CN116803503B - Catalyst, preparation method and application thereof in preparing 1, 4-butanediol by succinic acid hydrogenation - Google Patents
Catalyst, preparation method and application thereof in preparing 1, 4-butanediol by succinic acid hydrogenationInfo
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Abstract
本发明提供一种催化剂、制备方法及在琥珀酸加氢制备1,4‑丁二醇中的应用，属于催化剂制备技术领域。该催化剂的表达式为Co‑X‑M/SiO2，其中，SiO2为载体，X选自Cu、Ni、Fe、Zn、Mn、Mo、V或Cr金属元素中的一种或两种，M选自碱金属氧化物和碱土金属氧化物中的一种。本发明还提供上述催化剂的制备方法，本发明还提供所述的催化剂在琥珀酸加氢制备1,4‑丁二醇中的应用。本发明采用了非贵金属催化剂，制备简单，价格低廉，并且催化活性高，1,4‑丁二醇选择性好，能够在较低的反应温度，适中的氢气压力，和较短的反应时间内制得1,4‑丁二醇，并且收率可达95％以上。The present invention provides a catalyst, a preparation method and an application thereof in preparing 1,4-butanediol by hydrogenation of succinic acid, belonging to the field of catalyst preparation technology. The expression of the catalyst is Co-X-M/SiO 2 , wherein SiO 2 is a carrier, X is selected from one or both of Cu, Ni, Fe, Zn, Mn, Mo, V or Cr metal elements, and M is selected from one of alkali metal oxides and alkaline earth metal oxides. The present invention also provides a preparation method of the above-mentioned catalyst, and the present invention also provides the application of the catalyst in preparing 1,4-butanediol by hydrogenation of succinic acid. The present invention uses a non-precious metal catalyst, which is simple to prepare, low in price, and has high catalytic activity, good selectivity for 1,4-butanediol, and can be obtained at a lower reaction temperature, a moderate hydrogen pressure, and a shorter reaction time. 1,4-butanediol can be obtained in a yield of more than 95%.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a catalyst, a preparation method and application thereof in preparing 1, 4-butanediol by succinic acid hydrogenation.
Background
1, 4-Butanediol is an important raw material for industrially producing chemicals such as tetrahydrofuran, N-vinyl pyrrolidone and the like, is also a basic raw material for producing polybutylene terephthalate engineering plastics and fibers, and is widely used in the fields of pesticides, medicines, cosmetics and the like. In recent years, the demand for 1, 4-butanediol has been greatly increased and the price has been greatly increased as a core material for producing degradable plastics such as adipic acid butanediol diformate and poly (butylene succinate). The industrial preparation method of the 1, 4-butanediol mainly comprises four methods, namely an alkynal method, a butadiene method, a propylene oxide method and a maleic anhydride method. The alkynal method is a more traditional method, and the process has the advantages of wider application, harder preparation of raw materials, higher cost, higher safety risk and larger influence on the environment. The butadiene method has the advantages of rich raw material sources and mild reaction conditions, but the process adopts a noble metal catalyst, and has longer flow, large overall investment and high energy consumption. The catalyst in the epoxypropane method can be repeatedly used, has long service life, and the yield of 1, 4-butanediol can be adjusted, but the isomerisation product allyl alcohol has certain toxicity. The maleic anhydride method has the advantages of cheap raw materials and lower production cost, but adopts an acid process for production, and has higher requirement on corrosion resistance of equipment. At present, the methods take fossil resources as raw materials, and various problems exist. With the development of the chemical industry and the increasing demand for 1, 4-butanediol, further development of green synthesis and renewable synthesis processes of 1, 4-butanediol is required.
Succinic acid is an important renewable biomass-based platform molecule, and is one of the potential raw materials for the production of renewable 1, 4-butanediol. In recent years, the development and utilization of renewable resources such as biomass are gradually increased in China. Succinic acid can be produced from a lignocellulosic biomass feedstock, and succinic acid has been industrially produced by a biological method. Therefore, it is necessary, feasible, and of great research and application value to develop efficient techniques for the production of 1, 4-butanediol from succinic acid. Le et al prepared Cu-Pd/HAP catalyst by co-impregnation method for preparing 1, 4-butanediol by succinic acid hydrogenation. The presence of Cu and Pd in the alloying process has a synergistic effect, and the fine alloy structure with high Cu content is beneficial to prepare 1, 4-butanediol, and when the Cu and Pd contents are respectively 8wt.% and 2wt.%, the succinic acid conversion rate and the 1, 4-butanediol selectivity are respectively 100% and 82% under the hydrogen pressure conditions of 200 ℃ and 8MPa (ACS Sustainable Chemistry & Engineering,2019, 7:18483-18492). tapin and the like are adopted to prepare the Re-Pd/TiO 2 catalyst by adopting a continuous impregnation and catalytic reduction method, and the 1, 4-butanediol yield can reach 80-90 percent (MATERIALS CHEMISTRY AND PHYSICS,2020, 252:123225) under the conditions of 160 ℃ and 15MPa hydrogen pressure. Di and the like prepare Re-Ru/C bimetallic catalyst for succinic acid hydrogenation reaction by adopting a microwave pyrolysis method. Re-Ru bimetallic interaction changes the adsorption and activation of active components on the catalyst surface, and 1, 4-butanediol yield is 70.1% under hydrogen pressure conditions of 160 ℃ and 8MPa (Industrial & ENGINEERING CHEMISTRY RESEARCH,2017, 56:4672-4683). Vardon et al prepared a Ru-Sn/AC catalyst for succinic acid aqueous hydrogenation reaction by an immersion method. The catalytic activity is best when the metal mass ratio of Ru to Sn is 1:1, and the 1, 4-butanediol yield is 82% (ACS CATALYSIS,2017, 7:6207-6219) under the hydrogen pressure condition of 10MPa at 180 ℃. The Pt-Fe bimetallic catalyst is adopted in the process of muu and the like, and 1, 4-butanediol is prepared through succinic acid hydrogenation. The reaction was carried out at 180℃under a hydrogen pressure of 5MPa for 5,10,30 hours, with yields of 1, 4-butanediol of 22,40.7 and 90.7% (CN 104368358A), respectively. In the above studies, it is generally considered that gamma-butyrolactone is an intermediate in the hydrogenation of succinic acid to 1, 4-butanediol, and gamma-butyrolactone and tetrahydrofuran are major by-products in the reaction for producing 1, 4-butanediol. One U.S. patent reports that by performing a gas phase hydrogenation of gamma-butyrolactone over a magnesium silicate supported Cu-Pd-KOH catalyst, wherein Cu, pd, KOH mass% of the catalyst is 12, 0.5 and 2 mass%, the 1, 4-butanediol selectivity can reach 99.0% when the conversion of gamma-butyrolactone is 96.5% under hydrogen pressure conditions of 160 ℃ and 6.2MPa (US 4797382). In one Japanese patent, fuchigami et al, using Pd/C catalyst in the presence of tetrabutylammonium rhenium oxide in the presence of a mixture of water and ethanol as solvent, used to catalyze the hydrogenation of gamma-butyrolactone to prepare 1, 4-butanediol. The reaction was carried out at 180℃under a hydrogen pressure of 10MPa for 16 hours, with a conversion of gamma-butyrolactone and a selectivity of 1, 4-butanediol of 98% and 88.6%, respectively (JP 7082188).
In summary, in the reaction of preparing 1, 4-butanediol by taking succinic acid as a raw material, a noble metal catalyst is mainly adopted, the reaction temperature is 160-200 ℃, the hydrogen pressure is 5-15MPa, and the yield of 1, 4-butanediol can reach 80-90%. The reaction conditions are severe and generally require higher hydrogen pressures and longer reaction times. In view of the high price of noble metal catalysts, the production costs are greatly increased. Therefore, the development and application of non-noble metal catalysts, and the catalytic hydrogenation of succinic acid to prepare 1, 4-butanediol at lower temperature and hydrogen pressure, are effective ways of realizing industrial application of the reaction.
Disclosure of Invention
The invention aims to provide a catalyst, a preparation method and application thereof in preparing 1, 4-butanediol by hydrogenating succinic acid, wherein the catalyst can prepare the 1, 4-butanediol under relatively low temperature and hydrogen pressure and in a short reaction time.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
The invention firstly provides a catalyst, the expression formula of the catalyst is Co-X-M/SiO 2, wherein SiO 2 is a carrier, X is selected from one or two of Cu, ni, fe, zn, mn, mo, V or Cr metal elements, and M is selected from one of alkali metal oxides and alkaline earth metal oxides.
Preferably, in the catalyst, the content of the SiO 2 carrier is 60-89 wt%, the content of the Co component is 5-30 wt%, the content of the X component is 1-15 wt%, and the content of the M component is 5-20 wt%.
Preferably, M is selected from Li 2 O, mgO or CaO.
The invention also provides a preparation method of the catalyst, which comprises the following steps:
Dipping a metal solution of alkali metal or alkaline earth metal into a SiO 2 carrier, and drying and calcining to obtain an M/SiO 2 catalyst;
Step two, dipping the mixed metal solution of Co and the metal component X into the M/SiO 2 prepared in the step one according to the method of the step one, and drying, calcining and reducing to obtain the catalyst Co-X-M/SiO 2.
Preferably, the dipping in the first step is specifically to drop the metal solution of alkali metal or alkaline earth metal onto the surface of SiO 2 drop by drop uniformly, evaporate the solution under the condition of tungsten lamp irradiation and 65-75 ℃, stir SiO 2 until SiO 2 is dried uniformly, then drop the next time, and repeat until the metal solution is consumed.
Preferably, the calcination temperature of the first step is 200-800 ℃, the calcination time is 1-6h, the calcination temperature of the second step is 200-600 ℃, and the calcination time is 1-6h.
Preferably, the reduction temperature of the second step is 200-600 ℃ and the reduction time is 0.5-4h.
The invention also provides application of the catalyst in preparing 1, 4-butanediol by succinic acid hydrogenation.
Preferably, the method for preparing the 1, 4-butanediol by hydrogenating the succinic acid comprises the following steps:
and (3) taking H 2 as a hydrogen source to carry out succinic acid hydrogenation reaction, and adding the reduced Co-X-M/SiO 2 catalyst, succinic acid and a solvent into a reaction kettle to react to prepare the 1, 4-butanediol.
Preferably, the reaction temperature is 140-200 ℃, the hydrogen pressure is 3-10MPa, and the reaction time is 1-28h.
The beneficial effects of the invention are that
The invention provides a catalyst, a preparation method and application in preparing 1, 4-butanediol by succinic acid hydrogenation, wherein the catalytic activity can be greatly improved by adding two components of X and M into a Co-based catalyst, and the 1, 4-butanediol is prepared under the conditions of relatively low temperature and hydrogen pressure and in a relatively short reaction time. The method can reduce the use and dependence of 1, 4-butanediol on fossil raw materials in the production of the 1, 4-butanediol, has higher selectivity of the prepared 1, 4-butanediol, is milder in reaction conditions, can prepare the 1, 4-butanediol under lower temperature and hydrogen pressure conditions, can provide convenience for the subsequent separation process in industrial production, and can reduce the difficulty and energy consumption of the separation process.
Detailed Description
The invention firstly provides a catalyst, the expression formula is Co-X-M/SiO 2, wherein Co is a main metal component, siO 2 is a carrier, X and M respectively represent two other components, X is selected from one or two of Cu, ni, fe, zn, mn, mo, V or Cr metal elements, and M is selected from one of alkali metal oxides and alkaline earth metal oxides, preferably Li 2 O, mgO or CaO.
According to the invention, the catalyst preferably comprises 60-89wt.% of SiO 2 carrier, 5-30wt.% of Co component, 1-15wt.% of X component, 5-20wt.% of M component, more preferably 65-70wt.% of SiO 2 carrier, 15-22wt.% of Co component, 3-10wt.% of X component and 5-10wt.% of M component.
The invention also provides a preparation method of the catalyst, which comprises the following steps:
Dipping a metal solution of alkali metal or alkaline earth metal into a SiO 2 carrier, wherein the dipping is particularly preferably that the metal solution of the alkali metal or alkaline earth metal is dropwise and uniformly added onto the surface of SiO 2, the solution is evaporated under the conditions of tungsten lamp irradiation and 65-75 ℃ each time, siO 2 is stirred until the solution is uniform after SiO 2 is dried, the next dropwise addition is carried out again, the steps are repeated until the metal solution is consumed, and then the drying is carried out, wherein the drying is preferably carried out at 110 ℃ for one night, and then the M/SiO 2 catalyst is obtained after calcination, the calcination temperature is preferably 200-800 ℃, more preferably 400-600 ℃, and the calcination time is preferably 1-6h, more preferably 3-4 h;
The metal solution of the alkali metal or alkaline earth metal is nitrate solution or acetate solution of the alkali metal or alkaline earth metal, the concentration of the metal solution is preferably 0.03-0.15g/ml, and the mass ratio of the metal solution to the SiO 2 carrier is preferably 5-30:1;
Immersing the mixed metal solution of Co and the metal component X into the M/SiO 2 prepared in the first step according to the method of the first step, drying the mixed metal solution, preferably drying the mixed metal solution at 110 ℃ for one night, calcining the mixed metal solution, preferably at 200-600 ℃, more preferably 300-500 ℃, for preferably 1-6 hours, more preferably 3-4 hours, and reducing the calcined catalyst in a hydrogen atmosphere before using the catalyst to obtain a Co-X-M/SiO 2 catalyst, wherein the reduction temperature in the hydrogen atmosphere is preferably 200-600 ℃, more preferably 300-500 ℃, and the reduction time is preferably 0.5-4 hours, more preferably 1-2 hours;
The mixed metal solution of Co and the metal component X is nitrate solution or acetate solution of Co and the metal component X, the concentration of the mixed metal solution is preferably 0.03-0.15g/ml, and the mass ratio of the mixed metal solution to the SiO 2 carrier is preferably 5-30:1.
The invention also provides application of the catalyst in preparing 1, 4-butanediol by succinic acid hydrogenation.
The method for preparing the 1, 4-butanediol by hydrogenating the succinic acid preferably comprises the following steps:
Adding the reduced Co-X-M/SiO 2 catalyst, succinic acid and a solvent into a reaction kettle for reaction by taking H 2 as a hydrogen source, wherein the reaction temperature is preferably 140-200 ℃, more preferably 160-180 ℃, the hydrogen pressure is preferably 3-10MPa, more preferably 5-7MPa, and the reaction time is preferably 1-28H, more preferably 4-8H, so as to prepare the 1, 4-butanediol.
According to the invention, the solvent is preferably selected from the group consisting of 1, 4-dioxane, water and alcohol solvents. The mass ratio of the solvent to the succinic acid is preferably 1-50:1, and the mass ratio of the succinic acid to the catalyst is preferably 1-40:1.
The invention is further illustrated by the following specific examples, which do not limit the scope of the invention.
Comparative example 1
4G of SiO 2 support having an average pore diameter of 10nm, which SiO 2 support is purchased from FujiSilycia Chemical Ltd. Company, were weighed out with an analytical balance and placed in an evaporation pan. 4.26g of cobalt nitrate hexahydrate is added into a volumetric flask, 25ml of distilled water is added to prepare a cobalt nitrate aqueous solution, and ultrasonic oscillation is carried out for 30min. The crucible was placed under a 375W tungsten lamp to adjust the SiO 2 surface temperature to about 70 ℃. And (3) dropwise adding 25ml of the prepared cobalt nitrate aqueous solution onto the surface of SiO 2, wherein the volume of the solution added dropwise is about 0.3ml each time, uniformly stirring the SiO 2 carrier after the surface of SiO 2 is completely dried, and then carrying out the next dropwise adding operation, and performing the circulating operation until the cobalt nitrate aqueous solution is completely added dropwise. The impregnated catalyst was dried at 110 ℃ for 12 hours and subsequently calcined at 300 ℃ for 3 hours. Before the reaction, the catalyst was reduced at 400 ℃ under hydrogen atmosphere for 1h, and after cooling, a Co/SiO 2 catalyst sample with a Co loading of 25wt.% was prepared.
Comparative example 2
4G of SiO 2 support having an average pore diameter of 10nm were weighed out by means of an analytical balance and placed in an evaporation pan. 1.23g of lithium nitrate is added into a volumetric flask, 25ml of distilled water is added to prepare a lithium nitrate aqueous solution, and ultrasonic vibration is carried out for 30min. The crucible was placed under a 375W tungsten lamp to adjust the SiO 2 surface temperature to about 70 ℃. And (3) dropwise adding 25ml of the prepared lithium nitrate aqueous solution onto the surface of SiO 2, wherein the volume of the solution added dropwise is about 0.3ml each time, uniformly stirring the SiO 2 carrier after the surface of SiO 2 is completely dried, and then carrying out the next dropwise adding operation, and performing the circulating operation until the lithium nitrate aqueous solution is completely added dropwise. The impregnated catalyst was dried at 110 ℃ for 12 hours and then calcined at 500 ℃ for 3 hours to produce Li 2O/SiO2. 4g of the prepared Li 2O/SiO2 was weighed out by an analytical balance and placed in an evaporation pan. Into a volumetric flask, 4.26g of cobalt nitrate hexahydrate was added, and 25ml of distilled water was further added to prepare an aqueous solution of cobalt nitrate for secondary impregnation, followed by ultrasonic vibration for 30 minutes. The crucible was placed under a 375W tungsten lamp to adjust the Li 2O/SiO2 surface temperature to about 70 ℃. And (3) dropwise adding 25ml of the prepared cobalt nitrate aqueous solution onto the surface of Li 2O/SiO2, wherein the volume of the solution added dropwise is about 0.3ml each time, uniformly stirring the Li 2O/SiO2 after the surface is completely dried, and then carrying out the next dropwise adding operation, and performing the circulating operation until the cobalt nitrate aqueous solution is completely added dropwise. The impregnated catalyst was dried at 110 ℃ for 12 hours and subsequently calcined at 300 ℃ for 3 hours. Before the reaction, the catalyst was reduced for 1h under the conditions of 400 ℃ and hydrogen atmosphere, and after cooling, co-Li 2O/SiO2 catalyst samples with Co and Li 2 O loadings of 25wt.% and 10wt.% respectively were prepared.
Example 1
Li 2O/SiO2 was prepared in the same manner as in comparative example 2.4 g of the prepared Li 2O/SiO2 was weighed out by an analytical balance and placed in an evaporation pan. 3.52g of cobalt nitrate hexahydrate and 0.35g of copper nitrate are added into a volumetric flask, 25ml of distilled water is added to prepare a mixed solution of cobalt nitrate and copper nitrate for secondary impregnation, and ultrasonic vibration is carried out for 30min. The secondary impregnation was carried out in the same manner as in comparative example 2. The twice impregnated catalyst was dried at 110 ℃ for 12 hours and then calcined at 300 ℃ for 3 hours. Before the reaction, the catalyst was reduced at 400 ℃ under hydrogen atmosphere for 1h, and after cooling, co, cu and Li 2 O loading was 22wt.%,3wt.% and 10wt.% of Co-Cu-Li 2O/SiO2 catalyst samples, respectively, were prepared.
Example 2
Li 2O/SiO2 was prepared in the same manner as in comparative example 2.4 g of the prepared Li 2O/SiO2 was weighed out by an analytical balance and placed in an evaporation pan. 3.20g of cobalt nitrate hexahydrate and 1.12g of ferric nitrate nonahydrate are added into a volumetric flask, 25ml of distilled water is added to prepare a mixed solution of cobalt nitrate and ferric nitrate for secondary impregnation, and ultrasonic vibration is carried out for 30min. The secondary impregnation was carried out in the same manner as in comparative example 2. The twice impregnated catalyst was dried at 110 ℃ for 12 hours and then calcined at 300 ℃ for 3 hours. Before the reaction, the catalyst was reduced at 500 ℃ under hydrogen atmosphere for 1h, and after cooling, co, fe and Li 2 O loading amounts of 20wt.%,5wt.% and 10wt.% co—fe-Li 2O/SiO2 catalyst samples were prepared, respectively.
Example 3
Li 2O/SiO2 was prepared in the same manner as in comparative example 2.4 g of the prepared Li 2O/SiO2 was weighed out by an analytical balance and placed in an evaporation pan. 3.20g of cobalt nitrate hexahydrate and 0.99g of nickel nitrate hexahydrate are added into a volumetric flask, 25ml of distilled water is added to prepare a mixed solution of cobalt nitrate and nickel nitrate for secondary impregnation, and ultrasonic vibration is carried out for 30min. The secondary impregnation was carried out in the same manner as in comparative example 2. The twice impregnated catalyst was dried at 110 ℃ for 12 hours and then calcined at 300 ℃ for 3 hours. Before the reaction, the catalyst was reduced for 1h under the conditions of 400 ℃ and hydrogen atmosphere, and Co, ni and Li 2 O loading amounts were 20wt.%,5wt.% and 10wt.% of Co-Ni-Li 2O/SiO2 catalyst samples were prepared after cooling.
Example 4
Li 2O/SiO2 was prepared in the same manner as in comparative example 2.4 g of the prepared Li 2O/SiO2 was weighed out by an analytical balance and placed in an evaporation pan. 3.52g of cobalt nitrate hexahydrate and 0.60g of nickel nitrate hexahydrate are added into a volumetric flask, 25ml of distilled water is added to prepare a mixed solution of cobalt nitrate and nickel nitrate for secondary impregnation, and ultrasonic vibration is carried out for 30min. The secondary impregnation was carried out in the same manner as in comparative example 2. The twice impregnated catalyst was dried at 110 ℃ for 12 hours and then calcined at 300 ℃ for 3 hours. Before the reaction, the catalyst was reduced at 400 ℃ under hydrogen atmosphere for 1h, and after cooling, co, ni and Li 2 O loading was 22wt.%,3wt.% and 10wt.% of co—ni—li 2O/SiO2 catalyst samples, respectively, were prepared.
Example 5
Li 2O/SiO2 was prepared in the same manner as in comparative example 2.4 g of the prepared Li 2O/SiO2 was weighed out by an analytical balance and placed in an evaporation pan. 2.40g of cobalt nitrate hexahydrate and 2.00g of nickel nitrate hexahydrate are added into a volumetric flask, 25ml of distilled water is added to prepare a mixed solution of cobalt nitrate and nickel nitrate for secondary impregnation, and ultrasonic vibration is carried out for 30min. The secondary impregnation was carried out in the same manner as in comparative example 2. The twice impregnated catalyst was dried at 110 ℃ for 12 hours and then calcined at 300 ℃ for 3 hours. Before the reaction, the catalyst was reduced for 1h under the conditions of 400 ℃ and hydrogen atmosphere, and Co, ni and Li 2 O loading amounts were 15wt.%,10wt.% and 10wt.% of Co-Ni-Li 2O/SiO2 catalyst samples were prepared after cooling.
Example 6
4G of SiO 2 carrier were weighed out with an analytical balance and placed in an evaporation dish. 0.62g of lithium nitrate is added into a volumetric flask, 25ml of distilled water is added to prepare a lithium nitrate aqueous solution, and ultrasonic vibration is carried out for 30min. The crucible was placed under a 375W tungsten lamp to adjust the SiO 2 surface temperature to about 70 ℃. And (3) dropwise adding 25ml of the prepared lithium nitrate aqueous solution onto the surface of SiO 2, wherein the volume of the solution added dropwise is about 0.3ml each time, uniformly stirring the SiO 2 carrier after the surface of SiO 2 is completely dried, and then carrying out the next dropwise adding operation, and performing the circulating operation until the lithium nitrate aqueous solution is completely added dropwise. The impregnated catalyst was dried at 110 ℃ for 12 hours and then calcined at 500 ℃ for 3 hours to produce Li 2O/SiO2. 3.20g of cobalt nitrate hexahydrate and 0.99g of nickel nitrate hexahydrate are added into a volumetric flask, 25ml of distilled water is added to prepare a mixed solution of cobalt nitrate and nickel nitrate for secondary impregnation, and ultrasonic vibration is carried out for 30min. The secondary impregnation was carried out in the same manner as in comparative example 2. The twice impregnated catalyst was dried at 110 ℃ for 12 hours and then calcined at 300 ℃ for 3 hours. Before the reaction, the catalyst was reduced for 1h under the conditions of 400 ℃ and hydrogen atmosphere, and Co, ni and Li 2 O loading amounts were 20wt.%,5wt.% and 5wt.% of Co-Ni-Li 2O/SiO2 catalyst samples were prepared after cooling.
Example 7
4G of SiO 2 carrier were weighed out with an analytical balance and placed in an evaporation dish. 1.48g of magnesium nitrate is added into a volumetric flask, 25ml of distilled water is added to prepare magnesium nitrate aqueous solution, and ultrasonic vibration is carried out for 30min. The crucible was placed under a 375W tungsten lamp to adjust the SiO 2 surface temperature to about 70 ℃. And (3) dropwise adding 25ml of the prepared magnesium nitrate aqueous solution onto the surface of SiO 2, wherein the volume of the solution added dropwise is about 0.3ml each time, uniformly stirring the SiO 2 carrier after the surface of SiO 2 is completely dried, and then carrying out the next dropwise adding operation, and performing the circulating operation until the magnesium nitrate aqueous solution is completely added dropwise. The impregnated catalyst was dried at 110℃for 12h and then calcined at 500℃for 3h to produce MgO/SiO 2. 3.20g of cobalt nitrate hexahydrate and 0.99g of nickel nitrate hexahydrate are added into a volumetric flask, 25ml of distilled water is added to prepare a mixed solution of cobalt nitrate and nickel nitrate for secondary impregnation, and ultrasonic vibration is carried out for 30min. The secondary impregnation was carried out in the same manner as in comparative example 2. The twice impregnated catalyst was dried at 110 ℃ for 12 hours and then calcined at 300 ℃ for 3 hours. Before the reaction, the catalyst was reduced for 1h under the conditions of 400 ℃ and hydrogen atmosphere, and after cooling, co-Ni-MgO/SiO 2 catalyst samples with the loading of 20wt.%,5wt.% and 10wt.% of Co, ni and MgO were prepared, respectively.
Example 8
4G of SiO 2 carrier were weighed out with an analytical balance and placed in an evaporation dish. 1.68g of tetrawater and calcium nitrate are added into a volumetric flask, 25ml of distilled water is added to prepare a calcium nitrate aqueous solution, and ultrasonic vibration is carried out for 30min. The crucible was placed under a 375W tungsten lamp to adjust the SiO 2 surface temperature to about 70 ℃. And (3) dropwise adding 25ml of the prepared calcium nitrate aqueous solution onto the surface of SiO 2, wherein the volume of the solution added dropwise is about 0.3ml each time, uniformly stirring the SiO 2 carrier after the surface of SiO 2 is completely dried, and then carrying out the next dropwise adding operation, and repeating the operation until the calcium nitrate aqueous solution is completely added. The impregnated catalyst was dried at 110℃for 12 hours and then calcined at 500℃for 3 hours to give CaO/SiO 2. 3.20g of cobalt nitrate hexahydrate and 0.99g of nickel nitrate hexahydrate are added into a volumetric flask, 25ml of distilled water is added to prepare a mixed solution of cobalt nitrate and nickel nitrate for secondary impregnation, and ultrasonic vibration is carried out for 30min. The secondary impregnation was carried out in the same manner as in comparative example 2. The twice impregnated catalyst was dried at 110 ℃ for 12 hours and then calcined at 300 ℃ for 3 hours. Before the reaction, the catalyst was reduced for 1h under the conditions of 400 ℃ and hydrogen atmosphere, and after cooling, co-Ni-CaO/SiO 2 catalyst samples with the loadings of 20wt.%,5wt.% and 10wt.% of Co, ni and CaO were prepared.
Reaction examples
Comparative example 3
20G of 1, 4-dioxane solution having a succinic acid concentration of 5wt.% and 1g of the catalyst prepared in comparative example 1 were charged into a reaction vessel having a volume of 25ml and reacted for 12 hours under hydrogen pressure conditions of 5MPa at 200 ℃. After the reaction, separating the catalyst from the reaction liquid by centrifugation and suction filtration, quantitatively analyzing the reaction liquid by a gas chromatograph, and obtaining the conversion rate of succinic acid and the selectivity of each product by calculation. The reaction results are shown in Table 1, and under the reaction conditions, the conversion of succinic acid was 98.8%, and the selectivity and yield of 1, 4-butanediol were 35.3% and 34.8%, respectively. As shown in table 1.
Comparative example 4
20G of 1, 4-dioxane solution having a succinic acid concentration of 5wt.% and 1g of the catalyst prepared in comparative example 2 were charged into a reaction vessel having a volume of 25ml and reacted for 12 hours under hydrogen pressure conditions of 5MPa at 180 ℃. After the reaction, separating the catalyst from the reaction liquid by centrifugation and suction filtration, quantitatively analyzing the reaction liquid by a gas chromatograph, and obtaining the conversion rate of succinic acid and the selectivity of each product by calculation. Under the reaction conditions, the conversion of succinic acid was 91.6%, and the selectivity and yield of 1, 4-butanediol were 42.6% and 39.0%, respectively. As shown in table 1.
Example 9
20G of 1, 4-dioxane solution having a succinic acid concentration of 5wt.% and 1g of the catalyst prepared in example 1 were charged into a reaction vessel having a volume of 25ml and reacted for 8 hours at 180℃under a hydrogen pressure of 5 MPa. After the reaction, separating the catalyst from the reaction liquid by centrifugation and suction filtration, quantitatively analyzing the reaction liquid by a gas chromatograph, and obtaining the conversion rate of succinic acid and the selectivity of each product by calculation. Under this reaction condition, the conversion of succinic acid was 78.8%, and the selectivity and yield of 1, 4-butanediol were 72.5% and 57.1%, respectively. As shown in table 1.
Example 10
20G of 1, 4-dioxane solution having a succinic acid concentration of 5wt.% and 1g of the catalyst prepared in example 2 were charged into a reaction vessel having a volume of 25ml and reacted for 8 hours at 180℃under a hydrogen pressure of 5 MPa. After the reaction, separating the catalyst from the reaction liquid by centrifugation and suction filtration, quantitatively analyzing the reaction liquid by a gas chromatograph, and obtaining the conversion rate of succinic acid and the selectivity of each product by calculation. Under the reaction conditions, the conversion of succinic acid was 72.5%, and the selectivity and yield of 1, 4-butanediol were 52.4% and 38.0%, respectively. As shown in table 1.
Example 11
20G of 1, 4-dioxane solution having a succinic acid concentration of 5wt.% and 0.5g of the catalyst prepared in example 3 were charged into a reaction vessel having a volume of 25ml and reacted for 4 hours at 180℃under a hydrogen pressure of 5 MPa. After the reaction, separating the catalyst from the reaction liquid by centrifugation and suction filtration, quantitatively analyzing the reaction liquid by a gas chromatograph, and obtaining the conversion rate of succinic acid and the selectivity of each product by calculation. Under this reaction condition, the conversion of succinic acid was 88.9%, and the selectivity and yield of 1, 4-butanediol were 96.5% and 85.8%, respectively. The reaction time was prolonged to 8 hours, the conversion of succinic acid was 99.8%, and the selectivity and yield of 1, 4-butanediol were 96.1% and 94.2%, respectively. As shown in table 1.
Example 12
20G of 1, 4-dioxane solution having a succinic acid concentration of 5wt.% and 0.5g of the catalyst prepared in example 4 were charged into a reaction vessel having a volume of 25ml and reacted for 4 hours at 180℃under a hydrogen pressure of 5 MPa. After the reaction, separating the catalyst from the reaction liquid by centrifugation and suction filtration, quantitatively analyzing the reaction liquid by a gas chromatograph, and obtaining the conversion rate of succinic acid and the selectivity of each product by calculation. Under the reaction conditions, the conversion of succinic acid was 82.3%, and the selectivity and yield of 1, 4-butanediol were 90.4% and 74.4%, respectively. As shown in table 1.
Example 13
20G of 1, 4-dioxane solution having a succinic acid concentration of 5wt.% and 0.5g of the catalyst prepared in example 5 were charged into a reaction vessel having a volume of 25ml and reacted for 4 hours at 180℃under a hydrogen pressure of 5 MPa. After the reaction, separating the catalyst from the reaction liquid by centrifugation and suction filtration, quantitatively analyzing the reaction liquid by a gas chromatograph, and obtaining the conversion rate of succinic acid and the selectivity of each product by calculation. Under this reaction condition, the conversion of succinic acid was 83.0%, and the selectivity and yield of 1, 4-butanediol were 93.5% and 77.6%, respectively. As shown in table 1.
Example 14
20G of 1, 4-dioxane solution having a succinic acid concentration of 5wt.% and 0.5g of the catalyst prepared in example 6 were charged into a reaction vessel having a volume of 25ml and reacted for 4 hours at 180℃under a hydrogen pressure of 5 MPa. After the reaction, separating the catalyst from the reaction liquid by centrifugation and suction filtration, quantitatively analyzing the reaction liquid by a gas chromatograph, and obtaining the conversion rate of succinic acid and the selectivity of each product by calculation. Under this reaction condition, the conversion of succinic acid was 62.6%, and the selectivity and yield of 1, 4-butanediol were 78.2% and 49.0%, respectively. As shown in table 1.
Example 15
20G of 1, 4-dioxane solution having a succinic acid concentration of 5wt.% and 0.5g of the catalyst prepared in example 7 were charged into a reaction vessel having a volume of 25ml and reacted for 8 hours at 180℃under a hydrogen pressure of 5 MPa. After the reaction, separating the catalyst from the reaction liquid by centrifugation and suction filtration, quantitatively analyzing the reaction liquid by a gas chromatograph, and obtaining the conversion rate of succinic acid and the selectivity of each product by calculation. Under this reaction condition, the conversion of succinic acid was 75.3%, and the selectivity and yield of 1, 4-butanediol were 58.2% and 43.8%, respectively. As shown in table 1.
Example 16
20G of 1, 4-dioxane solution having a succinic acid concentration of 5wt.% and 0.5g of the catalyst prepared in example 8 were charged into a reaction vessel having a volume of 25ml and reacted for 8 hours at 180℃under a hydrogen pressure of 5 MPa. After the reaction, separating the catalyst from the reaction liquid by centrifugation and suction filtration, quantitatively analyzing the reaction liquid by a gas chromatograph, and obtaining the conversion rate of succinic acid and the selectivity of each product by calculation. Under this reaction condition, the conversion of succinic acid was 69.4%, and the selectivity and yield of 1, 4-butanediol were 49.1% and 34.1%, respectively. As shown in table 1.
Example 17
20G of 1, 4-dioxane solution having a succinic acid concentration of 5wt.% and 0.5g of the catalyst prepared in example 3 were charged into a reaction vessel having a volume of 25ml and reacted for 6 hours at 160℃under a hydrogen pressure of 7 MPa. After the reaction, separating the catalyst from the reaction liquid by centrifugation and suction filtration, quantitatively analyzing the reaction liquid by a gas chromatograph, and obtaining the conversion rate of succinic acid and the selectivity of each product by calculation. Under the reaction conditions, the conversion of succinic acid was 96.2%, and the selectivity and yield of 1, 4-butanediol were 98.8% and 95.0%, respectively. As shown in table 1.
TABLE 1
The foregoing has outlined rather broadly the more detailed description of embodiments of the invention, wherein the principles and embodiments of the invention are explained in detail using specific examples, the above examples being provided solely to facilitate the understanding of the method and core concepts of the invention; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present invention, the present description should not be construed as limiting the present invention in view of the above.
Claims (9)
1. A catalyst is characterized in that the expression formula of the catalyst is Co-X-M/SiO 2, wherein SiO 2 is a carrier, X is one or two of Cu, ni, fe, zn, mn, mo, V or Cr metal elements, M is one of alkali metal oxide and alkaline earth metal oxide, the content of the SiO 2 carrier is 60-89 wt%, the content of Co component is 5-30 wt%, the content of X component is 1-15 wt%, and the content of M component is 5-20 wt%.
2. A catalyst according to claim 1, wherein M is selected from Li 2 O, mgO or CaO.
3. A method for preparing a catalyst according to claim 1, comprising:
Dipping a metal solution of alkali metal or alkaline earth metal into a SiO 2 carrier, and drying and calcining to obtain an M/SiO 2 catalyst;
And step two, dipping the mixed metal solution of Co and the metal component X into the M/SiO 2 prepared in the step one according to the method of the step one, and drying, calcining and reducing to obtain the catalyst Co-X-M/SiO 2.
4. A process for preparing a catalyst according to claim 3, wherein the impregnation is carried out by uniformly dropping a metal solution of an alkali metal or an alkaline earth metal onto the surface of SiO 2 drop by drop, evaporating the solution under irradiation of a tungsten lamp at 65-75 ℃, stirring SiO 2 until SiO 2 is dried until it is uniform, and then dropping the solution again, and repeating the above steps until the metal solution is consumed.
5. A method for preparing a catalyst according to claim 3, wherein the calcination temperature in the first step is 200-800 ℃, the calcination time is 1-6 hours, and the calcination temperature in the second step is 200-600 ℃ and the calcination time is 1-6 hours.
6. A method for preparing a catalyst according to claim 3, wherein the reduction temperature in the second step is 200-600 ℃ and the reduction time is 0.5-4h.
7. Use of the catalyst of claim 1 in the preparation of 1, 4-butanediol by hydrogenation of succinic acid.
8. The use of the catalyst according to claim 7 for preparing 1, 4-butanediol by hydrogenating succinic acid, wherein the method for preparing 1, 4-butanediol by hydrogenating succinic acid comprises the following steps:
and (3) taking H 2 as a hydrogen source to carry out succinic acid hydrogenation reaction, and adding the reduced Co-X-M/SiO 2 catalyst, succinic acid and a solvent into a reaction kettle to react to prepare the 1, 4-butanediol.
9. The use of the catalyst according to claim 8 for preparing 1, 4-butanediol by hydrogenating succinic acid, wherein the reaction temperature is 140-200 ℃, the hydrogen pressure is 3-10MPa, and the reaction time is 1-28h.
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| GB969523A (en) * | 1960-06-27 | 1964-09-09 | Montedison Spa | Catalyst and process for hydrogenation of esters, acids, acetals and aldehydes |
| CN1114488C (en) * | 1999-08-30 | 2003-07-16 | 标准石油公司 | Improved catalyst for preparing 1,4-butanediol by hydrogenation of maleic acid |
| US10450252B2 (en) * | 2016-03-31 | 2019-10-22 | Basf Se | Method for hydrogenating carboxylic acids in order to form alcohols |
| CN112473709A (en) * | 2019-09-11 | 2021-03-12 | 王宏涛 | Catalyst for synthesizing succinic acid by aqueous phase catalytic hydrogenation and application thereof |
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| CN115448814A (en) * | 2022-10-14 | 2022-12-09 | 河北工业大学 | Method for preparing 1,4-butanediol through catalytic hydrogenation of gamma-butyrolactone |
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