Supported tantalum catalyst for 1,3-butadiene production

Abstract

The present invention relates to a process for producing 1,3-butadiene from a feed comprising ethanol and acetaldehyde in the presence of a supported tantalum catalyst obtainable by aqueous impregnation of the support with a water-soluble tantalum precursor. Furthermore, the present invention relates to a process for producing the supported tantalum catalyst, and to the supported tantalum catalyst. Finally, the present invention relates to the use of the supported tantalum catalyst for producing 1,3-butadiene from a feed comprising ethanol and acetaldehyde to increase either or both of the selectivity and yield of the reaction.

Description

[Technical Field]

[0001] The present invention relates to a process for producing 1,3-butadiene from a feed containing ethanol and acetaldehyde in the presence of a supported tantalum catalyst obtained by aqueous impregnation of the support with a water-soluble tantalum precursor. Furthermore, the present invention relates to a process for producing the supported tantalum catalyst and the supported tantalum catalyst. Finally, the present invention relates to the use of the supported tantalum catalyst for producing 1,3-butadiene from a feed containing ethanol and acetaldehyde to increase either or both of the selectivity and yield of the reaction. [Background technology]

[0002] 1,3-Butadiene is one of the most important raw materials in the rubber industry and is used as a monomer in the production of synthetic rubbers such as polybutadiene rubber (PBR), acrylonitrile-butadiene-styrene polymer (ABS), styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), and styrene-butadiene latex. Currently, 1,3-butadiene is mostly prepared from unsustainable sources such as crude C streams from steam cracking processes or by catalytic dehydration of butane and butene (Non-Patent Document 1).

[0003] In recent years, there has been growing interest in using ethanol as a renewable source of 1,3-butadiene. For example, M.D. Jones et al. (Non-Patent Document 2) investigated silica-supported binary and ternary catalyst systems for the conversion of ethanol to 1,3-butadiene. The highest selectivity to 1,3-butadiene in the systems investigated was achieved using copper oxide-doped ZrO x - This was achieved using a ZnO / SiO2 catalyst, resulting in a good yield of 1,3-butadiene of 30%.

[0004] In Patent Document 1, one-step catalytic conversion of ethanol over silica-supported two-way and three-way catalyst systems was reported. A zirconia-silica catalyst system was doped with gold or silver and ceria, and 9% acetaldehyde in the feed and 0.3 h - Using a WHSV of 1, the yields of 1,3-butadiene were 82% and 81%, respectively. However, the catalyst system requires reduction of the gold and silver oxides contained in the catalyst system prior to the one-step conversion of ethanol to 1,3-butadiene.

[0005] Starting from a mixture of ethanol and acetaldehyde, Ho-Jeong Chae et al. (Non-Patent Document 3) obtained 1,3-butadiene in 37% yield using a tantalum oxide catalyst on SBA-15 as a support. The catalyst was synthesized by impregnating the support with an ethanolic solution of tantalum chloride. The disadvantage of this method is that the synthesis must be carried out under anhydrous conditions, as tantalum chloride is susceptible to hydrolysis even in the presence of small amounts of water.

[0006] Patent Document 2 relates to, inter alia, a process that involves reacting a feed stream containing ethanol and optionally acetaldehyde in a dehydration reactor in the presence of a dehydration catalyst system having a Group 5 metal oxide and a zeolite support, and obtaining a product stream containing 1,3-butadiene from the dehydration reactor. The tantalum oxide catalyst was prepared by impregnating a silica support with an ethanolic solution of tantalum chloride. However, use of the resulting catalyst containing 2 wt. % tantalum oxide supported on silica in the process only resulted in a 1,3-butadiene yield of 2.1 to 8.1%, depending on the reaction conditions.

[0007] Patent Document 3 discloses the preparation of an aqueous tantalum peroxo complex solution by ammonia-assisted precipitation of Ta2O5xH2O from H2[TaF7]. The resulting solid is dissolved in a mixture of tetramethylammonium hydroxide (TMAOH), hydrogen peroxide, and water. The aqueous tantalum peroxo complex solution is used for the in situ generation of silica-supported tantalum catalysts with high BET specific surface area (e.g., Ta(6.8%) / MCM41 catalyst). For the production of 1,3-butadiene from ethanol, a Cu(10%) / Ta(6.8%) / MCM41 catalyst is prepared by incipient wetness impregnation of Ta(6.8%) / MCM41 with Cu(NO3)x2.5H2O.

[0008] Patent Document 4 relates to the photodeposition of various metal oxides / hydroxides other than CrO as a shell on a water-splitting photocatalyst to prevent the reverse reaction caused by oxygen reduction. The water-splitting photocatalyst is placed in a solution of an aqueous transition metal (Ti, Nb, or Ta) peroxo complex and irradiated with light. This reduces the peroxo complex, and the metal oxide / hydroxide in the complex coats the photocatalyst surface. The water-splitting rate achieved by photocatalysts carrying a shell of Ti oxide, Nb oxide, or Ta oxide is measured. The photocatalysts prepared in Patent Document 4 are not used for the production of 1,3-butadiene, and no drying or calcination steps are performed after the deposition of the aqueous transition metal peroxo complex on the photocatalyst. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] International Publication No. 2012 / 015340 [Patent Document 2] US Patent Application Publication No. 2019 / 0105634 [Patent Document 3] European Patent Application Publication No. 3476479 [Patent Document 4] Japanese Patent Application Laid-Open No. 2015-071128 [Non-patent literature]

[0010] [Non-Patent Document 1] Chem.Soc.Rev.,2014,43,7917 [Non-patent document 2] Catal.Sci.Technol.,2011,1,267 [Non-patent document 3] Appl. Catal. B, 2014, 150-151, 596 Summary of the Invention [Problem to be solved by the invention]

[0011] Therefore, there is a continuing need to provide a simple process for the preparation of supported metal oxide catalysts that enable the production of 1,3-butadiene in high yield and selectivity. [Means for solving the problem]

[0012] In accordance with the present invention, it has surprisingly been found that supported tantalum catalysts prepared by aqueous impregnation of a support with a water-soluble tantalum precursor (as described herein) lead to improved selectivity to and yield of 1,3-butadiene.

[0013] Thus, in a first aspect, the present invention relates to a process for producing 1,3-butadiene, the process comprising: i) contacting a feed comprising ethanol and acetaldehyde with a supported tantalum catalyst to obtain a crude product comprising 1,3-butadiene, the catalyst being obtainable (or obtained) by a process comprising: a) preparing a water-soluble tantalum precursor by reacting one or more tantalum compounds in an aqueous solution under oxidizing conditions; b) aqueous impregnation of a support with the water-soluble tantalum precursor obtained from step a); c) drying; and d) calcination.

[0014] In a second aspect, the present invention relates to a process for the preparation of a supported tantalum catalyst, comprising the steps of: a) preparing a water-soluble tantalum precursor by reacting one or more tantalum compounds in an aqueous solution under oxidizing conditions; b) aqueous impregnation of a support with the water-soluble tantalum precursor obtained from step a); c) drying; and d) calcination.

[0015] In a third aspect, the present invention also relates to a supported tantalum catalyst obtainable (or obtainable) according to the process of the second aspect. Finally, in a fourth aspect, the present invention relates to the use of a supported tantalum catalyst according to the third aspect for producing 1,3-butadiene from a feed comprising ethanol and acetaldehyde to increase one or both of the x. selectivity and y. yield of the reaction to 1,3-butadiene. DETAILED DESCRIPTION OF THE INVENTION

[0016] 1) 1,3-butadiene manufacturing process The process for producing 1,3-butadiene of the present invention comprises the steps of: i) contacting a feed comprising ethanol and acetaldehyde with a supported tantalum catalyst to obtain a crude product comprising 1,3-butadiene; The catalyst is a) preparing a water-soluble tantalum precursor by reacting one or more tantalum compounds in an aqueous solution under oxidizing conditions; b) aqueous impregnation of the support with the water-soluble tantalum precursor obtained from step a); c) drying the product of step b); d) calcining the product of step c); obtainable (or obtained) by a process comprising:

[0017] In a preferred embodiment, the supported tantalum catalyst has a tantalum content, calculated as Ta2O5, in the range of 0.1 to 10 wt%, preferably 0.5 to 5 wt%, more preferably 2 to 3 wt%, based on the total weight of the catalyst. Most preferably, the supported tantalum catalyst has a tantalum content, calculated as Ta2O5, of about 3 wt%, based on the total weight of the catalyst.

[0018] Preferably, the tantalum compound is selected from the group consisting of tantalum halides, tantalum hydroxide, and tantalum oxalate, preferably selected from the group consisting of tantalum(V) hydroxide and tantalum(V) chloride, more preferably the tantalum compound is tantalum(V) hydroxide.

[0019] Another preferred embodiment relates to the process defined herein, wherein the contacting in i) is carried out at a temperature in the range of 200 to 500°C, preferably 250 to 450°C, more preferably 300 to 400°C.

[0020] Preferably, the contacting in step i) is carried out for 0.2 to 10 hours. -1 , preferably 1 to 7 hours -1 The pressure is applied at a weight hourly space velocity in the range of Preferred is the process as defined herein, further comprising ii) separating the crude product into at least a first portion comprising 1,3-butadiene, a second portion comprising acetaldehyde, and a third portion comprising ethanol, wherein preferably at least a portion of the second portion, or at least a portion of the third portion, or at least a portion of the second and third portions, is recycled to the feed. Preferably, all of the second portion, or all of the third portion, or all of the second and third portions, are recycled to the feed.

[0021] Another preferred embodiment relates to the process as defined herein, wherein the contacting in i) is carried out in a continuous flow fixed bed reactor. 2) Process for the preparation of supported tantalum catalysts As indicated above, according to another aspect, the present invention provides a method for producing a medicament for the treatment of a pulmonary arthritis, comprising: a) preparing a water-soluble tantalum precursor by reacting one or more tantalum compounds in an aqueous solution under oxidizing conditions; b) aqueous impregnation of the support with the water-soluble tantalum precursor obtained from step a); c) drying the product of step b); d) calcination (of the product of step c) The present invention relates to a process for producing a supported tantalum catalyst comprising:

[0022] In a preferred embodiment, the supported tantalum catalyst obtainable or obtainable by the process according to the invention defined herein has a tantalum content, calculated as Ta2O5, in the range of 0.1 to 10 wt%, preferably 0.5 to 5 wt%, more preferably 2 to 3 wt%, based on the total weight of the catalyst. Most preferably, the supported tantalum catalyst has a tantalum content, calculated as Ta2O5, of about 3 wt%, based on the total weight of the catalyst.

[0023] Preferably, the tantalum compound reacted in step a) of the process is selected from the group consisting of tantalum halides, tantalum hydroxide, and tantalum oxalate, preferably selected from the group consisting of tantalum(V) hydroxide and tantalum(V) chloride, more preferably the tantalum compound is tantalum(V) hydroxide.

[0024] Preferably, reacting in aqueous solution and under oxidizing conditions includes the presence of one or both of persulfate ions and hydrogen peroxide. More preferably, reacting in aqueous solution and under oxidizing conditions includes the presence of hydrogen peroxide.

[0025] Ammonium persulfate is a preferred starting material to provide persulfate ions in the aqueous solution. If sodium and / or potassium persulfate are used, these cations should be removed from the supported tantalum catalyst prior to the calcination step d). Removal of sodium and potassium can be carried out before or after the drying step c) of the process of the present invention, and is preferably achieved by washing the (dried) impregnated support with one or more organic and / or inorganic acids.

[0026] Preferably, the combined content of the supported tantalum catalyst in sodium and potassium is less than 0.05 wt.% (based on the total weight of the catalyst) after calcination step d). Preferably, sulfur, preferably in the form of sulfur oxides, should also be removed from the catalyst at elevated temperatures, preferably in the drying and calcination process (as described below).

[0027] The use of basic metal peroxides to generate hydrogen peroxide in aqueous solution can produce a pH above 7, for example, where sodium peroxide hydrolyzes to sodium hydroxide and hydrogen peroxide in a violent reaction.

[0028] If the water-soluble tantalum compound is reacted with aqueous sodium hydroxide in step a) (or step a1) or step a2)) of the process defined herein, sodium must be removed from the supported tantalum catalyst prior to calcination step d). Sodium removal can occur before or after drying step c) of the process defined herein, and is preferably achieved by washing the impregnated (dried) support with one or more organic and / or inorganic acids. Preferably, after calcination step d), the sodium content of the resulting supported tantalum catalyst is less than 0.05 wt.%, based on the total weight of the catalyst.

[0029] Preferably, the water-soluble tantalum precursor is prepared in step a) of the process according to the invention by reacting at a pH of the aqueous solution above 7. In one preferred embodiment of the process defined herein, the water soluble tantalum precursor is a1) reacting the tantalum compound with aqueous hydrogen peroxide, followed by reaction with one or both of aqueous ammonia and aqueous sodium hydroxide; or a2) reacting the tantalum compound with an aqueous solution of hydrogen peroxide and one or both of an aqueous solution of ammonia and an aqueous solution of sodium hydroxide simultaneously; It is prepared by

[0030] Preferably, the weight ratio of tantalum to ammonia is in the range of 3:1 to 1:1, and this weight ratio is calculated as tantalum metal and pure ammonia, and preferably is about 2:1 calculated as tantalum metal and pure ammonia.

[0031] According to another preferred embodiment, the weight ratio of tantalum to hydrogen peroxide in step a) or step a1) or step a2) is in the range of 1:10 to 1:40, calculated as tantalum metal and pure hydrogen peroxide, and is preferably about 1:20.

[0032] If the water-soluble tantalum compound is reacted with aqueous sodium hydroxide in step a) or step a1) or step a2) of the process defined herein, sodium must be removed from the supported tantalum catalyst before calcination step d). Sodium removal can be performed before or after drying step c) of the process defined herein, and is preferably achieved by washing the (dried) impregnated support with one or more organic and / or inorganic acids. Preferably, after calcination step d), the sodium content of the resulting supported tantalum catalyst is less than 0.05 wt.%, based on the total weight of the catalyst.

[0033] Therefore, a preferred embodiment of the process defined herein comprises (in addition to steps a) and b) c) drying the product of step b); c') sodium removal (from the product of step c); d) calcination step (of the product of step c'); Includes.

[0034] A preferred alternative embodiment of the process defined herein comprises (in addition to steps a) and b) c') sodium removal (from the product of step b); c) drying the product of step c'); d) calcination (of the product of step c) Includes.

[0035] According to an alternative preferred embodiment of the process defined herein, in process step b), aqueous impregnation of the support with the tantalum precursor obtained from step a) further comprises co-impregnation of said support with an aqueous solution of one or more cesium compounds. Preferably, the cesium compounds are one or more organic or inorganic salts. More preferably, the cesium compounds are selected from the group consisting of cesium nitrate, cesium formate, cesium oxalate, cesium carbonate, cesium hydroxide, and cesium acetate.

[0036] Thus, according to an alternative preferred embodiment of the process defined herein, step b) comprises: b) aqueous impregnation of the support with the water-soluble tantalum precursor obtained from step a), preferably simultaneously with one or more cesium compounds (as defined herein); It comprises or consists of:

[0037] According to another preferred alternative embodiment of the process defined herein, a cesium compound as defined herein may be reacted with a tantalum compound as defined herein in step a) or a1) or a2) of the process defined herein. Preferably, the supported tantalum catalyst obtainable or obtainable by the process defined herein has a cesium content, calculated as CsO, in the range of 0.02 to 1.5 wt%, preferably 0.05 to 1 wt%, more preferably 0.1 to 0.5 wt%, based on the total weight of the catalyst, and / or preferably the weight ratio of CsO to TaO in the catalyst is in the range of 1:6 to 1:30.

[0038] Without wishing to be bound by any particular theory, it appears that the functionalization of the catalyst with cesium leads to the blocking of strongly acidic sites that are responsible for the production of by-products in the conversion of ethanol and acetaldehyde to 1,3-butadiene, such as ethylene and diethyl ether. Another advantage of cesium doping of supported tantalum catalysts relates to the possibility of carrying out the process for the production of 1,3-butadiene defined herein at higher temperatures, at which higher conversions can be obtained and therefore higher yields can be achieved, without a significant loss or even an increase in selectivity.

[0039] Preferably, the support is selected from ordered and irregular porous silica supports, aluminosilicate supports, and other porous oxide supports and mixtures thereof, more preferably selected from Al2O3, ZrO2, TiO2, MgO, ZnO, NiO, CeO2, clays, and mixtures thereof.

[0040] The support impregnated in step b) of the process of the present invention can be synthesized or purchased from a commercial supplier. Preferably, the carrier as defined herein has a molecular weight of 130 to 550 m 2 / g, more preferably 190 to 280 m 2 / g。 In the framework of the present text, the term "specific surface area" refers to the BET specific surface area (m 2 / g).

[0041] Preferably, the supports defined herein have an average pore size (as determined by the method of Barrett, Joyner and Halenda) of 30 to 300 Å. Preferably, the support as defined herein has a pore volume (as determined by the method of Barrett, Joyner and Halenda) of 0.2 to 1.5 ml / g.

[0042] More preferably, the carrier as defined herein has a molecular weight of 130 to 550 m 2 / g, most preferably 190 to 280 m 2 / g, an average pore diameter of 30 to 300 Å, and a pore volume of 0.2 to 1.5 ml / g.

[0043] Reacting one or more tantalum compounds as defined herein with hydrogen peroxide and ammonia in steps a), a1) or a2) of the process as defined herein is particularly advantageous because said compounds are readily commercially available, can be easily removed after impregnation step b), by heat treatment during calcination step d) of the process, and do not alter the surface chemistry of the supported catalyst.

[0044] Also, the process for preparing a catalyst in aqueous solution according to the present invention, which includes the preparation of a water-soluble tantalum precursor from one or more tantalum compounds, can be used to form TaO on the surface of a support. x Advantageously, this allows for better distribution of sites and therefore provides higher selectivity to 1,3-butadiene.

[0045] Therefore, the aqueous impregnation of the support with the water-soluble tantalum precursor obtained from step a) is preferably carried out in step b) of the process according to the invention in a completely homogeneous aqueous solution.

[0046] Tantalum(V) chloride is known to be moisture-sensitive, difficult to handle, and usually hydrolyzes in water to form a precipitate. However, in the process according to the present invention defined herein, a water-soluble tantalum precursor is prepared in step a) of the process, for example, by using hydrogen peroxide and ammonia as complexing agents. After an optional step of diluting the water-soluble tantalum precursor obtained from step a) of the process with water to an appropriate concentration, it is used to impregnate a support in step b) of the process. Various tantalum compounds as defined herein, including tantalum(V) chloride, can be used to prepare the water-soluble tantalum precursor in step a) of the process defined herein. However, the use of tantalum(V) hydroxide in step a) of the process defined herein is particularly preferred, as it avoids the generation of corrosive gases and a strong exothermic reaction.

[0047] According to one preferred embodiment of the process according to the invention as defined herein, between steps a) and b) of the process, additional water is added to the partially or preferably completely dissolved water-soluble tantalum precursor obtained from step a) to preferably adjust the volume of the impregnation solution to the pore volume of the support to be impregnated in step b).

[0048] According to another preferred embodiment of the process according to the invention as defined herein, the support as defined herein is washed with one or more organic or inorganic acids, optionally followed by a heat treatment with the water-soluble tantalum precursor obtained from step a), optionally with one or more cesium salts, before being impregnated in step b).

[0049] 3) Supported tantalum catalyst According to another aspect, the present invention relates to a supported tantalum catalyst obtainable (or obtainable) by the process defined herein.

[0050] In a preferred embodiment of the supported catalyst defined herein, the support is selected from ordered and irregularly porous silica supports, aluminosilicate supports, and other porous oxide supports and mixtures thereof, more preferably selected from Al2O3, ZrO2, TiO2, MgO, ZnO, NiO, CeO2, clays, and mixtures thereof.

[0051] Preferably, the carrier as defined herein has a molecular weight of 130 to 550 m 2 / g, more preferably 190 to 280 m 2 / g specific surface area. Preferably, the support as defined herein has an average pore size of 30 to 300 Å.

[0052] Preferably, the support as defined herein has a pore volume of 0.2 to 1.5 ml / g. More preferably, the carrier as defined herein has a molecular weight of 130 to 550 m 2 / g, most preferably 190 to 280 m 2 / g, and an average pore diameter of 30 to 300 Å and a pore volume of 0.2 to 1.5 ml / g.

[0053] Preferably, the supported tantalum catalyst has a tantalum content, calculated as Ta2O5, in the range of 0.1 to 10 wt%, preferably 0.5 to 5 wt%, more preferably 2 to 3 wt%, based on the total weight of the catalyst. Most preferably, the supported tantalum catalyst has a tantalum content, calculated as Ta2O5, of about 3 wt%, based on the total weight of the catalyst.

[0054] Preferably, the supported tantalum catalyst defined herein further comprises cesium, and preferably the cesium content of the catalyst, calculated as CsO, is in the range of 0.02 to 1.5 wt%, preferably 0.05 to 1 wt%, more preferably 0.1 to 0.5 wt%, based on the total weight of the catalyst, and / or preferably the weight ratio of CsO to TaO in the catalyst is in the range of 1:6 to 1:30.

[0055] 4) Use of supported tantalum catalysts In another aspect, the present invention relates to using a supported tantalum catalyst as defined herein for producing 1,3-butadiene from a feed comprising ethanol and acetaldehyde, to increase one or both of the x. selectivity and y. yield of the reaction to 1,3-butadiene.

[0056] Preferred embodiments of the process for producing 1,3-butadiene according to the invention correspond to or can be derived from preferred embodiments of the process for producing the supported tantalum catalyst according to the invention, or vice versa, and preferred embodiments of the process according to the invention correspond to or can be derived from preferred embodiments of the supported tantalum catalyst or use according to the invention described above, or vice versa.

[0057] The following examples illustrate the advantages of the present invention. Unless otherwise indicated, all percentages are by weight. Example 1. Preparation of Supported Catalysts Tantalum chloride 99.99% was supplied by Acros Organics. Wet tantalum hydroxide, also called Ta2O5*nH2O, with a composition of about 40 to about 50 wt.% Ta2O5, was supplied by H.C. Starck (trade name "Tantalum Oxihydrate moist").

[0058] Silica CARiACT Q-15 and Q-10 were supplied by Fuji Silysia Chemical Co. CARiACT Q-15 had a particle size of 1.18–2.36 mm, a bulk density of 0.43 g / ml, an average pore diameter of 150 Å, a pore volume of 0.99 ml / g, and a viscosity of 190 m 2 CARiACT Q-10 is a spherical silica catalyst support with a specific surface area of ​​1.18-2.36 mm, a bulk density of 0.43 g / ml, an average pore diameter of 100 Å, a pore volume of 0.99 ml / g, and a surface area of ​​280 m 2 / g specific surface area.

[0059] The supported catalysts of Examples 1 to 8 were prepared as follows. 1a) Comparative Example 1 The catalyst for Comparative Example 1, having a composition of 3 wt% Ta2O5 / SiO2, was prepared based on the teachings of Chae et al. (Appl. Catal. B, 2014, 150-151, 596) using tantalum chloride as the tantalum compound and absolute ethanol as the solvent. The specific surface area of ​​the silica support was 280 m 2 / g.

[0060] 1b) Examples 2 and 3 according to the invention Since the supplied tantalum hydroxide was wet, thermogravimetric analysis was performed prior to synthesis to estimate the concentration of tantalum pentoxide contained in the compound. In this case, the concentration of tantalum pentoxide was 47.4 wt%, so 45 g of CALiACT Q-10 silica support (described above) was heated at room temperature with 50 cm 3 The carrier was impregnated with the solution by dropping a portion of the impregnation solution onto the carrier.

[0061] The impregnation solution was prepared by first dissolving 2.94 g of tantalum hydroxide in 41 cm 3 After treatment with a 30% aqueous solution of hydrogen peroxide, 4.1 cm 3 After complete dissolution, water was added to obtain a 50 cm 3A solution of

[0062] The resulting impregnated support was dried at 120°C for 10 h and then calcined at 500°C for 5 h at a heating rate of 5°C / min in an air atmosphere. 1c) Examples 4 and 5 according to the invention Since the supplied tantalum hydroxide was wet, thermogravimetric analysis was performed before synthesis to estimate the concentration of tantalum pentoxide contained in the compound. In this case, the concentration of tantalum pentoxide was 47.4 wt%, so 45 g of CAriACT Q-15 silica support (described above) was added at room temperature to a 50 cm3 solution obtained by dropping a portion of the impregnation solution onto the support as follows: 3 The resulting mixture was impregnated with a solution of

[0063] The impregnation solution was prepared by first dissolving 2.94 g of tantalum hydroxide in 41 cm 3 After treatment with a 30% aqueous solution of hydrogen peroxide, 4.1 cm 3 After complete dissolution, water was added to obtain a 50 cm 3 A solution of

[0064] The resulting impregnated support was dried at 120°C for 10 h and then calcined at 500°C for 5 h at a heating rate of 5°C / min in an air atmosphere. 1d) Example 6 according to the invention Since the supplied tantalum hydroxide was wet, thermogravimetric analysis was performed before synthesis to estimate the concentration of tantalum pentoxide contained in the compound. In this case, the concentration of tantalum pentoxide was 47.4 wt%, so 45 g of CAriACT Q-10 silica support (described above) was added at room temperature to a 50 cm3 solution obtained by dropping a portion of the impregnation solution onto the support as follows: 3 The resulting mixture was impregnated with a solution of

[0065] The impregnation solution was prepared by first dissolving 2.94 g of tantalum hydroxide and 0.06 g of cesium formate in 41 cm 3 After treatment with a 30% aqueous solution of hydrogen peroxide, 4.1 cm 3After complete dissolution, water was added to obtain a 50 cm 3 A solution of

[0066] The resulting impregnated support was dried at 120°C for 10 h and then calcined at 500°C for 5 h at a heating rate of 5°C / min in an air atmosphere. 1e) Example 7 according to the invention Since the supplied tantalum hydroxide was wet, thermogravimetric analysis was performed before synthesis to estimate the concentration of tantalum pentoxide contained in the compound. In this case, the concentration of tantalum pentoxide was 47.4 wt%, so 45 g of CAriACT Q-10 silica support (described above) was added at room temperature to a 50 cm3 solution obtained by dropping a portion of the impregnation solution onto the support as follows: 3 The resulting mixture was impregnated with a solution of

[0067] The impregnation solution was prepared by first dissolving 2.94 g of tantalum hydroxide and 0.29 g of cesium formate in 41 cm 3 After treatment with a 30% aqueous solution of hydrogen peroxide, 4.1 cm 3 After complete dissolution, water was added to obtain a 50 cm 3 A solution of

[0068] The resulting impregnated support was dried at 120°C for 10 h and then calcined at 500°C for 5 h at a heating rate of 5°C / min in an air atmosphere. 1f) Example 8 according to the invention Since the supplied tantalum hydroxide was wet, thermogravimetric analysis was performed before synthesis to estimate the concentration of tantalum pentoxide contained in the compound. In this case, the concentration of tantalum pentoxide was 47.4 wt%, so 45 g of CAriACT Q-15 silica support (described above) was added at room temperature to a 50 cm3 solution obtained by dropping a portion of the impregnation solution onto the support as follows: 3 The resulting mixture was impregnated with a solution of

[0069] The impregnation solution was prepared by first dissolving 2.94 g of tantalum hydroxide and 0.06 g of cesium formate in 41 cm 3After treatment with a 30% aqueous solution of hydrogen peroxide, 4.1 cm 3 After complete dissolution, water was added to obtain a 50 cm 3 A solution of

[0070] The resulting impregnated support was dried at 120°C for 10 h and then calcined at 500°C for 5 h at a heating rate of 5°C / min in an air atmosphere. 2. Catalyst Testing Comparative Example 1 The catalyst synthesized using absolute ethanol (as described above) as the solvent was placed in a continuous-flow stainless steel reactor. The reactor was heated to 350 °C with a nitrogen flow rate of 20 ml / min. A 96% ethanol-acetaldehyde mixture was used as the feed in a volume ratio of 2.5:1 for 1 h. -1 The reaction was carried out at a weight hourly space velocity (WHSV) of 1000 kJ / min.

[0071] The results were calculated as follows and are shown in Table 1 below:

[0072]

number

[0073] Example 2 The reaction was carried out as in Example 1, except that the catalyst was prepared using a water-soluble tantalum precursor obtained from tantalum hydroxide as described above.

[0074] Example 3 The reaction was carried out as in Example 2, except that the reactor was heated to 375°C. Example 4 As above, 190m 2 The reaction was carried out as in Example 2, except that the catalyst was prepared using silica with a specific surface area of ​​100000000 / g.

[0075] Example 5 The reaction was carried out as in Example 4, except that the reactor was heated to 375°C. Example 6 The reaction was carried out as in Example 3, except that the catalyst was 0.1% Cs2O-3% Ta2O5 / SiO2 (prepared as above).

[0076] Example 7 The reaction was carried out as in Example 6, except that the catalyst was 0.5% Cs2O-3% Ta2O5 / SiO2 (prepared as above).

[0077] Example 8 The reaction was carried out as in Example 5, except that the catalyst was 0.1% Cs2O-3% Ta2O5 / SiO2 (prepared as above).

[0078] [Table 1]

[0079] Comparing Example 1 (Comparative) with Examples 2-8 demonstrates that the use of a supported tantalum catalyst prepared according to the present invention increases the yield of 1,3-butadiene. For Examples 2, 4, and 8, it also increases the selectivity to 1,3-butadiene. Example 2, in particular, demonstrates a significant increase in selectivity to 1,3-butadiene and an improved yield compared to Comparative Example 1. Comparing Example 2 with Example 3 demonstrates that increasing the reaction temperature from 350°C to 375°C increases conversion, resulting in the same improved yield of 41% 1,3-butadiene (compared to Comparative Example 1), even with a decrease in selectivity. Both were 190 m 2 A comparison of Examples 4 and 5, which use catalysts according to the invention with a lower specific surface area support of 190 m / g, also shows that increasing the reaction temperature from 350°C to 375°C increases the conversion, leading to a high yield of 1,3-butadiene of 43%, albeit with somewhat lower selectivity. The highest yields of 1,3-butadiene, 43% and 44%, respectively, were obtained at 190 m 2This is achieved in Examples 5 and 8 according to the invention at a low specific surface area support of 0.1 wt. / g and a high reaction temperature of 375° C. In particular, Example 8 showed improved selectivity to 1,3-butadiene and significantly improved yield of 1,3-butadiene compared to Comparative Example 1 at a CsO loading of 0.1 wt.% based on the total weight of the catalyst.

Claims

1. i) contacting a feed comprising ethanol and acetaldehyde with a supported tantalum catalyst to obtain a crude product comprising 1,3-butadiene, The catalyst a) preparing a water-soluble tantalum precursor by reacting one or more tantalum compounds in an aqueous solution under oxidizing conditions; b) aqueous impregnation of a support with the water-soluble tantalum precursor obtained from step a), wherein the support is selected from ordered porous silica supports, irregular porous silica supports, ordered porous aluminosilicate supports, irregular porous aluminosilicate supports, and other porous oxide supports, and mixtures thereof; c) a drying step; d) a calcination step; The manufacturing process is obtainable by a process comprising:

2. The supported tantalum catalyst is Ta ２ O ５ 2. The process of claim 1, wherein the tantalum content, calculated as tungsten, is in the range of 0.1 to 10 wt %, based on the total weight of the catalyst.

3. The supported tantalum catalyst is Ta ２ O ５ 2. The process of claim 1, wherein the tantalum content, calculated as tungsten, is in the range of 0.5 to 5 wt %, based on the total weight of the catalyst.

4. The supported tantalum catalyst is Ta ２ O ５ 2. The process of claim 1, wherein the tantalum content, calculated as tungsten, is in the range of 2 to 3 wt %, based on the total weight of the catalyst.

5. The process of any one of claims 1 to 4, wherein the tantalum compound is selected from the group consisting of tantalum halides, tantalum hydroxide, and tantalum oxalate.

6. The process of any one of claims 1 to 4, wherein the tantalum compound is selected from the group consisting of tantalum(V) hydroxide and tantalum(V) chloride.

7. The process of any one of claims 1 to 4, wherein the tantalum compound is tantalum(V) hydroxide.

8. The process of any one of claims 1 to 7, wherein the contacting in i) is carried out at a temperature in the range of 200 to 500°C.

9. The process of any one of claims 1 to 7, wherein the contacting in i) is carried out at a temperature in the range of 250 to 450°C.

10. The process of any one of claims 1 to 7, wherein the contacting in i) is carried out at a temperature in the range of 300 to 400°C.

11. The contacting step i) is carried out for 0.2 to 10 hours. －１ The process of any one of claims 1 to 10, carried out at a weight hourly space velocity in the range of

12. The contacting step i) is carried out for 1 to 7 hours. －１ The process of any one of claims 1 to 10, carried out at a weight hourly space velocity in the range of

13. ii) separating the crude product into at least a first portion comprising 1,3-butadiene, a second portion comprising acetaldehyde, and a third portion comprising ethanol.

14. 14. The process of claim 13, wherein at least a portion of the second portion, or at least a portion of the third portion, or at least a portion of the second portion and the third portion, is recycled to the feed.

15. 15. The process of any one of claims 1 to 14, wherein the contacting in i) is carried out in a continuous flow fixed bed reactor.

16. A process for producing a supported tantalum catalyst for the production of 1,3-butadiene, comprising: a) preparing a water-soluble tantalum precursor by reacting one or more tantalum compounds in an aqueous solution under oxidizing conditions; b) aqueous impregnation of a support with the water-soluble tantalum precursor obtained from step a), wherein the support is selected from ordered porous silica supports, irregular porous silica supports, ordered porous aluminosilicate supports, irregular porous aluminosilicate supports, and other porous oxide supports, and mixtures thereof; c) a drying step; d) a calcination step; A process for producing a supported tantalum catalyst for the production of 1,3-butadiene, comprising:

17. 17. The process of claim 16, wherein said reacting in aqueous solution and under oxidizing conditions comprises the presence of one or both of persulfate ions and hydrogen peroxide.

18. 17. The process of claim 16, wherein said reacting in an aqueous solution and under oxidizing conditions comprises the presence of hydrogen peroxide.

19. 19. The process of any one of claims 16 to 18, wherein said reacting in aqueous solution is at a pH greater than 7.

20. The water-soluble tantalum precursor is a1) reacting the tantalum compound with aqueous hydrogen peroxide followed by reaction with one or both of aqueous ammonia and aqueous sodium hydroxide; or a2) The process of any one of claims 16 to 19, wherein the tantalum compound is prepared by simultaneously reacting an aqueous solution of hydrogen peroxide with one or both of an aqueous solution of ammonia and an aqueous solution of sodium hydroxide.

21. 21. The process of claim 20, wherein the weight ratio of tantalum to ammonia is in the range of 3:1 to 1:1 calculated as tantalum as metal and pure ammonia.

22. 21. The process of claim 20, wherein the weight ratio of tantalum to ammonia is 2:1, calculated as tantalum metal and pure ammonia.

23. 23. The process of any one of claims 17 to 22, wherein the weight ratio of tantalum to hydrogen peroxide in step a) is in the range of 1:10 to 1:40 calculated as tantalum as metal and pure hydrogen peroxide.

24. 23. The process of any one of claims 17 to 22, wherein the weight ratio of tantalum to hydrogen peroxide in step a) is 1:20 calculated as tantalum as metal and pure hydrogen peroxide.

25. The carrier is 130 to 550 m ２ The process according to any one of claims 16 to 24, wherein the carbon black has a BET specific surface area of ​​1 / 2g.

26. The carrier is 190 to 280 m ２ The process according to any one of claims 16 to 24, wherein the carbon black has a BET specific surface area of ​​1 / 2g.

27. A supported tantalum catalyst for the production of 1,3-butadiene obtainable by the process according to any one of claims 16 to 26.

28. 28. The supported tantalum catalyst of claim 27, wherein the support is selected from ordered porous silica supports and non-ordered porous silica supports.

29. 29. The supported tantalum catalyst of claim 27 or 28, further comprising cesium.

30. The cesium content of the catalyst is Cs ２ 30. The supported tantalum catalyst of claim 29, wherein the amount of O is in the range of 0.02 to 1.5 wt %, calculated as O, based on the total weight of the catalyst.

31. The cesium content of the catalyst is Cs ２ 30. The supported tantalum catalyst of claim 29, wherein the amount of O is in the range of 0.05 to 1 wt %, based on the total weight of the catalyst.

32. The cesium content of the catalyst is Cs ２ 30. The supported tantalum catalyst of claim 29, wherein the amount of O is in the range of 0.1 to 0.5 wt %, based on the total weight of the catalyst.

33. The supported tantalum catalyst is Ta ２ O ５ and the cesium content of the catalyst is ２ Converted to O, Cs ２ O and Ta in the supported tantalum catalyst ２ O ５ The supported tantalum catalyst according to any one of claims 29 to 32, wherein the weight ratio of

34. Use of the supported tantalum catalyst according to any one of claims 27 to 33 for producing 1,3-butadiene from a feed containing ethanol and acetaldehyde, to increase one or both of the selectivity and yield of the reaction to 1,3-butadiene.

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