CN117816179A - Catalyst for preparing 1, 4-butanediol from dimethyl succinate and preparation method thereof - Google Patents

Catalyst for preparing 1, 4-butanediol from dimethyl succinate and preparation method thereof Download PDF

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CN117816179A
CN117816179A CN202311536648.6A CN202311536648A CN117816179A CN 117816179 A CN117816179 A CN 117816179A CN 202311536648 A CN202311536648 A CN 202311536648A CN 117816179 A CN117816179 A CN 117816179A
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catalyst
salt
preparing
carbonate
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刘佳
卢文新
胡四斌
肖敦峰
朱凡
夏智
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China Wuhuan Engineering Co Ltd
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China Wuhuan Engineering Co Ltd
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Abstract

The invention discloses a catalyst for preparing 1, 4-butanediol from dimethyl succinate and a preparation method thereof, wherein the catalyst comprises the following components in percentage by weight: 31.4 to 43.8 weight percent of ZnO:12.4 to 18.6 weight percent of Co 3 O 4 :4.1 to 10.9 weight percent of MgO:3.3 to 8.2 weight percent of carbon nano tube: 8-15 wt% and the balance of alumina. Cu is adopted as active metal, and the addition of the auxiliary agent can promote Cu atoms to be dispersed more uniformly and the grains to be smaller; the preparation process comprises kneading, drying and roasting, and the preparation process is simple: the preparation of solution, chemical reaction, washing and filtering are not needed, the process is easy to control, and almost no salt-containing wastewater is produced and is convenient to treat; the preparation method is simple, and the water is used in the preparation processLess and environment-friendly.

Description

Catalyst for preparing 1, 4-butanediol from dimethyl succinate and preparation method thereof
Technical Field
The invention belongs to the technical field of catalyst production and preparation, and particularly relates to a catalyst for preparing 1, 4-butanediol from dimethyl succinate and a preparation method thereof.
Background
1, 4-Butanediol (BDO) is an important organic and fine chemical raw material, is widely used in the fields of medicine, chemical industry, textile, papermaking, automobiles, daily chemical industry and the like, and can be used for producing Tetrahydrofuran (THF), PTEMG-spandex, polybutylene terephthalate (PBT), gamma-butyrolactone (GBL), polyurethane Resin (PU Resin), polybutylene terephthalate-adipate (PBAT), paint, plasticizer, and the like as a solvent, a brightening agent in the electroplating industry and the like.
The technological route for industrially producing the 1, 4-butanediol mainly comprises the following steps: an alkynal method using formaldehyde and acetylene as raw materials, a butadiene acetoxylation method using butadiene and acetic acid as raw materials, a propylene oxide method using propylene oxide/allyl alcohol as raw materials, and a maleic anhydride method using n-butane/maleic anhydride as raw materials. The maleic anhydride process is carried out under the action of catalyst to produce 1, 4-butanediol, and copper catalyst is generally adopted. Copper-containing catalysts are usually prepared by the coprecipitation method, i.e. adding alkaline coprecipitators such as sodium carbonate, sodium bicarbonate and ammonium carbonate salt into a mixed solution of water-soluble copper salt and aluminum salt, precipitating copper and aluminum in the form of insoluble basic carbonate, and then filtering, washing, drying, shaping and roasting to prepare the catalyst.
CN103801321a discloses a catalyst Cu-Ni-Zn-M-O type catalyst for preparing 1, 4-butanediol, wherein M is manganese or magnesium, the preparation process is: the soluble salts of Cu, ni, zn and M are prepared into a mixed solution, the mixed solution is mixed with a precipitant solution under the stirring of 50-70 ℃, the pH value is controlled to be 7-9, the mixed solution is stirred for 1-3 hours, the temperature is increased to 80-90 ℃, the ageing is carried out for 2-10 hours, the precipitate is obtained after filtration, and the precipitate is washed, dried, baked and molded to obtain the product. CN101502803a discloses a Cu-Zn-Al-M-O type catalyst for preparing 1, 4-butanediol or tetrahydrofuran by selective hydrogenation of dimethyl maleate, M is any one of Mn, mg or Cr, the preparation process is: and (3) at 50-90 ℃, the mixed solution of Cu, zn and M soluble salts and the precipitant are added in parallel and are subjected to coprecipitation, the pH value of a precipitation system is kept to be 6.8-7.2, the mixture is aged and washed at constant temperature after the dripping is finished, aluminum hydroxide and deionized water are added into the precipitate, and the mixture is mixed, heated and stirred, dried and roasted to obtain the catalyst. The catalyst prepared by the precipitation method has the advantages of high active metal load and distribution, but the preparation process is complex, the process control requirement is high, a large amount of salt-containing waste liquid is generated in the precipitation and washing processes, and the environmental protection pressure exists.
Besides the precipitation method, the impregnation method is also a common catalyst production method, CN1935375A discloses a novel catalyst for preparing 1, 4-butanediol by hydrogenating dimethyl maleate, mesoporous molecular sieve MCM-41 is adopted as a carrier to impregnate Cu salt solution for preparing a catalyst precursor, and the catalyst precursor is roasted to obtain the Cu/MCM-41 catalyst. Compared with the precipitation method, the impregnation method is simple to operate, but active metal solution gathers and has limited loading capacity to metals, thereby affecting the performance of the catalyst.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a catalyst for preparing 1, 4-butanediol from dimethyl succinate, which has high active metal load, high dispersity and good catalytic performance, and a preparation method thereof.
In order to achieve the above purpose, the invention provides a catalyst for preparing 1, 4-butanediol from dimethyl succinate, which is characterized in that: the catalyst comprises CuO in percentage by weight: 31.4 to 43.8 weight percent of ZnO:12.4 to 18.6 weight percent of Co 3 O 4 :4.1 to 10.9 weight percent of MgO:3.3 to 8.2 weight percent of carbon nano tube: 8-15 wt% and the balance of alumina.
The preparation method of the catalyst is characterized in that Cu salt, zn salt, mg salt, co salt, carbon nano tube and pseudo-boehmite are mixed, then nitric acid aqueous solution is added for kneading, and the catalyst is obtained after drying and roasting; the addition amount of the nitric acid aqueous solution is 1 to 4 times of the total mass of Cu salt, zn salt, mg salt, co salt, carbon nano tube and pseudo-thin aluminum.
Further, the concentration of the nitric acid aqueous solution is 1-5 wt%.
Further, the kneading time is 0.5 to 3 hours.
Further, the drying temperature is 80-110 ℃ and the drying time is 3-12 h.
Further, the roasting atmosphere is N 2 、CO 2 One or more inert atmospheres in Ar, the roasting temperature is 300-550 ℃, the roasting time is 3-6 h, the roasted Cu is active metal, the Co, zn and Mg elements are auxiliary agents, the carbon nano tube and the Al 2 O 3 Is a carrier.
Further, the Cu salt is one or a mixture of more of copper carbonate, basic copper carbonate and copper oxalate.
Further, the Zn salt is one or a mixture of more of zinc carbonate, basic zinc carbonate and zinc oxalate.
Further, the Mg salt is one or a mixture of more of magnesium carbonate, basic magnesium carbonate and magnesium oxalate.
Further, the Co salt is one or two of cobalt carbonate and cobalt oxalate.
Compared with the prior art, the invention has the beneficial effects that:
1) The catalyst adopts carbonate, basic carbonate and oxalate as raw materials, is not easy to produce explosive chemicals, has short purchase period and has no emission of nitrogen oxides in the roasting process; the prepared catalyst has the advantages of high active metal load, high dispersity and good catalytic performance;
2) The preparation process of the catalyst comprises kneading, drying and roasting, and the preparation process is simple: the preparation of solution, chemical reaction, washing and filtering are not needed, the process is easy to control, and almost no salt-containing wastewater is produced and is convenient to treat; the preparation method is simple, the water consumption in the preparation process is low, and the preparation method is environment-friendly;
3) The catalyst adopts Cu as active metal, and the addition of the auxiliary agent can promote Cu atoms to be dispersed more uniformly and grains to be smaller, so that exposed active sites are more, in addition, co element is a valence-changing metal and can interact with C=O bonds in the raw material ester to activate C=O, thereby being beneficial to the raw material esterCarrying out hydrogenation to form alcohol; the presence of Mg can effectively improve the acidity of the catalyst surface and inhibit the generation of tetrahydrofuran, thereby improving the BDO selectivity. The addition range of the auxiliary agent is as follows: cuO:31.4 to 43.8 weight percent of ZnO:12.4 to 18.6 weight percent of Co 3 O 4 :4.1 to 10.9 weight percent of MgO:3.3 to 8.2 weight percent, 12.4 to 18.6 weight percent is the range with better ZnO content, and too little or too much can not achieve the optimal effect of dispersing active metal Cu, co 3 O 4 The content is preferably 4.1 to 10.9 weight percent, the auxiliary effect is limited when the content is too small, and side reactions can be possibly caused when the content is too large; the MgO content is 3.3-8.2 wt% and too little catalyst shows limited acid-base regulation and control, and too much MgO covers active sites and weakens the activity of the catalyst;
4) The addition of the carbon nano tube improves the adsorption of the catalyst H 2 The adsorption concentration of hydrogen on the surface of the catalyst and the hydrogen overflow capacity can be improved 2 The ability to migrate to the active site, thereby enhancing the hydrogenation performance of the catalyst;
5) The dimethyl succinate hydrogenation reaction is an exothermic reaction, if heat cannot be removed in time, local hot spots can be formed, the reaction selectivity is influenced, and the activity of the catalyst is reduced after active metal grains grow up. Carbon nanotubes and Al 2 O 3 The pore canal combination of the catalyst has high heat dissipation efficiency, avoids the occurrence of local hot spots on the catalyst, and effectively prolongs the service life of the catalyst.
Detailed Description
For the purpose and advantages of the present invention, the present invention will be specifically described below with reference to examples, wherein the salts used in the comparative examples and examples are calculated as 100% pure.
Comparative example
Mixing 6.81g copper carbonate and 7.30g pseudo-boehmite uniformly, adding 56g1wt% nitric acid aqueous solution for kneading for 3 hours, then sending into a 110 ℃ oven for baking for 12 hours, and adding the mixture into N 2 Roasting in a protective inert atmosphere at 500 ℃ for 4 hours, cooling and taking out to obtain 10g of catalyst Cu 35 /Al 2 O 3 。
Example 1
6.09g is takenUniformly mixing basic copper carbonate, 1.62g of cobalt carbonate, 2.01g of basic zinc carbonate, 0.59g of basic magnesium carbonate, 2.56g of pseudo-boehmite and 0.80g of carbon nano tube, adding 25g of 3wt% nitric acid aqueous solution for kneading for 0.5h, putting into a 100 ℃ oven for baking for 12h, and then putting into CO 2 Roasting for 3 hours at 550 ℃ in atmosphere, cooling and taking out to obtain 10g of catalyst Cu 35 Co 8 Zn 12 Mg 2 /Al 2 O 3 -8CNT。
Example 2
Mixing 4.86g of copper carbonate, 0.61g of cobalt carbonate, 1.92g of zinc carbonate, 1.73g of magnesium carbonate, 4.42g of pseudo-boehmite and 1.01g of carbon nano tube uniformly, adding 58g of 5wt% nitric acid aqueous solution, kneading for 3 hours, sending into an 80 ℃ oven for baking for 12 hours, then baking for 6 hours at 300 ℃ under Ar atmosphere, cooling and taking out to obtain 10g of catalyst Cu 25 Co 3 Zn 10 Mg 5 /Al 2 O 3 -10CNT。
Example 3
Mixing 8.58g anhydrous copper acetate, 2.11g cobalt acetate tetrahydrate, 2.81g anhydrous zinc acetate, 2.34g magnesium acetate, 3.11g pseudo-boehmite and 1.30g carbon nano tube uniformly, adding 40g1wt% nitric acid aqueous solution, kneading for 3h, sending into a 100 ℃ oven for baking for 8h, then adding N 2 Roasting for 6 hours at 500 ℃ in atmosphere, cooling and taking out to obtain 10g of catalyst Cu 30 Co 5 Zn 10 Mg 4 /Al 2 O 3 -13CNT。
Example 4
Mixing 5.44g copper carbonate, 1.41g cobalt carbonate, 2.51g basic zinc carbonate, 0.88g basic magnesium carbonate, 2.45g pseudo-boehmite and 1.35g carbon nano tube uniformly, adding 42g3wt% nitric acid aqueous solution, kneading for 0.5h, sending into a 90 ℃ oven for baking for 8h, and then adding CO 2 Roasting for 5 hours at 350 ℃ in atmosphere, cooling and taking out to obtain 10g of catalyst Cu 28 Co 7 Zn 15 Mg 3 /Al 2 O 3 -13.5CNT。
Example 5
Mixing 4.52g basic copper carbonate, 2.54g cobalt acetate tetrahydrate, 3.65g anhydrous zinc acetate, 1.76g magnesium acetate, 3.46g pseudo-boehmite and 1.20g carbon nano tube uniformly, adding 25g1.5wt% nitric acid aqueous solution, kneading for 1h, sending into a 100 ℃ oven for baking for 6h, then baking for 4h at 450 ℃ under Ar atmosphere, cooling, and taking out to obtain 10g of catalyst Cu 26 Co 6 Zn 13 Mg 3 /Al 2 O 3 -12CNT。
Example 6
Mixing 9.15g anhydrous copper acetate, 1.69g cobalt acetate tetrahydrate, 2.88g zinc carbonate, 0.73g basic magnesium carbonate, 2.72g pseudo-boehmite and 1.10g carbon nano tube uniformly, adding 35g2wt% nitric acid aqueous solution, kneading for 1.5h, then sending into a 110 ℃ oven for baking for 10h, then adding CO 2 Roasting for 5 hours at 500 ℃ in atmosphere, cooling and taking out to obtain 10g of catalyst Cu 32 Co 4 Zn 15 Mg 2.5 /Al 2 O 3 -11CNT。
Example 7
Mixing 4.87g basic copper carbonate, 1.21g cobalt carbonate, 2.30g zinc carbonate, 2.34g magnesium acetate, 2.70g pseudo-boehmite and 1.49g carbon nano tube uniformly, adding 26g1wt% nitric acid aqueous solution, kneading for 1h, sending into a 110 ℃ oven for baking for 8h, then adding N 2 Roasting for 6 hours at 450 ℃ in the atmosphere, cooling and taking out to obtain 10g of catalyst Cu 28 Co 6 Zn 12 Mg 4 /Al 2 O-15CNT。
Example 8
Mixing 5.22g of basic copper carbonate, 1.00g of cobalt carbonate, 2.52g of basic zinc carbonate, 0.88g of basic magnesium carbonate, 2.65g of pseudo-boehmite and 1.50g of carbon nano tube uniformly, adding 20g of 3wt% nitric acid aqueous solution, kneading for 2 hours, sending into a 100 ℃ oven for baking for 9 hours, and then adding the mixture into N 2 Roasting for 3 hours at 550 ℃ in atmosphere, cooling and taking out to obtain 10g of catalyst Cu 30 Co 5 Zn 15 Mg 3 /Al 2 O 3 -12CNT。
Example 9
Mixing 5.25g copper carbonate, 2.11g cobalt acetate tetrahydrate, 3.08g zinc acetate, 1.38g magnesium carbonate, 3.68g pseudo-boehmite and 1.11g carbon nano tube uniformly, adding 30g1wt% nitric acid aqueous solution, kneading for 3h, sending into an 80 ℃ oven for baking for 12h, then adding CO 2 Roasting for 5 hours at 500 ℃ in atmosphere, cooling and taking out to obtain 10g of catalyst Cu 27 Co 5 Zn 11 Mg 4 /Al 2 O 3 -11CNT。
Example 10
Mixing 4.52g basic copper carbonate, 3.38g cobalt acetate tetrahydrate, 2.45g zinc carbonate, 1.39g magnesium carbonate, 3.44g pseudo-boehmite and 0.80g carbon nano tube uniformly, adding 34g3wt% nitric acid aqueous solution, kneading for 3h, sending into a 90 ℃ oven for baking for 10h, then adding CO 2 Roasting for 3 hours at 550 ℃ in atmosphere, cooling and taking out to obtain 10g of catalyst Cu 26 Co 8 Zn 13 Mg 4 /Al 2 O 3 -8CNT。
Example 11
The catalysts of the comparative example and the example are crushed into particles of 20 to 40 meshes, and are respectively filled into a constant temperature area of a fixed bed reactor, and are supported by inert components with the same particle size up and down. Using atmospheric 10% H 2 -N 2 The catalyst is reduced by the normal pressure mixed gas, the reduction temperature is 240 ℃, and the reduction time is 12 hours. After the reduction is finished, the mixture is treated by pure H 2 The temperature of the catalyst bed is reduced to 180 ℃ under the condition of atmosphere reduction, then the reaction pressure is increased to 6MPa, dimethyl succinate methanol solution is introduced, the catalyst activity is evaluated, and the space-time velocity of the dimethyl succinate solution is 0.3h -1 The hydrogen-ester ratio was 50. And (5) taking a liquid-phase product for analysis after the reaction is stable. The product was analyzed using gas chromatography with acetonitrile as internal standard.
The properties of each catalyst are shown in Table 1
Life experiments were performed with the catalyst of example 3, after 1000 hours, the DMS conversion was 99.2% and the BDO selectivity was 86.9%.

Claims (10)

1. A catalyst for preparing 1, 4-butanediol from dimethyl succinate is characterized in that: the catalyst comprises CuO in percentage by weight: 31.4 to 43.8 weight percent of ZnO:12.4 to 18.6 weight percent of Co 3 O 4 :4.1 to 10.9 weight percent of MgO:3.3 to 8.2 weight percent of carbon nano tube: 8-15 wt% and the balance of alumina.
2. A method for preparing the catalyst according to claim 1, wherein: mixing Cu salt, zn salt, mg salt, co salt, carbon nano tube and pseudo-boehmite, adding aqueous solution of nitric acid for kneading, drying and roasting to obtain a catalyst; the addition amount of the nitric acid aqueous solution is 1 to 4 times of the total mass of Cu salt, zn salt, mg salt, co salt, carbon nano tube and pseudo-thin aluminum.
3. The method for preparing the catalyst according to claim 1, wherein: the concentration of the nitric acid aqueous solution is 1-5 wt%.
4. The method for preparing the catalyst according to claim 1, wherein: the kneading time is 0.5 to 3 hours.
5. The method for preparing the catalyst according to claim 1, wherein: the drying temperature is 80-110 ℃ and the drying time is 3-12 h.
6. The method for preparing the catalyst according to claim 1, wherein: the roasting atmosphere is N 2 、CO 2 One or more inert atmospheres in Ar, the roasting temperature is 300-550 ℃ and the roasting time is 3-6 h.
7. The method for preparing the catalyst according to claim 1, wherein: the Cu salt is one or a mixture of more of copper carbonate, basic copper carbonate and copper oxalate.
8. The method for preparing the catalyst according to claim 1, wherein: the Zn salt is one or a mixture of more of zinc carbonate, basic zinc carbonate and zinc oxalate.
9. The method for preparing the catalyst according to claim 1, wherein: the Mg salt is one or a mixture of more of magnesium carbonate, basic magnesium carbonate and magnesium oxalate.
10. The method for preparing the catalyst according to claim 1, wherein: the Co salt is one or two of cobalt carbonate and cobalt oxalate.
CN202311536648.6A 2023-11-17 2023-11-17 Catalyst for preparing 1, 4-butanediol from dimethyl succinate and preparation method thereof Pending CN117816179A (en)

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