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    • 专利摘要:
    the invention relates to catalysts for the heterogeneous hydrogenation of aldehydes in the oxo process. the problem addressed by the present invention is to develop a catalyst containing neither chromium nor nickel. in addition, the economically viable hydrogenation of mixtures of aldehydes from industrial oxo processes on an industrial scale should be allowed. for this purpose, the catalyst should not be dependent on expensive precious metals such as ru, pd or pt. this problem was solved by omitting chromium and nickel in the preparation of a conventional cu/ni/cr system, so that a catalyst in which only copper occurs as the active hydrogenation component in its support material, and not chromium or nickel, is obtained. what is surprising is that a working catalyst for the intended purpose would by no means be possible even though two of the three hydrogenation active metals are omitted. however, this requires conditions as needed that the support material used is silicon dioxide and that the Cu and Sodium 2 content in the active catalyst is precisely defined within very tight limits.
    公开号:BR102017023944B1
    申请号:R102017023944-6
    申请日:2017-11-07
    公开日:2022-01-04
    发明作者:Florian Klasovsky；Robert Franke；Frank Geilen；Andreas Jess；Wolfgang Korth；Thomas Quandt；Arne Reinsdorf
    申请人:Evonik Operations Gmbh；
    IPC主号:
    专利说明:

    [0001] The invention relates to a process for preparing alcohols by hydrogenation of aldehydes, in which a feed mixture comprising at least one aldehyde and at least one attached component is brought into contact with a heterogeneous catalyst in the presence of hydrogen, producing a mixture of products comprising at least the alcohol corresponding to the hydrogenated aldehyde and at least one by-product, wherein the catalyst comprises a support material and copper applied thereto.
    [0002] The invention further relates to the preparation of the corresponding catalyst and the corresponding precursor, the optional activation of the precursor and the use of the active catalyst in the process.
    [0003] The elimination of hydrogen (dehydrogenation) from an alcohol gives rise to an aldehyde. On the other hand, alcohols can be prepared from aldehydes by hydrogenation (addition of hydrogen).
    [0004] Hydrogenation is, in general, a reaction carried out very frequently in the industry. Another specific reaction practiced on an industrial scale is the hydrogenation of aldehydes, namely in the preparation of the so-called Oxo process alcohols.
    [0005] The alcohols of the Oxo process are alcohols that are prepared by means of hydroformylation (Oxo reaction). In hydroformylation, an olefin (alkene) is reacted with a synthesis gas (a mixture of carbon monoxide and hydrogen) to produce an aldehyde. Subsequent hydrogenation yields the actual Oxo process alcohol. The alcohols from the Oxo process serve as intermediates for the production of surfactants and/or plasticizers for plastics. Several million metric tons of oxo alcohols are produced globally each year.
    [0006] Since the hydrogenation of the aldehydes obtained by hydroformylation is a necessary step in the preparation of alcohols in the oxo process, the present invention concerns a process of relevance on an industrial scale.
    [0007] In industrial practice, the aldehydes of the oxo process are generally hydrogenated in the liquid phase over heterogeneous fixed bed catalysts. Due to the large production volumes, the catalyst is of crucial importance to the process, as it determines the reaction rate and also the selectivity of the hydrogenation. The selection of a suitable catalyst is not trivial, since the aldehydes to be hydrogenated never occur in pure form, but as a mixture of structurally isomeric aldehydes that is always accompanied by a large number of problematic components that accompany it that first of all , cause unwanted side reactions in the hydrogenation and, secondly, damage the hydrogenation catalyst. Since the composition of the feed mixture comprising the aldehydes to be hydrogenated is determined by the upstream hydroformylation, the hydrogenation catalyst has to be adjusted exactly with respect to the specific hydroformylation.
    [0008] For the hydrogenation of aldehydes in the oxo process, it was found that useful catalysts are those that comprise a support material to which copper, chromium and nickel have been applied as active components.
    [0009] A corresponding catalyst is disclosed in DE19842370A1. It comprises copper and nickel each in a concentration range of 0.3% to 15% by weight and chromium in a weight ratio of 0.05% by weight to 3.5% by weight. The support material used is porous silicon dioxide or aluminum oxide.
    [0010] US 4,677,234 describes a process for the preparation of ethylene glycol in the presence of a supported copper catalyst.
    [0011] Although these catalysts have proven useful in the industrially practiced oxo process hydrogenation of aldehydes, there is still a need for an alternative. The reason for this is the chromium content of these catalysts.
    [0012] According to Annex XIV of the REACH directive, substances containing chromium, such as the catalysts described above, must only be used in the European Union after authorization by the Commission. The granting of authorization is associated with great complexity and high costs; moreover, the granting of authorization cannot be expected a priori. In addition, the application procedure must be repeated every five years.
    [0013] The reason for these strict conditions is the indisputable carcinogenicity of the chromium used. This is relevant, firstly, when the hydrogenation catalyst has to be discarded after deactivation and, secondly, when it is freshly produced by impregnation with alkali metal chromates or alkali metal dichromates.
    [0014] The chromium problem was solved with the catalyst described in EP3037400A1, which is virtually chromium free. However, there is still a need for improvement in this system, as nickel and nickel compounds used in the production of the chromium-free catalyst are equally carcinogenic.
    [0015] In this regard, the problem addressed is to specify a suitable catalyst system for industrial hydrogenation of aldehydes, which is chromium-free and nickel-free.
    [0016] EP2488478B1 describes a two-stage hydrogenation of C10 aldehydes, wherein a catalyst that is free of copper, chromium and nickel but does not contain ruthenium is used in the second hydrogenation stage. Ruthenium (Ru) is comparatively expensive and, for that reason, this process is not always economically viable on an industrial scale. Furthermore, the process is not nickel-free either, as a nickel-containing catalyst must be used in the first stage to obtain acceptable hydrogenation results.
    [0017] WO95/32171A1 describes various hydrogenation catalysts comprising copper and silicon dioxide, in the presence or absence of other elements, including chromium. The specific chromium-free variants are notable for very high levels of CuO (well above 20% by weight). The raw material costs for these copper-rich catalysts are quite high.
    [0018] US 3,677,969 describes an organometallic hydrogenation catalyst. A disadvantage of this system is that its production is comparatively expensive, as it involves additional sulfidation and has to be heat treated at very high temperatures (400°F to 1000°F [204.4°C to 537.8° Ç]). In addition, an optional chromium and nickel content is recommended.
    [0019] In view of the above, it has not yet been possible to find a chromium and nickel-free catalyst suitable for the hydrogenation of hydroformylation mixtures on an industrial scale.
    [0020] In light of this prior art, the problem addressed by the invention is the development of a catalyst that contains neither chromium nor nickel. Other substances known to be carcinogens are also absent. Furthermore, the economically viable hydrogenation of aldehyde mixtures from industrial oxo processes on an industrial scale should be allowed. For this purpose, the catalyst should not rely on expensive precious metals such as Ru, Pd or Pt. The copper content of the catalyst should be kept to a minimum to reduce raw material costs. Also considering the production costs of the catalyst, its preparation can be carried out at low temperatures and the catalyst does not have to be sulfated.
    [0021] This problem was solved by omitting chromium and nickel in the preparation of a conventional Cu/Ni/Cr system, such that a catalyst in which only copper occurs as an active hydrogenation component in its support material, and not chromium or nickel, is obtained. What is surprising is that a working catalyst for the intended purpose would by no means be possible even though two of the three hydrogenation active metals are omitted. However, this requires conditions as needed that the support material used is silicon dioxide and that the Cu and SiO2 content in the active catalyst is precisely defined within very tight limits. The reason why SiO2 is particularly suitable as a support is probably because it contains very few acidic Bronsted sites or basic Bronsted sites, which accelerate the formation of by-products.
    [0022] The invention therefore provides a process for preparing alcohols by hydrogenation of aldehydes, wherein a feed mixture comprising at least one aldehyde and at least one attached component is contacted with a heterogeneous catalyst in the presence of hydrogen, producing a mixture of products comprising at least the alcohol corresponding to the hydrogenated aldehyde and at least one by-product, wherein the catalyst comprises a support material and copper applied thereto, wherein the support material is silicon dioxide, and wherein the catalyst in the activated form it has the following composition that adds up to 100% by weight: silicon dioxide: from 86% by weight to 90% by weight; copper: from 10% by weight to 14% by weight; nickel: from 0 ppm by weight to 50 ppm by weight; chromium: from 0 ppm by weight to 50 ppm by weight; aluminum oxide: from 0 ppm by weight to 1000 ppm by weight; other substances: from 0 ppm by weight to 1% by weight.
    [0023] "Other substances" that are cited in this context are always understood to mean chemical compounds or elements thereof that are present in the catalyst, but are explicitly mentioned in the enumeration. In the case of the above composition, "other substances" therefore means a collective term for all components except SiO2, Cu, Ni, Cr, Al2O3.
    [0024] Examples of "other substances" can be carbonates, hydroxides or simply interspersed water. Precious metals detectable in traces, such as Pt, Ru or Pd, are also covered by the term "other substances". For reasons of cost, in accordance with the invention, the deliberate addition of precious metals in the preparation of the catalyst is dispensed with. However, it cannot be excluded that traces of Pt, Ru or Pd can be detected in the prepared catalyst with the currently available analysis options. However, these would then be classified, as well as nickel and chromium residues, as unintentional contamination (by materials from appliances or jewelry worn by personnel). Ideally, the content of "other substances" is zero.
    [0025] A catalyst particularly suitable for the task of hydrogenation has been found to be one which, in activated form, has the following composition adding up to 100% by weight: silicon dioxide: from 87% by weight to 89% by weight; copper: from 11% by weight to 13% by weight;nickel: from 0 ppm by weight to 50 ppm by weight; chromium: from 0 ppm by weight to 50 ppm in hydroxides: weight; from 0 ppm by weight to 100 ppm in ruthenium: weight; from 0 ppm by weight to 50 ppm empalladium: weight; from 0 ppm by weight to 50 ppm in platinum: weight; from 0 ppm by weight to 50 ppm in aluminum oxide: weight; from 0 ppm by weight to 100 ppm in water: weight; from 0 ppm by weight to 100 ppm in carbonates: weight; from 0 ppm by weight to 100 ppm in other substances: weight from 0 ppm by weight to 0.5% by weight
    [0026] The weight support material used in accordance with the invention is silicon dioxide. It is possible to use any of fumed silica (SiO 2 ) or precipitated silica as a support material. Regardless of SiO2 synthesis, the catalyst is always used in solid form with a major or minor crystalline component in the support material. The catalyst in hydrogenation is therefore a heterogeneous catalyst as it is not dissolved in the reaction mixture but is present in another phase.
    [0027] Preference is given to the use of a support material having a specific pore volume between 0.8 cm3/g and 1.2 cm3/g, determined by the method of immersion in cyclohexane, and having a specific surface area ( surface area BET) between 130 m2/g and 170 m2/g, determined by the ISO 9277 method. Such a material is available as Aerolyst® 3041 from Evonik Resource Efficiency GmbH. It is based on smoked silicon dioxide.
    [0028] Considering the high intensity of the process, the hydrogenation is carried out at a pressure between 15 x 105 Pa and 25 x 105 Pa and at a temperature between 140 °C and 180 °C. Pressure and temperature must be chosen here so that the feed mixture and the product mixture are in a liquid phase.
    [0029] Preferably, the hydrogen is supplied in a superstoichiometric amount so as to ensure substantially complete hydrogenation. However, the hydrogen concentration must be adjusted such that at least some of the hydrogen is dissolved in the liquid phase. Some of the hydrogens may also be in the gas phase and therefore may form bubbles in the reaction mixture. In this case, the reaction is carried out in what is called a "drip bed" operation.
    [0030] The catalyst system according to the invention was developed for the hydrogenation of feed mixtures that originate from a hydroformylation and, as such, contain a plurality of aldehydes with the same number n of carbon atoms , and corresponding alcohols and high-boilers, where n is a natural number between three and eighteen.
    [0031] This has been particularly optimized for the hydrogenation of C9 aldehyde mixtures having the following specification which adds up to 100% by weight: total fraction of aldehydes having nine carbon atoms: from 25% by weight to 75% by weight; total alcohols having nine carbon atoms: from 10% by weight to 55% by weight;total fraction of acetals: from 0.5% by weight to 5.5% by weight;total fraction of additional hydrocarbons: from 0% by weight weight to 40% by weight; water: from 0% by weight to 3% by weight.
    [0032] This feed mixture is typically formed in the cobalt-catalyzed hydroformylation of C8 olefins.
    [0033] This is particularly suitable for the hydrogenation of C9 aldehyde mixtures having the following specification which adds up to 100% by weight:total fraction of aldehydes having nine carbon atoms: from 15% by weight to 65% by weight;total fraction of alcohols having nine carbon atoms: from 20% by weight to 65% by weight;total fraction of acetals: from 0.5% by weight to 5.5% by weight;total fraction of additional hydrocarbons: from 0% by weight to 40% by weight; water: from 0% by weight to 1% by weight.
    [0034] This feed mixture is typically formed in the rhodium-catalyzed hydroformylation of C8 olefins.
    [0035] The chemical and physical properties of a catalyst and, consequently, its suitability for the task of hydrogenation are determined to a crucial degree by its preparation.
    [0036] Therefore, the preparation of the catalyst is an essential aspect of the invention. This is achieved according to the claims essentially by the following steps: a) providing a support material containing at least 99% by weight of silicon dioxide; b) providing copper (II) hydroxycarbonate, ammonium hydrogen carbonate and/or ammonia, ammonia and water; c) prepare a solution of copper (II) hydroxycarbonate, ammonium hydrogen carbonate and/or ammonia carbonate, ammonia and water, in such a way that the solution has a copper content between 10% by weight and 15% by weight, where the proportion of chromium in the solution is between 0 ppm by weight and 50 ppm by weight, and where the proportion of nickel in the solution is between 0 ppm by weight and 50 ppm by weight; d) impregnating the material with support with the solution;e) drying the impregnated support material at temperatures between 50°C and 150°C;f) calcining the dry and impregnated support material at temperatures between 300°C and 600°C to obtain a precursor;g ) activate the precursor by reduction with hydrogen to obtain the active catalyst.
    [0037] More specifically, steps a) to f) refer to the preparation of the precursor, and step g) to the preparation of the actual catalyst from the precursor.
    [0038] This distinction is important, as activation is often performed at a different location than the precursor preparation. Activation is usually carried out in situ, that is, at the place where the hydrogenation is carried out later, more specifically, in the reactor. In this case, the catalytically inactive precursor is installed in the hydrogenation reactor, then brought into contact with hydrogen for the purpose of reduction and thus activated. This has the advantage that copper oxides are not formed again by contact with atmospheric oxygen.
    [0039] Alternatively, the catalyst is activated ex situ, that is, reduced outside the hydrogenation reactor and actively supplied and installed. However, this must be carried out under a protective atmosphere, which is correspondingly expensive and inconvenient.
    [0040] Copper is required in the catalyst as the active metal for hydrogenation. Considering the catalyst costs, however, the copper content must be reduced to the minimum necessary. For this reason, it is advisable in preparing the solution in step c) to form the solution in such a way that the copper content is between 10.5% by weight and 11.5% by weight. It has been found that an optimal solution is one that has a copper content of 11% by weight.
    [0041] The impregnation of the support material with the solution can be carried out in different ways. The solution is to penetrate and fill the pores very substantially. The following impregnation procedure was found to be useful: The support is introduced into a rotating drum. The solution is sprayed onto the support and fills the pores. During the spraying phase, hot air can be passed through the rotating bed of the impregnated support. Warm air is generally air at a temperature in the region of ambient temperature.
    [0042] The impregnation in step d) and at least some of the drying of the support material impregnated in step e) is suitably carried out in accordance with the invention in a drum, in such a way that the support material is introduced into the drum for impregnation, that the drum is rotated, that the solution is sprayed into the drum, and that, during the drying phase, a stream of air at a temperature between 50 °C and 100 °C, preferably at a temperature of about 80 °C, is passed through the drum. Steps d) and e) are thus carried out with little manual work on the apparatus (the drum). This reduces production costs.
    [0043] In another embodiment of the present invention, it is also possible to remove the impregnated support material from the drum before drying is complete and dry it to completion in a dryer in an air stream within the temperature range of 100°C to 150°C. Transfer from the drum to the dryer is an additional process step, but can lead to low water content.
    [0044] The handling of the catalyst in its preparation and installation in the reactor is significantly facilitated when the support material provided comprises cylindrical extrudates with a diameter between 1 mm and 2 mm. The catalyst can then be handled as a bulk material. In liquid phase hydrogenation, cylindrical extrudates are favorable in terms of flow dynamics. Evonik's Aerolyst® 3014 is available in this preferred presentation form. As an alternative form of catalyst, it is also possible to use spheres with a diameter ranging between 1 mm and 2 mm.
    [0045] Prior to activation, the precursor preferably has the following weight: the following composition which adds up to 100% of silicon dioxide: from 84% by weight to 86% by weight; copper oxide: from 14% by weight to 16% by weight weight; nickel: from 0 ppm by weight to 50 ppm by weight; chromium: from 0 ppm by weight to 50 ppm by weight; aluminum oxide: from 0 ppm by weight to 1000 ppm by weight; other substances: from 0 ppm by weight to 1% by weight.
    [0046] It is important that the copper in this precursor is still in the oxidizing form. Due to the bound oxygen, there is a difference in the total weight of the active catalyst precursor, and for that reason there is also a difference in the relative amounts indicated.
    [0047] On activation, CuO is reduced with H2 to Cu. The water formed at the same time is withdrawn. As the copper catalyst is now metallic, the catalyst is now an active hydrogenation catalyst. On completion of activation, oxygen has been removed and therefore the active catalyst has the composition of the invention. Preferably, the catalyst is reduced in situ with liquid hydrogen. Alternatively, the catalyst can be efficiently activated in the gas phase.
    [0048] The invention also provides the use of the catalysts prepared in this way in processes for the preparation of alcohols by hydrogenation of aldehydes according to the present invention.
    [0049] The described preparation of the precursor, its activation and the use of the active catalyst in the hydrogenation of aldehydes together solve the indicated problem.
    [0050] The invention therefore also provides a combined process for preparing a precursor, activating the precursor to produce an active catalyst and using the catalyst for the hydrogenation of aldehydes. The process for the hydrogenation of aldehydes according to the invention thus comprises the following steps: a) providing a support material containing at least 99% by weight of silicon dioxide; b) providing copper (II) hydroxycarbonate, hydrogen carbonate of ammonia and/or ammonia carbonate, ammonia and water; c) preparing a solution comprising copper(II) hydroxycarbonate, ammonium hydrogen carbonate and/or ammonia carbonate, ammonia and water, such that the solution has a copper between 10% by weight and 15% by weight, where the proportion of chromium in the solution is between 0 ppm by weight and 50 ppm by weight, and where the proportion of nickel in the solution is between 0 ppm by weight and 50 ppm by weight ;d) impregnating the support material with the solution;e) drying the impregnated support material at temperatures between 50°C and 150°C; f) calcining the dry impregnated support material at temperatures between 300°C and 600°C to obtain a precursor especially having the following composition which adds up to 100% by weight:silicon dioxide: from 84% by weight to 86% by weight; oxide copper: from 14% by weight to 16% by weight;nickel: from 0 ppm by weight to 50 ppm by weight;chromium: from 0 ppm by weight to 50 ppm by weight;aluminium oxide: from 0 ppm by weight to 1000 ppm weight; other substances: from 0 ppm by weight to 1 % by weight. g) transfer the precursor to a reactor; h) activate the precursor in the reactor by means of reduction with hydrogen to obtain the active catalyst especially having the following composition which adds up to 100 by weight: silicon dioxide: from 86% by weight to 90% by weight; copper: from 10% by weight to 14% by weight; nickel: from 0% by weight; ppm by weight to 50 ppm in chromium: from 0 ppm by weight to 50 ppm by weight; aluminum oxide: from 0 ppm by weight to 1000 ppm by weight; other substances: from 0 ppm by weight to 1% by weight. i) contacting the active catalyst in the reactor with a feed mixture comprising at least one aldehyde and at least one attached component, in the presence of hydrogen, especially producing a mixture of products comprising at least the alcohol corresponding to the hydrogenated aldehyde and at least one by-product, wherein the impregnation and at least some part of the drying is carried out in a drum , in such a way that the support material is introduced into the drum for impregnation, that the drum is rotated, that the solution is sprayed into the drum, and that, during the drying phase, an air stream at a temperature between 50 °C and 100 °C is passed through the drum.
    [0051] The invention will now be elucidated in detail with reference to the examples. For this purpose, the figures show: Figure 1: Plant flow diagram of the used high pressure batch hydrogenation apparatusFigure 2: Conversion and selectivity graph in the batch hydrogenation of a mixture of C9 aldehyde with a catalyst containing chromium and nickelFigure 3 : Graph of conversion and selectivity in the batch hydrogenation of a mixture of C9 aldehyde with a catalyst containing chromium and nickel (“catalyst A”)Figure 4: Graph of conversion and selectivity in the continuous hydrogenation of a mixture of C9 aldehyde with a catalyst A containing chromium and nickel and a chromium and nickel-free C catalyst.Example 0: Preparation of a precursor of a chromium-free and nickel-free Cu/SiO2 catalyst
    [0052] A SiO2 support is impregnated with an aqueous solution of tetraamine copper carbonate (prepared according to the invention from copper (II) hydroxycarbonate, ammonium hydrogen carbonate and/or ammonium carbonate, ammonia and water) at room temperature. This is followed by drying in a stream of air at moderate temperatures. Finally, the calcination is carried out in air at 450 °C.
    [0053] The support material used is Aerolyst® 3041 from Evonik. Typical properties of the same are a SiO 2 content greater than 99%, cylindrical extrudates with a diameter of about 1.7 mm, pore volumes of about 1 cm 3 /g and a BET surface area of about 150 m 2 /g.
    [0054] Copper hydroxycarbonate, concentrated ammonia solution, ammonium hydrogen carbonate and/or ammonium carbonate and water are used to prepare a copper tetraamine solution containing about 13% copper by weight. The solution was then diluted once more with water to about 11% copper by weight.
    [0055] For the purpose of impregnation, the dilute solution of tetraamine copper carbonate was then sprayed onto the support material. In impregnation, the support rotates on a drum. During the spraying operation, a certain amount of air passed through the fixed bed. The amount of spray solution applied is such that, after impregnation, practically all the pores have been filled with liquid and the copper saline solution is distributed throughout the grain.
    [0056] Drying was performed in the same drum. For this purpose, the air stream which is passed through the drum and fixed bed was heated to temperatures of about 75°C. In this specific case, the catalyst, before calcination, was subjected to additional drying in another reactor at 120 °C in an air stream.
    [0057] The calcination, in which the copper salt is essentially converted to copper oxide, was carried out in an oven through which a continuous stream of air flowed; the GHSV (gas hourly space velocity) was 2000 h-1; the catalyst was calcined at 450°C for 10 h in air.
    [0058] In principle, the catalyst can be prepared by any impregnation processes in which the pores of the support are filled with the solution; examples thereof also include vacuum impregnation or immersion of the support with excess solution.
    [0059] Drying can also be performed in other usual industrial units (shaft dryers, chamber ovens, belt dryers, drum dryers, vacuum dryers); typical drying temperatures are between 50°C and 150°C.
    [0060] It is also possible to use different units in the calcination: shaft kilns, chamber kilns, rotary kilns, etc. The 450°C temperature is certainly not extremely crucial either; slightly lower temperatures or else higher temperatures are conceivable here as well.
    [0061] The precursor prepared in this way contained 15% by weight of CuO and about 85% by weight of SiO2.
    [0062] For the purpose of activation to produce the catalyst, the precursor is contacted with a stream of hydrogen gas at 10*105 Pa at 60 l/h (STP). The temperature was increased here in steps of 30 K every hour from 60 °C to 180 °C and held constant for 12 h.Example 1 (non-inventive): Hydrogenation of C9 aldehydes from a Co-catalyzed hydroformylation at 180 °C with a catalyst containing chromium and nickel
    [0063] Catalyst A used is a chromium-containing catalyst as also used for the experiments described in DE19842370A1.
    [0064] For the performance of the batch hydrogenation experiments, a 1 L high pressure stainless steel reactor stirred by means of an external circuit was used. The reactor has a catalyst filling insert with a diameter of 4 cm and a length of 30 cm. A simplified flow diagram of the plant is shown in Figure 1.
    [0065] The reactor and the conduits were heated by means of wound heating tapes and the temperature was controlled and regulated by means of PT100 thermocouples. The liquid phase was circulated through a Gather DS2X30 gear pump with circulation rates of 45 l/h. The temperature of the liquid phase was controlled with the aid of a LAUDA LTH350s thermostat. The heat carrier used was MARLOTHERM SH. For phase separation, a stainless steel vessel (2 l capacity) was installed and continuously cooled with water. The phase separator simultaneously served as a reservoir for the liquid reagent. The supply of hydrogen and nitrogen was regulated using Bronkhorst F231M or F231C mass flow meters. Before carrying out the batch experiments, 90 ml of catalyst A (dry) were introduced into the catalyst basket and installed in the reactor. The freshly prepared hydrogenation catalysts were reduced in a hydrogen stream at 10*105 Pa at 60 l (STP)/h. The temperature was increased here in steps of 30 K every hour from 60 °C to 180 °C and held constant for 12 h. The phase separator was charged with 1 L of reagent and the liquid phase was heated in circulation through the reactor bypass. Upon reaching the desired reaction temperature, a bypass sample was taken and the reaction was started by opening the reactor cock. During the reaction, samples were taken at defined times and analyzed by offline GC (7890B GC; from Agilent Technologies).
    [0066] The conversions and selectivities obtained in this experiment are shown in the form of a graph in Figure 2.Example 2 (inventive): Hydrogenation of C9 aldehydes from a Co-catalyzed hydroformylation at 180 °C with a chromium-nickel-free catalyst
    [0067] Batch hydrogenation with the chromium-nickel-free catalyst of Example 0 ("catalyst C") is conducted as described in Example 1. Catalyst A is substituted here for catalyst C. The conversion and selectivity graph shows that much higher alcohol selectivity can be achieved with catalyst C.Example 3: Long-term comparison of a chromium-nickel-containing catalyst with a chromium-nickel-free catalyst
    [0068] Parallelized evaluation of alternative hydrogenation catalysts was performed on a continuously operated 16-channel system to test heterogeneous catalyst systems. The system has a central reactor block with 16 separate stainless steel reactors with a length of 96 cm and an internal diameter of 5 mm. The reactor block is electrically heated and allows isothermal operation of the reactors with an accuracy of ± 1 °C. A capillary restrictor system is used for dispensing and measuring in the liquid and gaseous reactants; the pressure retention of the reactors is based on Equilibrium back pressure membrane modules. For the evaluation of hydrogenation catalysts, after estimating the catalyst activity from the batch experiments described in Examples 1 and 2, 0.2 g to 0.6 g of catalyst (in dry form) was used in the form of a sieve fraction ( 0.2 mm to 0.4 mm) and diluted with crushed quartz (0.3 mm to 0.5 mm). The catalysts used were always diluted in such a way that a constant length of the catalytically active bed of 10 cm was produced. The hydrogenation of the liquid phase is conducted in the drip bed operation; the hydrogen must be fed in gaseous form here. The hydrogen is then partially dissolved in the liquid phase and partially in the form of bubbles in the gas phase. In addition, there is a flow of exhaust gases to prevent the accumulation of gaseous by-products. The test was thus carried out at a temperature of 180 °C and a hydrogen pressure of 25x105 Pa at an LHSV (liquid hourly space velocity) of 6 h-1 and a GHSV (gas hourly space velocity of gaseous hydrogen) of 2000 h-1. All measurements were performed as a double determination. Product samples were analyzed by offline GC (7890B GC; from Agilent Technologies), analogously to the hydrogenation experiments according to Example 1 and Example 2.
    [0069] As shown by the conversion and selectivity diagram of this comparison shown in Figure 4, it is possible, with the inventive chromium and nickel-free catalyst C, to achieve consistently high alcohol selectivity superior to that of the comparative catalyst A containing chromium and nickel compared to throughout the duration of the experiment. At the same time, catalyst C is notable for a much smaller decrease in the degree of conversion compared to catalyst A. Conclusion
    [0070] The comparison of the examples shows that it is possible, using the Cr- and Ni-free Cu catalyst, according to the invention, to hydrogenate C5, C9, C13 and C17 aldehyde mixtures obtained from industrial hydroformylation, at the same time obtaining product mixtures containing a high proportion of the corresponding aldehydes, although the proportion of undesirable by-products is small.
    [0071] Viewed over an extended period, the aldehyde yields from the chromium and nickel-free experiments are not significantly poorer than the comparative experiments with conventional Ni/Cu/Cr systems.
    [0072] In the preparation of the chromium and nickel-free catalyst, it is possible to avoid the handling of carcinogenic substances. The use of precious metals is unnecessary. No additional work steps in the preparation of the catalyst, for example a sulfidation, were necessary. In preparation, no elevated temperature was required. The hydrogenation results are entirely satisfactory. The catalyst appears to be economically usable in industry.
    权利要求:
    Claims (12)
    [0001]
    1. Process for preparing alcohols by hydrogenation of aldehydes, wherein a feed mixture comprising at least one aldehyde and at least one annex component is contacted with a heterogeneous catalyst in the presence of hydrogen, producing a mixture of products comprising at least the alcohol corresponding to the hydrogenated aldehyde and at least one by-product, wherein the catalyst comprises a support material and copper applied thereto, characterized in that the support material is silicon dioxide; and the catalyst in activated form has the following composition summing 100% by weight:silicon dioxide: from 86% by weight to 90% by weight;copper: from 10% by weight to 14% by weight;nickel: from 0% by weight; ppm by weight to 50 ppm in chromium: from 0 weight; ppm by weight to 50 ppm in aluminum oxide: from 0 weight; ppm by weight to 1000 ppm in other substances: from 0 ppm by weight to 1% by weight.
    [0002]
    2. Process, according to claim 1, characterized by the fact that the catalyst in activated form has the following composition that adds up to 100% by weight: silicon dioxide: from 87% by weight to 89% by weight; copper: from 11 % by weight to 13% by weight; nickel: from 0 weight; ppm by weight to 50 ppm in chromium: from 0 weight; ppm by weight to 50 ppm in ruthenium: from 0 weight; ppm by weight to 50 ppm palladium: from 0 ppm by weight to 50 ppm by weight; platinum: from 0 weight; ppm by weight to 50 ppm in aluminum oxide: from 0 ppm by weight to 100 ppm in water: weight; from 0 ppm by weight to 100 ppm in carbonates: weight; from 0 ppm by weight to 100 ppm in hydroxides: weight; from 0 ppm in weight to 100 ppm in other substances: weight; from 0 ppm by weight to 0.5% by weight.
    [0003]
    3. Process according to claim 1 or 2, characterized in that the specific volume of the pores of the support material is between 0.8 cm3/g and 1.2 cm3/g, determined by the cyclo-immersion method. hexane, and where the specific surface area of the support material (BET surface area) is between 130 m2/g and 170 m2/g, determined by the ISO 9277 method.
    [0004]
    Process according to any one of claims 1 to 3, characterized in that it is carried out at a pressure between 15x105 Pa and 25x105 Pa and at a temperature between 140°C and 180°C, the pressure and temperature being chosen accordingly. that the feed mixture and the product mixture are in a liquid phase.
    [0005]
    5. Process according to claim 4, characterized in that hydrogen is present in a superstoichiometric amount, the concentration of hydrogen being chosen so that at least part of the hydrogen is dissolved in the liquid phase.
    [0006]
    6. Process according to any one of claims 1 to 5, characterized in that the feed mixture originates from a hydroformylation and, as such, comprises a plurality of aldehydes with the same number n of carbon atoms , and corresponding alcohols and high-boiling components, where n is a natural number between three and eighteen.
    [0007]
    7. Process according to claim 6, characterized in that the feed mixture has the following composition that adds up to 100% by weight: total fraction of aldehydes having nine carbon atoms: from 25% by weight to 75% by weight ;total fraction of alcohols having nine carbon atoms: from 10% by weight to 55% by weight;total fraction of acetals: from 0.5% by weight to 5.5% by weight;total fraction of additional hydrocarbons: from 0% weight to 40% by weight; water: from 0% by weight to 3% by weight.
    [0008]
    8. Process according to claim 6, characterized in that the feed mixture has the following composition that adds up to 100% by weight: total fraction of aldehydes having nine carbon atoms: from 15% by weight to 65% by weight;total fraction of alcohols having nine carbon atoms: from 20% by weight to 65% by weight;total fraction of acetals: from 0.5% by weight to 5.5% by weight;total fraction of additional hydrocarbons: from 0 % by weight to 40% by weight; water: from 0% by weight to 1% by weight.
    [0009]
    9. Process for the preparation of a catalyst comprising the following steps: a) providing a support material containing at least 99% by weight of silicon dioxide; b) providing copper (II) hydroxycarbonate, ammonium hydrogen carbonate and/or carbonate of ammonia, ammonia and water; c) prepare a solution of copper(II) hydroxycarbonate, ammonium hydrogencarbonate and/or ammonia carbonate, ammonia and water, in such a way that the copper content of the solution is between 10% by weight and 15% by weight, where the proportion of chromium in the solution is between 0 ppm by weight and 50 ppm by weight, and where the proportion of nickel in the solution is between 0 ppm by weight and 50 ppm by weight; d) impregnating the support material with the solution;e) drying the impregnated support material at temperatures between 50°C and 150°C;f) calcining the dry and impregnated support material at temperatures between 300°C and 600°C to obtain a precursor;g) activating the precursor by reduction with hydrogen to obtain the active catalyst, characterized by the fact that that the impregnation and at least part of the drying is carried out in a drum in such a way that the support material is introduced into the drum for impregnation, that the drum is rotated, that the solution is sprayed into the drum, and that, during the drying phase, a stream of air at a temperature between 50°C and 100°C is passed through the drum.
    [0010]
    10. Process according to claim 9, characterized in that the copper content in the solution is between 10.5% by weight and 11.5% by weight.
    [0011]
    11. Process according to claim 9 or 10, characterized in that the support material provided comprises cylindrical extrudates having a diameter between 1 mm and 2 mm.
    [0012]
    12. Process according to any one of claims 9 to 11, characterized in that the precursor has the following composition, which adds up to 100% by weight: silicon dioxide: from 84% by weight to 86% by weight; copper: from 14% by weight to 16% by weight;nickel: from 0 ppm by weight to 50 ppm by weight; chromium: from 0 ppm by weight to 50 ppm by weight; aluminum oxide: from 0 ppm by weight to 1000 ppm by weight; other substances: from 0 ppm by weight to 1% by weight.
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    MX2017014306A|2018-10-02|
    JP2018158915A|2018-10-11|
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    法律状态:
    2018-08-14| B03A| Publication of a patent application or of a certificate of addition of invention [chapter 3.1 patent gazette]|
    2020-02-27| B25D| Requested change of name of applicant approved|Owner name: EVONIK OPERATIONS GMBH (DE) |
    2020-03-31| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2021-08-10| B06W| Patent application suspended after preliminary examination (for patents with searches from other patent authorities) chapter 6.23 patent gazette]|
    2021-11-30| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2022-01-04| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 07/11/2017, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP16197935.6|2016-11-09|
    EP16197935|2016-11-09|
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