochemical industry and organic synthesis. PRIOR ART Isobutene is a key molecule in petrochemistry and for the synthesis of gasoline additives such as ETBE and MTBE. The vast majority of publications focus on the production of isobutene from linear butanols, which are more easily produced by classical fermentation routes (ABE) than isobutanol. Recent developments, however, have greatly improved the fermentative yields of isobutanol, making this load accessible and available at attractive cost. The document WO2009 / 079213 describes the sequence of dehydration reactions of biosourced alcohols (C2-C7) on an acidic catalyst to form olefins followed by the oligomerization of olefins on an acid oligomerization catalyst (zeolite or alumina).
    [0004] The intended application is Jet fuel fuel preparation. EP 2348 005 describes the dehydration of alcohols containing from 2 to 10 carbon atoms in the corresponding olefin on a zeolitic FER catalyst having an Si / Al atomic ratio of less than 100. The weight hourly space velocity according to US Pat. the English name, or WHSV) in relation to the alcohol is at least 411-1 and the temperature is 320 to 600 ° C. WO 2011/089235 extends this invention to other structural types of zeolites all belonging to the family of zeolites with average channel size (10MR), Si / Al molar ratio of less than 100. Zeolites may be modified by different post treatments. The inventor claims the dehydration of alcohols containing from 2 to 10 carbon atoms to the corresponding olefin.
    [0005] Document WO 2011/113834 describes the simultaneous dehydration and skeletal isomerization of isobutanol in the presence of crystalline silicate catalysts, average channel size (10MR) dealuminized or not, phosphorus modified or otherwise, of the FER group, MWW, EUO, MFS, ZSM-48, MIT, MFI, MEL or TON having Si / Al ratio greater than 10, AEL group silicoaluminophosphate molecular sieves, or silica, zirconia, titanium or fluorine-alumina, on zeolitic catalysts. The WHSV with respect to alcohol is at least 11-1 and the temperature is 200-600 ° C. The proportion of n-butenes attained in butenes is 58.4% at 375 ° C at high WHSV (12.6h-1) on a powdered Si / Al Zeolite FER 33. No notion of stability of these performances as a function of under load is not mentioned in this document. The only other catalyst exemplified is gamma alumina. The dehydration of acidic acid alcohols is generally accompanied by the positional isomerization of the formed alkene. These two reactions are indeed concomitant, since the position isomerization of the double bond of the alkene is as fast as the dehydration reaction of the monoalcohol in 04. In the case of isobutanol, the initially formed isobutene is protonated. easily (formation of a tertiary carbocation) and can then undergo secondary reactions, including dimerization, then cyclization, which may result in the formation of undesired by-products. Kotsarenko et al., Kin. Katal. 24, 877 (1983) describes, however, in the particular case of simultaneous dehydration and skeletal isomerization of isobutanol on non-zeolitic solids, a mechanism in which a primary carbocation type intermediate species formed by dehydration at an acidic site of the alcohol is rearranged via a methyl shift reaction to form a secondary carbocation and promote the formation of linear butenes. The most efficient catalysts are unorganized mixed oxides based on alumina and silica, with an alumina content of less than 5%. The maximum proportion of n-butenes in butenes is 32.7% at temperatures between 275 and 350 ° C. The document FR2733701 describes a selectivating pretreatment for the isomerization of linear olefins to isobutene by bringing the catalyst into contact with one or more hydrocarbon molecules, thus comprising no oxygen, containing from 4 to 10 carbon atoms at a pressure comprised between between 0.1 and 1 MPa and at a temperature of between 300 and 550 ° C. This results in an increase in isobutene selectivity and a decrease in butene conversion. The present invention aims on the contrary to improve the selectivity to linear butenes. The present invention relates to a set of operating conditions, process choices and zeolitic catalyst preparation which make it possible, by converting a primary mono-alcohol substituted at the 2-position with an alkyl-alkene group, to reach a proportion of linear alkenes in the alkenes fraction is well above the expected value at thermodynamic equilibrium, with total conversion of the alcohol and selectivity to total alkenes greater than 97%.
    [0006] OBJECT AND INTEREST OF THE INVENTION The invention relates to a process for thermally integrated transformation of a feedstock comprising a primary monoalcohol substituted in position 2 by an alkyl group on a pre-coked catalyst comprising a zeolite comprising at least one series of Channels whose opening is defined by an 8-atom oxygen ring (8MR) which produces a mixture of alkenes rich in linear alkenes. The process according to the invention makes it possible to obtain, at the end of the reaction step, an effluent comprising a proportion of linear alkenes beyond that expected if we consider the thermodynamic equilibrium between the alkenes at room temperature. reactor output, with excellent conversion and very good selectivity. The method according to the invention also makes it possible to limit the thermal degradation of the charge by the implementation of an appropriate heating, as well as an overall reduction in the amount of hot and cold utilities required. DETAILED DESCRIPTION OF THE INVENTION The invention relates to a process for the isomerization dehydration of a feedstock comprising from 40 to 100% by weight of primary alcohol substituted in the 2-position by an alkyl group comprising at least the following stages: a) Pressurization said charge then preheating the compressed charge by heat exchange with the dehydration effluent from step c) in a heat exchanger to produce a preheated charge; b) vaporizing said preheated charge by mixing with the diluent effluent from step f), the ratio of mass flow rates diluent effluent on preheated charge being between 5/95 and 60/40; C) dehydration of the effluent from step b) in at least one dehydration reactor operating in the gas phase at a weighted average temperature of between 250 and 375 ° C., at a pressure of between 2 MPa and 1 MPa, and at a PPH between 1 and 18 h -1, in the presence of a catalyst comprising a zeolite having at least one series of channels whose opening is defined by an 8-atom oxygen ring (8MR), said catalyst being previously coked in-situ or ex-situ, so as to produce a dewatering effluent; d) cooling said dehydration effluent by at least three indirect indirect heat exchanges with at least the water effluent from step e), then said compressed charge of step a), then a cold utility so as to produce a cooled effluent; e) decanting said cooled effluent into an aqueous phase and an organic phase, a portion of said aqueous phase being purged for treatment outside said dewatering process and the other part, forming the water effluent being recycled via the step f); f) recycling of the effluent water from step e) and at least partial vaporization by heat exchange in a heat exchanger with the dehydration effluent from step c), separation of the liquid fraction possibly present then compressing and superheating the vapor fraction to form a diluent effluent, said diluent effluent being recycled to step b); g) Separation of the organic phase extracted from step e) in at least one distillation column so as to produce an effluent alkenes and a heavy hydrocarbon effluent. Charge According to the invention, the feedstock treated in the process according to the invention is a feedstock comprising from 40 to 100% by weight of at least one primary monoalcohol substituted in the 2-position by an alkyl group. Said monoalcohol is preferably isobutanol or 2-methyl-1-butanol, taken alone or as a mixture, and very preferably isobutanol. In the remainder of the description, the term "primary alcohol" denotes the primary monoalcohol. The term alkyl denotes a hydrocarbon compound of general formula C, 112'1 where n is an integer between 1 and 20, preferably between 1 and 10, preferably between 1 and 5.
    [0007] Said feedstock can come from chemical or biochemical processes, for example fermentation processes. In particular, this feedstock can be derived from fermentation processes of lignocellulosic biomass.
    [0008] Said filler also advantageously comprises 0 to 60% by weight of water. Said filler may also comprise impurities of mineral type (such as Na, Ca, P, Al, Si, K, SO 4) and of organic type (such as methanol, ethanol, n-butanol, aldehydes, ketones, and the corresponding acids, for example furanic acid, acetic acid, isobutyric acid). Step a) of preheating According to the invention, said feedstock comprising a primary monoalcohol substituted in the 2-position by an alkyl group is pressurized in a pump and then preheated by heat exchange with the dehydration effluent from step c ) in at least one heat exchanger to produce a preheated charge.
    [0009] Said pump makes it possible to increase the pressure of said load to a pressure of between 2 and 10 bar. The heat exchange allows the charge to be heated to a temperature between 100 and 250 ° C, preferably between 100 and 150 ° C. Step b) Spraying According to the invention, the preheated feedstock from step a) is vaporized by mixing with the diluent effluent from step f). The diluent effluent from step f) consists of water and dissolved impurities at their solubility under the conditions of the decantation step e). This effluent is vaporized, compressed, and superheated in step d) so as to provide sufficient energy for the vaporization of the diluent effluent and preheated charge mixture. The temperature of the diluent effluent as a result of its overheating is between 400 and 650 ° C, preferably between 425 and 550 ° C.
    [0010] The ratio of diluent effluent mass flow rates on preheated charge is between 5/95 and 60/40. The preheated feed mixture / diluent effluent is then heated in an oven to a temperature between 250 and 375 ° C.
    [0011] When the target for the heated fluid is a temperature at the outlet of a heating equipment, for example an oven, the temperature of the exchange surface is often much higher than the target temperature, the difference being order of 100 ° C. In contact with the walls, the heated fluid is therefore subjected to high temperatures. Thus, if it is aimed at 250 to 375 ° C at the furnace outlet, the hot mixture is exposed to contact with the walls at temperatures of the order of 350 to 475 ° C. The three-stage charge heater comprising a first heating step by heat exchange in a heat exchanger followed by a second heating step by mixing with the hot diluent effluent and a third heating step in an oven allows to avoid that the primary monoalcohol substituted in the 2-position by an alkyl group is found exposed concentrated, that is to say in a mixture comprising more than 95% by weight of primary monoalcohol substituted in position 2 by an alkyl group, at temperatures above 280 ° C. The primary monoalcohol substituted in the 2-position by an alkyl group is thus protected from the risks of thermal degradation, which improves the overall yield of the process. Step c) dehydration According to the invention, the effluent from step b) then feeds a dehydration step. The dehydration step comprises at least one dehydration reactor. When this step comprises more than one reactor, the temperature at the inlet of each of the reactors is adjusted to a value between 250 and 375 ° C. by heating means, the isomerizing dehydration reaction being endothermic, and each reactor is operated under identical conditions. Thus, in the remainder of the description, the term "the reactor" designates both the reactor of said step c), when it comprises only one reactor, and each of the reactors of said step c), when the reactor it comprises more than one reactor.
    [0012] The reactor is operated in the gas phase, at a weighted average temperature of between 250 and 375 ° C., at a pressure of between 0.2 MPa and 1 MPa, at a PPH of between 1 and 18 h -1, in the presence of a catalyst comprising a zeolite comprising at least one series of channels whose opening is defined by an 8-atom oxygen ring (8MR).
    [0013] Said catalyst is arranged in one or more fixed beds, which can be operated in ascending, descending or radial flow. By PPH is meant "Weight per Weight per Hour", that is to say the mass flow rate of primary alcohol substituted in position 2 by an alkyl group in the reactor inlet charge divided by the mass of catalyst in said reactor. This concept is also sometimes referred to by its acronym WHSV, or "Weight Hourly Space Velocity". By weighted average temperature is meant the average of the temperature in the catalytic bed calculated along the flow axis in said bed. Let a bed of length L and of surface S, the reactive mixture flowing along the longitudinal axis x of this bed, the entry into the catalytic bed forming the origin of the axis (x = 0), the weighted average temperature is expressed according to: TMP = - Li. T (x) dx 1 Li ° According to the invention, said catalyst is pre-coked in situ or ex situ with a feed comprising primary alcohol substituted in position 2 by an alkyl group at a partial pressure of said primary alcohol strictly greater than that of the feedstock of the process, or with said pure primary alcohol. By said pure primary alcohol is meant that said primary alcohol substituted in position 2 by an alkyl group comprises less than 1% mass of compounds other than said primary alcohol, preferably less than 1000 ppm, preferably less than 100 ppm, very preferably less than 10 ppm and very preferably that it does not include other detectable compounds. In another arrangement, the pre-coking may be carried out with the heavy hydrocarbon effluent from the separation step g).
    [0014] In a first embodiment of the invention, the pre-coking is carried out at a weighted average temperature strictly greater than the reaction temperature and between 250 and 450 ° C., advantageously between 300 and 450 ° C., and advantageously between 400 and 450 ° C., a pressure of between 0.1 and 3 MPa, advantageously between 0.1 and 0.5 MPa, and a PPH of between 0.1 and 10 h -1, advantageously between 0.1 and 311-1. In a second embodiment, the pre-coking is carried out at a weighted average temperature strictly lower than the weighted average operating temperature of the reaction, and between 200 and 350 ° C, preferably between 225 and 325 ° C, a pressure strictly greater than the operating pressure of the reaction and between 0.1 and 3 MPa, advantageously between 1.1 and 3 MPa, preferably between 1.2 and 3 MPa, and a PPH between 0.1 and 10 h -1 preferably between 0.1 and 311-1. This embodiment makes it possible in particular to avoid the deposit of heavy coke on the catalyst.
    [0015] In these two embodiments, the pre-coking is carried out for a period of 1 to 30 h, preferably 2 to 24 h. This pre-coking, carried out either at a weighted average temperature strictly greater than the weighted average operating temperature of the isomerizing dehydration reaction, or at a strictly lower weighted average temperature and a pressure strictly greater than the weighted average temperature and pressure of operation of the isomerizing dehydration reaction can significantly improve the selectivity of the catalyst to linear alkenes, beyond that expected if we consider the thermodynamic equilibrium between the alkenes at the reactor outlet temperature. It is carried out prior to the implementation of said catalyst to carry out the isomerizing dehydration reaction of the feedstock comprising primary alcohol substituted in the 2-position by an alkyl group. The conversion drops steadily during the operation. The catalyst is regularly regenerated by burning the coke in the presence of oxygen diluted in nitrogen, the dilution being adjusted so as to maintain a temperature in the catalytic bed of between 400 and 600 ° C. This regeneration is followed by pre-coking according to the invention before reactivating the catalyst. The pre-coking time is considered sufficient if, during the operation of the reactor so as to carry out the isomerizing dehydration reaction of said process feedstock, the C5 + selectivity is less than 1% for a conversion of said substituted primary monoalcohol. in position 2 by an alkyl group included in said process feed greater than 97%. The selectivity for C5 + is defined as the ratio of the difference between the mass flow rate of carbon element included in the hydrocarbons having at least 5 carbon atoms in the dewatering effluent and the mass flow rate of carbon element included in the hydrocarbons having at least 5 carbon atoms in the effluent from step b), the difference between the mass flow rate of carbon element included in the primary alcohol substituted in position 2 by an alkyl group included in the effluent from step b) and the mass flow rate of carbon element included in the primary alcohol substituted in the 2-position by an alkyl group included in the dehydration effluent. According to the invention, the catalyst used in step c) comprises a zeolite having at least one series of channels whose opening is defined by an 8-atom oxygen ring (8MR) as defined in the According to a particular embodiment, the zeolite can also advantageously contain at least one series of channels, of which the zeolite may advantageously contain at least one series of channels, of which the zeolite may also advantageously contain at least one series of channels. the pore opening is defined by a ring containing 10 oxygen atoms (10 MR).
    [0016] Said zeolite is advantageously chosen from the zeolites of the FER and MFS structural type, and more advantageously from the ferrierite, FU-9, ISI-6, NU-23, ZSM-35 and ZSM-57 zeolites, taken alone or as a mixture. Said zeolite is very advantageously ferrierite.
    [0017] Said catalyst comprises said zeolite shaped in a matrix consisting of an inert binder. Indeed, said zeolite can not be used industrially in powder form. The binder makes it possible to confer on the final solid an increased resistance in the presence of water.
    [0018] The zeolite binder mass ratio of said catalyst is between 50/50 and 10/90. Very advantageously, said catalyst consists of ferrierite zeolite and silicic binder.
    [0019] Said catalyst used in the process according to the invention is advantageously prepared according to a preparation process comprising at least the following steps: 1) a step of mixing at least one powder of zeolite in proton or ammonium form with at least one powder of at least one binder, for example an amorphous silica powder, which contributes to controlling the porosity of the final solid, and at least one solvent in the presence of a peptizing agent; 2) a step of adding a solvent, advantageously water, in order to modulate the loss on fire of the paste and to obtain the desired textural properties for the final solid; 3) a step of forming the pasty mixture obtained at the end of step 2), for example by extrusion; 4) a step of drying the shaped material obtained at the end of step 3), advantageously at a temperature of between 50 and 200 ° C., preferably between 80 and 150 ° C., advantageously for a duration of between 1 and 24 h, and advantageously under air; 5) an optional calcination step at a temperature ranging from 400 to 800 ° C for a period of 2 to 12 hours; 6) an optional thermal treatment step, such as steaming at a temperature between 500-700 ° C in humid air, that is to say comprising from 6 to 50% volume of water in the air.
    [0020] The binder used in step 1 may be chosen from binders well known to those skilled in the art, and more particularly from those having an "inertia" vis-à-vis the operating conditions and in particular the presence of water in the process. Thus, it is advantageous to use a silicic binder, an aluminophosphate binder or a clay. A source of silicic binder may be a precipitated silica or a silica derived from by-products such as fly ash, for example silico-aluminous or silico-calcic particles, and silica fumes. It is advantageous to use a colloidal silica, for example in the form of a stabilized suspension, such as for example commercial products such as Ludox® or Klebosol®.
    [0021] The amorphous silica powder advantageously used in step 1) of the process for preparing the catalyst used according to the invention preferably has a particle size of 1.4 or 1.8. The powders are advantageously kneaded in the presence of a solvent. (Step 2), preferably water in which a peptizing agent can advantageously be dissolved in order to obtain a better dispersion of the binder. The consistency of the dough is adjusted through the amount of solvent. The peptizing agent used during this stage may advantageously be an acid, an organic or inorganic base such as acetic acid, hydrochloric acid, sulfuric acid, formic acid, citric acid and acid. nitric, alone or in mixture, sodium hydroxide, potassium hydroxide, ammonia, an amine, a quaternary ammonium compound, chosen from alkylethanol amines or ethoxylated alkylamines, tetraethylammonium hydroxide and tetramethylammonium.
    [0022] The solid shaping protocol must not modify the access to the active part of the solid: the zeolite, and must facilitate the diffusion of the reagents into the solid. The shaped catalyst can take any form known to those skilled in the art, such as tablet, granule, extruded mono or multi-lobed, sphere.
    [0023] Said catalyst is micro / meso / macroporous. Cooling step d) The effluent from the last reactor of step c) is at a temperature of about 250 ° C. in the vapor phase.
    [0024] According to the invention, the effluent of step c) is cooled by at least three successive heat exchanges, with at least the effluent water resulting from step e), and then said compressed charge of step a ), then a cold utility so as to produce a cooled effluent. The heat exchanges are carried out in heat exchangers whose technology is well known to those skilled in the art (plate exchangers, tube-shell exchangers or other suitable systems). The effluent of step c) is cooled and partially condensed after the first heat exchange with the effluent water from step e). The cooling is continued with the second heat exchange with the load of step a) pressurized, then with the third exchange with the cold utility. After the third heat exchange, the effluent of step c) is completely condensed, and at a temperature below 50 ° C. It is then directed to step e) of decantation.
    [0025] Heat exchanges are carried out in heat exchangers known to those skilled in the art, which may include several calenders and possibly an avoidance circuit bypassing one or more of these calenders in order to adjust the temperature of the flow output. The cold utility may be air, cooling water, and / or any other available fluid allowing the effluent from step c) to reach a temperature below 50 ° C. Step e) of decantation In accordance with the invention, the effluent of stage c), cooled and condensed in stage d), feeds a stage e) of decantation. A demixing takes place and the decantation step e) makes it possible to separate an aqueous phase and an organic phase. The aqueous phase comprises more than 90% by weight of water, preferably more than 95% by weight of water. The water content of the aqueous phase is strongly dependent on the presence of non-reactive species in the dehydration stage c) and soluble in water, all of which are found in said aqueous phase, such as, for example, methanol, ethanol, acetaldehyde, acetone and the corresponding acids. It also comprises the compounds present in the organic phase at their solubility, mainly a few ppm of oxygenated compounds and approximately 5 ppm of primary alcohol substituted in the 2-position by an alkyl group. The organic phase contains the primary alcohol substituted in the organic phase. position 2 by an unreacted alkyl group, as well as alkenes and heavy products produced in step c) of dehydration.
    [0026] The aqueous phase is withdrawn for recycling. Part of this phase is purged in order to maintain the content of heavy compounds in recycling at a value of a few ppm. This purged portion can be processed outside the process. The non-purged portion, which forms the water effluent, is recycled via the recycling step f). The organic phase is treated in the separation step g) to produce at least one effluent alkenes.
    [0027] The purged fraction represents from 0 to 30% of the extracted aqueous phase, advantageously from 5 to 20% of this phase. Recycling step f) The effluent water withdrawn in the decantation stage e) is expanded. Relaxed means that its pressure is lowered. The trigger determines the low pressure point of the water recycle loop. The expanded water effluent is heated by heat exchange in a heat exchanger with the effluent of step c) dehydration, during which it is at least partially vaporized. By partially vaporized, it is meant that at least 90% by weight of the expanded water effluent is vaporized. The pressure of expansion of the effluent water is adjusted so as to recover the maximum heat during the heat exchange with the effluent of step c), that is to say that the vaporization at the resulting from the heat exchange is at least 90% by weight of the effluent water, but it is not total. The liquid fraction that may be present is separated in a separator flask intended to protect the compressor from any presence of liquid ("K.O. Drum" according to the English terminology). The vapor fraction, freed of the liquid fraction, is compressed in a compressor. The compressor sets the high pressure point of the recycling loop.
    [0028] The adjustment of the high point and the low pressure point of the process makes it possible, on the one hand, to ensure a sufficient pressure in the dehydration step c), but also to ensure maximum recovery of the heat of the effluent from the process. dehydration by spraying at least 90% of the water effluent. This adjustment is also performed in such a way that, while recovering the maximum heat of the dehydration effluent, the temperature of the vapor fraction of the effluent water is such that, after compression, the temperature does not exceed 300 ° C in order not to endorrmage the equipment.
    [0029] The compressed vapor fraction, at a temperature not exceeding 300 ° C, is superheated in a heat exchanger, for example an oven, at a temperature between 400 and 650 ° C.
    [0030] In a preferred arrangement, only one furnace is used for heating the preheated feed mixture / diluent effluent during step b) and for superheating of the compressed vapor fraction, the latter being superheated in the hot part of the furnace, while that said mixture is put in temperature in the cold part.
    [0031] The compressed and superheated vapor fraction forms the diluent effluent. This effluent is then mixed with the preheated charge from step a) to ensure its evaporation. Separation step g) According to the invention, the organic phase extracted from step e) is treated in a separation step so as to produce an alkenic effluent and a heavy hydrocarbon effluent. Said separation step comprises at least one distillation column. Said organic phase is separated by distillation and is recovered at the head a distillate comprising alkenes and in the bottom a residue comprising the heavy products and the primary alcohol substituted in position 2 by an unreacted alkyl group. This column has from 5 to 20 theoretical plates, advantageously from 5 to 15. The column is operated at a pressure of between 0.5 and 1 MPa, with a head temperature of between 50 and 90 ° C., and a background temperature of between between 100 and 150 ° C. The distillate is advantageously directed to a dryer, necessary to adjust the water content as a function of the downstream applications.
    [0032] The primary alcohol substituted in the 2-position by an unconverted alkyl group included in the residue may advantageously be recycled in admixture with the feedstock of the process according to the invention.
    [0033] EXAMPLES Example 1 (non-compliant): heating of isobutanol: This example illustrates the thermal decomposition of pure isobutanol when it is heated to high temperature. Pure isobutanol, that is to say in particular water-free, is vaporized in an oven in which an inert carborundum bed (SiC) has been installed to promote heat exchange. It is exposed to several temperatures at a pressure of 0.1 MPa. The PPH is 1h-1. The composition of the effluent is analyzed. The results are shown in Table 1. 1.5% of the isobutanol is converted at 300 ° C into dehydrogenation, dehydration and isomerization procbits of isobutene, and other unidentified products. 4.5% of the isobutanol is converted at 400 ° C. % molar charge 300 ° C 350 ° C 400 ° C 450 ° C Isobutanol 99.35 98.93 98.99 95.51 86.22 2-butanone 0.55 0.61 0.29 0.42 0.45 1-butanol 0.07 0.07 0.07 0.06 0.05 2-butanol 0.02 0.02 0.09 0.13 Isobutyraldehyde 0.1-0.31 0.43 2.59 8.24 Isobutene + 1-butene 0.04 0.18 1.05 3.39 2-butenes 0.02 0.12 0.42 propane 0.01 0.01 0.07 0.6 methane 0.02 0.14 Table 1 - Analysis of the effluent leaving the heating zone The surface ratio A (H2) / A (N2 ) and the ratio H2 output / iC4OH input to highlight the occurrence of the dehydrogenation reaction and the impact of temperature thereon. Description of the Catalytic Test Unit and the Catalysts Used for Examples 2 to 5 Examples 2 to 5 are carried out on a test unit comprising a fixed bed operating in "down flow" mode, that is to say in downflow. The catalyst is loaded in the form of extrudates of length 3 mm in a 316L stainless steel reactor with an internal diameter of 13 mm. The catalyst is then activated at 450 ° C. under 61 / h of air for a period of one hour, after a rise in temperature of 10 ° C./min, the temperature is then lowered to the test temperature under 61 / h. nitrogen to remove air from the system before the charge is injected. The feed is vaporized in the lines heated to 150-180 ° C upstream of the reactor and then injected into the catalytic reactor. Each temperature and pph condition is maintained for a minimum of 24 hours (the minimum duration of a test is 96 hours). The catalyst is regenerated several times in air at 500 ° C. Catalyst A is prepared by comalaxing 80% ferrierite having an Si / Al atomic ratio of 20 and 20% silicic binder. The solid was extruded, dried at 80 ° C for 12h and then calcined in dry air for 2h at 600 ° C. Catalyst A obtained had a SBET surface area of 321 m 2 / g, a mesoporous volume of 0.11 cc / g, macroporous 0.35 cc / g and microporous 0.11 cc / g.
    [0034] EXAMPLE 2 Dehydration of an isobutanol / water filler in 95/5 mass ratio on the catalyst A and on a catalyst B. This example shows the advantage of pre-coking. Catalyst B is prepared by comalaxing 80% ferrierite having an Si / Al atomic ratio of 10 and 20% of silicic binder. The solid was extruded, dried at 80 ° C for 12h and then calcined in dry air for 2h at 600 ° C. The catalyst B obtained has a surface area SBET of 320 m 2 / g, a mesoporous volume of 0.09 cc / g, macroporous of 0.19 cc / g and microporous of 0.11 cc / g.
    [0035] The catalysts were first tested without pre-coking at 0.2 MPa, pph 311-1, and a weighted average temperature (TMP) of 350 ° C. The same catalysts were pre-coked beforehand under isobutanol + water feed at 1.2 MPa, TMP at 350 ° C. for 3 hr for 6 h and then tested at 0.2 MPa, pph 311-1, TMP at 350 ° C. The catalytic performances of the pre-coked or non-coked catalysts were measured. The results are given for the two catalysts A and B pre-coked or not in the table below. The data below was obtained after 6 hours under load. By C3 = propene is meant by C4 = butenes, and C5 + means hydrocarbons having at least 5 carbon atoms. Description Isobutene selectivity Salt yield C3r. C5 salt + C4- salt: Conversion isobutanol% butenes to linear butenes in linear C4 (%) (%) (% wt) "(%) (%) (%) olefins No Catalyst A pre-coked 24.5 72.4 0.05 2.4 96.9 100.0 74.7 pre-coked 18.7 80.6 0.0 0.4 99.5 99.9 81.2 No Catalyst B pre-coked 24.9 50.1 2.03 19.7 75 100 50.1 pre-coked 18.2 80.5 0.05 1.0 98 99.7 80.4 * calculated on a carbon basis, irrespective of the water fraction removed On a pre-coked catalyst under load, the conversion of the alcohol remains total, the selectivity to total butenes increases thanks to a significant lowering of the selectivity in products C5 + and 03 = which it is commonly admitted that they come from the dimerization-cracking of butenes in propylene plus 05. Thus, for a zeolite regardless of its starting Si / Al and its initial selectivity, pre-coking under selected conditions makes it possible to obtain a much more selective catalyst for the transformation of isobutanol to linear butenes s by limiting the formation of products heavier than the 04. This makes it possible to bring the selectivity of a catalyst initially not very selective to that of a more selective catalyst. Example 3 Dehydration of an isobutanol / water filler in 95: 5 mass ratio on catalyst A. This example shows that ferrierite catalyzes a reaction in which linear olefins are a primary product of the reaction. The operating conditions and the catalytic results are given below. The reactor is maintained at an operating pressure of 0.2 MPa. The catalyst is not pre-coked. The data are obtained by averaging the values over 24 hours. pph Salt, Salt C5 + Salt C4 = Alcohol conversion linear butenes in C4 olefins isobutene (° C) h ("70) (° / 0) (`) / 0) (° / 0) (%) 300 21 23.65 2.2 97.4 99.1 75.7 300 12 24.16 2.4 97.3 99.8 75.2 300 5 25.24 2.6 97.0 100.0 74.0 300 3 27.43 3.2 96.3 100.0 71.5 300 1 32.34 5.0 94.1 100.0 65.6 * the other secondary products that make it possible to complete the sum of the selectivities at 100% are mainly isobutyraldehyde, isobutane and propane / propylene.
    [0036] An increase in the pph results in a decrease in isobutene selectivity and an increase in the selectivity to linear butenes. This indicates that isobutene is not a primary product of the reaction, which would undergo skeletal isomerization to form linear butenes. On the contrary, it is the linear olefins which are the primary products of the reaction. The catalyst according to the invention makes it possible to obtain a proportion of linear butenes in the total butenes which is much greater than the expected value at thermodynamic equilibrium which is between 45 and 55% and a selectivity for butenes of greater than 96%. except for the pph 111-1. The dehydration of isobutanol is complete whatever the operating conditions, except for the highest pph.
    [0037] EXAMPLE 4 Dehydration of a 1-butanol / water filler in 95/5 mass ratio and of an isobutanol / water filler in 95/5 mass ratio on catalyst A. This example shows that the catalyst according to the invention does not promote the skeletal isomerization of linear butenes.
    [0038] An experiment was carried out using a 1-butanol feed diluted with 5% water or with an isobutanol feed diluted with 5% water which is reacted in the presence of the catalyst A under 0.2 MPa operating pressure. .
    [0039] Catalyst A is pre-coked with the feed at 1.2 MPa, 350 ° C, pph 3h1 for 6h. It is therefore used in accordance with the invention. TMP pph (h'1) Isobutene salt C5 + salt (%) C4 salt = conversion Butenes (° C) (%) (%) linear alcohols in (%) C4 olefins Charge 1 butanol / water 350 6 12.6 2.6 97.0 99.9 84.1 375 6 15.6 2.2 97.3 100.0 81.7 375 12 10.3 1.9 97.9 99.9 87.6 350 3 7.9 1.2 98.6 100.0 90.6 Isobutanol load / water 350 6 19.8 0.6 99.1 99.1 80.1 375 6 20.9 0.4 99.4 99.5 78.9 375 12 20.4 0.3 99.5 99.0 79.5 350 3 18.7 The catalyst used according to the invention makes it possible to obtain a proportion of linear butenes in the total butenes which is much greater than the expected value at the thermodynamic equilibrium which is between 45 and 55%, as well as a selectivity in terms of butenes greater than 97%. The dehydration of isobutanol is complete whatever the operating conditions. The selectivity in linear butenes is almost identical whether one starts from the butanol or isobutanol feedstock. The catalyst does not promote the skeletal isomerization of linear butenes to isobutene, even by lengthening the contact time (lowering the pph). This indicates that the catalyst used according to the ferrierite-based invention has a particular shape selectivity favoring the formation of linear butenes and not isobutene from isobutanol or 1-butanol under the chosen operating conditions. Example 5 (Comparative) This example shows the interest of the FER structural type zeolites having 8 and 10MR channels on zeolites of structural type TON and MTT having only 10MR channels. Four zeolites containing 10MR channels of FER structural type (two-dimensional ferrierite 8-10MR), TON (10MR monodimensional Nu-10) and MIT (10MR one-dimensional ZSM-23) were compared. These zeolites were tested in the form of a powder with a particle size of 400-500 μm at a TMP of 350 ° C. and at a pH of 3 h -1, 0.2 MPa.
    [0040] The catalysts are pre-coked with the feed at 1.2 MPa, 350 ° C, pph 3111 for 6 hours. Catalysts A and B are therefore used in accordance with the invention. Ref pph Salt C3 = Salt C5 + Salt C4 = Conversion% butenes Catalyst (til) (%) (%) (%) isobutanol. . (c% o) linear in C4 olefins B 3 0.05 1.0 98 99.7 80.4 A 3 0.0 0.4 99.5 99.9 81.2 Nu-10 Si / AI 3 1.1 14.8 82.7 100.0 57.8 30 ZSM-23 3 8.2 59.5 16.5 99.3 44.5 Si / AI 22 Only ferrierite makes it possible to attain proportions of linear butenes in the C4 olefin section greater than the equilibrium thermodynamic composition, as well as a high butene selectivity. On all zeolites, the conversion of alcohol is total. ZSM-23 zeolites on the other hand has a very degraded selectivity and promote the formation of C5 + and C3 =. Zeolite Nu-10 is slightly more selective but still strongly favors the formation of by-products. 10
    权利要求:
    Claims (6)
    [0001]
    REVENDICATIONS1. A process for the isomerizing dehydration of a feedstock comprising from 40 to 100% by weight of primary alcohol substituted in the 2-position by an alkyl group comprising at least the following stages: a) Pressurization of said feedstock and then preheating of the compressed feedstock by exchange heat with the dewatering effluent from step c) in a heat exchanger to produce a preheated charge; b) vaporizing said preheated charge by mixing with the diluent effluent from step f), the ratio of mass flow rates diluent effluent on preheated charge being between 5/95 and 60/40; c) Dehydration of the effluent from step b) in at least one dehydration reactor operating in the gas phase at a weighted average temperature of between 250 and 375 ° C., at a pressure of between 0.2 MPa and 1 MPa and at a PPH between 1 and 1811-1, in the presence of a catalyst comprising a zeolite comprising at least one series of channels whose opening is defined by an 8-atom oxygen ring (8MR), said catalyst being previously coked in-situ or ex-situ, so as to produce a dewatering effluent; d) cooling said dehydration effluent by at least three successive heat exchanges with at least the water effluent from step e), then said compressed charge of step a), then a cold utility so as to produce a cooled effluent; e) decanting said cooled effluent into an aqueous phase and an organic phase, a portion of said aqueous phase being purged for treatment outside said dewatering process and the other part, forming the water effluent being recycled via the step f); f) recycling of the effluent water from step e) and at least partial vaporization by heat exchange in a heat exchanger with the dehydration effluent from step c), separation of the liquid fraction possibly present then compressing and superheating the vapor fraction to form a diluent effluent, said diluent effluent being recycled to step b); g) Separation of the organic phase extracted from step e) in at least one distillation column so as to produce an effluent alkenes and a heavy hydrocarbon effluent.
    [0002]
    2. A process according to claim 1 wherein said catalyst of said step c) is pre-coked with a feedstock comprising primary alcohol substituted in the 2-position by an alkyl group at a partial pressure to said primary alcohol strictly greater than that of the charge of said process according to claim 1, at a weighted average temperature strictly greater than the operating temperature and between 250 and 450 ° C, a pressure of between 0.1 and 3 MPa, a PPH between 0.1 and 10 h -1 and a duration between 1 and 30 h.
    [0003]
    3. A process according to claim 1 wherein said catalyst of said step c) is precocarded with a feedstock comprising primary alcohol substituted in the 2-position by an alkyl group at a partial pressure to said primary alcohol strictly greater than that of the charge of said process according to claim 1, at a weighted average temperature strictly below the operating temperature and between 200 and 350 ° C, a pressure strictly greater than the operating pressure and between 0.1 and 3 MPa, a PPH included between 0.1 and 10 h-1 and a duration of between 1 and 30 h.
    [0004]
    4. A process according to claim 1 wherein said catalyst of said step c) is pre-coked with a primary alcohol substituted in the 2-position by a pure alkyl group, at a weighted average temperature strictly above the operating temperature and between 250 and 450 ° C., a pressure of between 0.1 and 3 MPa, a PPH of between 0.1 and 10 h -1 and a duration of between 1 and 30 h.
    [0005]
    The process according to claim 1 wherein said catalyst of said step c) is precocarded with a primary alcohol substituted in the 2-position by a pure alkyl group, at a weighted average temperature strictly below the operating temperature and between 200 and 350 ° C, a pressure strictly greater than the operating pressure and between 0.1 and 3 MPa, a PPH between 0.1 and 10 h -1 and a duration between 1 and 30 h.
    [0006]
    6. The process as claimed in claim 1, wherein said catalyst of said step c) is precoked with the heavy hydrocarbon effluent resulting from the separation step g), at a weighted average temperature strictly greater than the operating temperature and between 250 and 450 ° C., a pressure of between 0.1 and 3 MPa, a PPH of between 0.1 and 10 h -1 and a duration of between 1 and 30 h. The process according to claim 1, wherein said catalyst of said step c) is precooked with the heavy hydrocarbon effluent from the separation step g), at a weighted average temperature strictly below the operating temperature and between 200 and 350 ° C, a pressure strictly greater than the operating pressure and between 0.1 and 3 MPa, a PPH between 0.1 and 1011-1 and a duration between 1 and 30 h. Process according to one of claims 1 to 7 wherein said zeolite included in the catalyst used in said step c) is selected from zeolites of structural type FER and MFS, taken alone or in mixture. Process according to one of claims 1 to 7 wherein said zeolite included in the catalyst used in said step c) is selected from ferrierite, NU-23, FU-9, ISI-6, ZSM-35 and ZSM zeolites. -57, taken alone or in a mixture. Process according to one of Claims 1 to 9, in which a single oven is used for heating the preheated feed mixture / diluent effluent during step b) and for the superheating of the compressed vapor fraction, the latter being overheated in the hot part of the oven, while said mixture is put in temperature in the cold part.
    类似技术:
    公开号 | 公开日 | 专利标题
    EP3197850B1|2018-11-21|Method for isomerizing dehydration of a primary alcohol substituted in position 2 by an alkyl group on a catalyst comprising an iron zeolite
    EP1862528B1|2011-10-26|Process for transforming ethanol in a base for diesel fuel
    KR101217957B1|2013-01-02|Dehydration of alcohols on crystalline silicates
    DK2547638T3|2016-12-12|SIMULTANEOUS dehydration and skeletal isobutanol ON ACID CATALYSTS
    CA2797748C|2018-05-08|Process for dehydration and isomerization of c4 alcohols using an amorphous solid with suitable porosity
    FR2998568A1|2014-05-30|PROCESS FOR THE DEHYDRATION OF LOW CONSUMPTION ETHYLENE ETHANOL
    CA2931704A1|2015-06-04|Method for dehydrating a mixture containing ethanol and isopropanol
    EP3240769B1|2020-05-06|Process for preparing olefins by dehydrating alcohols with less side effects comprising addition of sulfur containing compounds
    CA2931705C|2021-09-21|Method for dehydrating a mixture containing ethanol and n-propanol
    EP3538502A1|2019-09-18|Method for the isomerisation dehydration of a non-linear primary alcohol feedstock in the presence of water injection and a catalyst comprising an fer or mfs zeolite
    WO2018087032A1|2018-05-17|Method for isomerising dehydration of non-linear primary monoalcohols on an alkali-doped zeolitic catalyst
    FR3071250B1|2019-09-13|PROCESS FOR THE DEHYDRATION OF ALCOHOLS INTO OLEFINS COMPRISING THE RECYCLING OF ALCOHOLS
    FR3068692B1|2019-08-16|METHOD FOR DEHYDRATING ALCOHOLS INTO OLEFINS COMPRISING A CATALYST SELECTIVE STEP
    WO2019206591A1|2019-10-31|Method for isomerising dehydration of a non-linear primary monoalcohol on a quadrilobed iron zeolite catalyst
    BR112017005670B1|2021-10-26|ISOMERIZING DEHYDRATION PROCESS OF PRIMARY ALCOHOL CHARGE, REPLACED IN POSITION 2 BY AN ALKYL GROUP ON A CATALYST, INCLUDING IRON-TYPE ZEOLITE
    FR2973394A1|2012-10-05|METHOD OF OLIGOMERIZING AN OLEFINIC HYDROCARBON LOAD USING A CATALYST COMPRISING A STRUCTURAL TYPE ZIF FAMILY MATERIAL
    同族专利:
    公开号 | 公开日
    BR112017005670A2|2017-12-12|
    US10099969B2|2018-10-16|
    EP3197850A1|2017-08-02|
    FR3026406B1|2016-12-09|
    RU2694062C2|2019-07-09|
    US20170341996A1|2017-11-30|
    CA2960785A1|2016-03-31|
    RU2017114374A|2018-10-26|
    CN107001178B|2020-06-05|
    RU2017114374A3|2019-02-25|
    EP3197850B1|2018-11-21|
    KR20170063853A|2017-06-08|
    CN107001178A|2017-08-01|
    JP2017534587A|2017-11-24|
    JP6778677B2|2020-11-04|
    WO2016046242A1|2016-03-31|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2011113834A1|2010-03-15|2011-09-22|Total Petrochemicals Research Feluy|Simultaneous dehydration and skeletal isomerisation of isobutanol on acid catalysts|
    WO2013011208A1|2011-07-21|2013-01-24|IFP Energies Nouvelles|Low-energy consumption method for dehydrating ethanol into ethylene|FR3058413A1|2016-11-08|2018-05-11|IFP Energies Nouvelles|METHOD FOR ISOMERIZING DEHYDRATION OF A NON-LINEAR PRIMARY MONOALCOOL CHARGE ON A CATALYST COMPRISING IRON ZEOLITHE AND ALKALINE|
    FR3058414A1|2016-11-08|2018-05-11|IFP Energies Nouvelles|METHOD FOR ISOMERIZING DEHYDRATION OF NON-LINEAR PRIMARY ALCOHOL ON A CATALYST COMPRISING IRON TYPE ZEOLITHE AND ALUMINUM BINDER|
    US10604456B2|2017-09-19|2020-03-31|Total Research & Technology Feluy|Method for dehydrating alcohols into olefins comprising the recycling of alcohols|
    WO2020126374A1|2018-12-20|2020-06-25|IFP Energies Nouvelles|Method for treating an alcohol feedstock for the production of olefins|BRPI0907446B1|2008-02-07|2020-09-29|Total Petrochemicals Research Feluy|ALCOHOL DEHYDRATION PROCESS|
    EP2585422B1|2010-06-23|2018-01-10|Total Research & Technology Feluy|Dehydration of alcohols on poisoned acidic catalysts|
    FR3001968B1|2013-02-12|2015-02-27|IFP Energies Nouvelles|PROCESS FOR PRODUCING ETHYLENE OXIDE FROM A THERMO-MECHANICALLY INTEGRATED ETHANOL FLOW|
    FR3001969B1|2013-02-12|2015-08-21|IFP Energies Nouvelles|PROCESS FOR PRODUCING ETHYLENE OXIDE FROM A THERMALLY INTEGRATED ETHANOL FLOW|
    US10472300B2|2014-12-31|2019-11-12|Total Research & Technology Feluy|Process for preparing olefins by dehydrating alcohols with less side effects comprising addition of sulfur containing compounds|FR3058415B1|2016-11-08|2018-12-07|IFP Energies Nouvelles|METHOD FOR ISOMERIZING DEHYDRATION OF NON-LINEAR PRIMARY ALCOHOL LOAD IN THE PRESENCE OF WATER INJECTION AND A CATALYST COMPRISING IRON TYPE ZEOLITHE OR MFS|
    FR3068692B1|2017-07-10|2019-08-16|IFP Energies Nouvelles|METHOD FOR DEHYDRATING ALCOHOLS INTO OLEFINS COMPRISING A CATALYST SELECTIVE STEP|
    CN108358740A|2018-02-09|2018-08-03|安徽海德化工科技有限公司|A kind of auxiliary agent preparing isobutene for isobutyl dehydration of alcohols|
    FR3080546A1|2018-04-25|2019-11-01|IFP Energies Nouvelles|PROCESS FOR ISOMERIZING DEHYDRATION OF NON-LINEAR PRIMARY MONOALCOOL ON A FERRY-TYPE QUADRILOBE ZEOLITHIC CATALYST|
    法律状态:
    2015-09-15| PLFP| Fee payment|Year of fee payment: 2 |
    2016-04-01| PLSC| Search report ready|Effective date: 20160401 |
    2016-09-22| PLFP| Fee payment|Year of fee payment: 3 |
    2017-09-14| PLFP| Fee payment|Year of fee payment: 4 |
    2018-09-17| PLFP| Fee payment|Year of fee payment: 5 |
    2019-09-25| PLFP| Fee payment|Year of fee payment: 6 |
    2020-09-28| PLFP| Fee payment|Year of fee payment: 7 |
    2021-09-27| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1459113A|FR3026406B1|2014-09-26|2014-09-26|METHOD FOR ISOMERIZING DEHYDRATION OF A PRIMARY ALCOHOL LOAD SUBSTITUTED IN POSITION 2 BY AN ALKYL GROUP ON A CATALYST COMPRISING AN IRON TYPE ZEOLITHE|FR1459113A| FR3026406B1|2014-09-26|2014-09-26|METHOD FOR ISOMERIZING DEHYDRATION OF A PRIMARY ALCOHOL LOAD SUBSTITUTED IN POSITION 2 BY AN ALKYL GROUP ON A CATALYST COMPRISING AN IRON TYPE ZEOLITHE|
    RU2017114374A| RU2694062C2|2014-09-26|2015-09-22|Method for dehydration isomerisation of source mixture of primary alcohol substituted in position 2 with alkyl group, on catalyst containing zeolite of fer type|
    KR1020177011472A| KR20170063853A|2014-09-26|2015-09-22|Method for isomerizing dehydration of a primary alcohol substituted in position 2 by an alkyl group on a catalyst comprising an iron zeolite|
    PCT/EP2015/071802| WO2016046242A1|2014-09-26|2015-09-22|Method for isomerizing dehydration of a primary alcohol substituted in position 2 by an alkyl group on a catalyst comprising an iron zeolite|
    JP2017516404A| JP6778677B2|2014-09-26|2015-09-22|A method for isomerizing and dehydrating a primary alcohol feedstock substituted at the 2-position with an alkyl group on a catalyst containing iron-type zeolite.|
    EP15770500.5A| EP3197850B1|2014-09-26|2015-09-22|Method for isomerizing dehydration of a primary alcohol substituted in position 2 by an alkyl group on a catalyst comprising an iron zeolite|
    US15/514,280| US10099969B2|2014-09-26|2015-09-22|Process for the isomerizing dehydration of a primary alcohol feedstock substituted in position 2 by an alkyl group on a catalyst comprising an iron-type zeolite|
    CA2960785A| CA2960785A1|2014-09-26|2015-09-22|Method for isomerizing dehydration of a primary alcohol substituted in position 2 by an alkyl group on a catalyst comprising an iron zeolite|
    CN201580051717.1A| CN107001178B|2014-09-26|2015-09-22|Method for isomerizing and dehydrating a primary alcohol feedstock substituted in the 2-position by an alkyl group, based on a catalyst comprising an iron-type zeolite|
    BR112017005670-4A| BR112017005670B1|2014-09-26|2015-09-22|ISOMERIZING DEHYDRATION PROCESS OF PRIMARY ALCOHOL CHARGE, REPLACED IN POSITION 2 BY AN ALKYL GROUP ON A CATALYST, INCLUDING IRON-TYPE ZEOLITE|
    [返回顶部]