CN116474790A - Catalyst for producing succinic anhydride by maleic anhydride high-selectivity hydrogenation and preparation thereof - Google Patents

Catalyst for producing succinic anhydride by maleic anhydride high-selectivity hydrogenation and preparation thereof Download PDF

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CN116474790A
CN116474790A CN202310298987.9A CN202310298987A CN116474790A CN 116474790 A CN116474790 A CN 116474790A CN 202310298987 A CN202310298987 A CN 202310298987A CN 116474790 A CN116474790 A CN 116474790A
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catalyst
temperature
maleic anhydride
carrier
succinic anhydride
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唐明兴
李学宽
王福江
周立公
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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Abstract

The invention belongs to the technical field of succinic anhydride production by maleic anhydride hydrogenation, and particularly relates to a catalyst for producing succinic anhydride by maleic anhydride high-selectivity hydrogenation and a preparation method thereof. It is composed of active component and carrier, and the active component is complexed with the carrierThe mixture is highly dispersed on the carrier in an alloy state, the dosage of the mixture is 1-30wt% of the total weight of the catalyst, and the rest is the carrier; the specific surface area of the catalyst is 30-200m 2 Per g, the surface acid amount is 0.01-1.2mmol NH 3 And/g, wherein the average pore diameter is 9-30nm, and pores with the pore diameter of 10-20nm account for 50-80% of the total pore channels of the catalyst. The catalyst regulates and controls the performance of the catalyst by alloying active components and controlling the combination of the specific surface area, the surface acid amount and the pore diameter of the catalyst, can effectively improve the hydrogenation activity of maleic anhydride and the selectivity of succinic anhydride of a product, and greatly reduces the separation cost of the product, and the purity of the succinic anhydride reaches the requirement of a polymerization grade.

Description

Catalyst for producing succinic anhydride by maleic anhydride high-selectivity hydrogenation and preparation thereof
Technical Field
The invention belongs to the technical field of succinic anhydride production by maleic anhydride hydrogenation, and particularly relates to a catalyst for producing succinic anhydride by maleic anhydride high-selectivity hydrogenation and a preparation method thereof.
Background
Succinic anhydride is an important organic synthesis intermediate and fine chemical raw material, and is widely applied to the fields of foods, surfactants, coatings, medicines, agriculture, plastics and the like. With the growing problems of white pollution and non-renewable energy crisis, the development and use of biodegradable plastics is an essential requirement for plastics production and commercial fields. Polybutylene succinate (PBS) is a novel full-biodegradable plastic with excellent performance, and has the advantages of high melting point, good heat resistance, excellent mechanical property and relatively low price (1/3 of the existing biodegradable plastic) compared with the traditional biodegradable plastic. The succinic anhydride is used as a main raw material of the Poly Butylene Succinate (PBS), has great development prospect in the field of biodegradable plastics, greatly increases the demand, and is expected to reach 300 ten thousand tons/year within five years.
At present, the industrial succinic anhydride production method mainly comprises a biological fermentation method, a succinic anhydride dehydration method, a maleic anhydride hydrogenation method and the like. The technical route of the biological fermentation method has the advantages that the yield of the succinic anhydride is about 85 percent, the process has the problems of low product extraction efficiency, low yield and conversion rate, high cost and large amount of waste water and byproducts generated in the production process, and the industrial production needs are difficult to meet. The succinic acid dehydration method is divided into a direct dehydration method and a chemical dehydration method, and the method is limited to be popularized due to the defects of high equipment and capital investment, high product cost, unstable quality, high energy consumption in the production process, easy corrosion of equipment and the like. The maleic anhydride hydrogenation method has the advantages of simple process flow, obvious economic and ecological benefits and the like, and has higher industrialized application prospect. In recent years, attention has been paid to researchers.
Patent SU1541210, ru2058311 and EP0691335 disclose catalysts having a noble metal Pd content of 2-10 wt%. By adopting the catalyst, the yield of succinic anhydride is 90-95% under the condition that the reaction pressure is 4.0-6.0 MPa.
Patents US5952514 and US5770744 disclose a catalyst made by pressing iron and inert elements aluminum, silicon, titanium or iron, cobalt, nickel and carbon alloy powder, by which maleic anhydride conversion is 99% and succinic anhydride selectivity is 98% at a reaction temperature of 60-180 ℃ and a pressure of 380 bar.
Patent CN114471638A discloses a catalyst for synthesizing succinic acid (anhydride) and its preparation process, in which the catalyst is prepared by activating Ni, mo, co, W metal compound into metal phosphide, using alkali metal salt as solid alkali oxide and using auxiliary salt as auxiliary oxide Nd 2 O 3 Or La (La) 2 O 3 The catalyst is immobilized on a catalyst, and the catalyst has the function of selective hydrogenation of C=C bonds at low temperature to generate succinic acid (anhydride) under the synergistic effect of metal phosphide, solid alkali and auxiliary agent, and the yield of the succinic acid anhydride is over 99 percent under the conditions of the reaction temperature of 70-150 ℃ and the pressure of 1.0-5.0 MPa.
Patent CN111841551A discloses a high-efficiency catalyst for preparing succinic anhydride by maleic anhydride hydrogenation and a preparation method thereof. The catalyst is prepared by taking hydrotalcite-like compound as a precursor, and has high dispersity of active components, uniformity and two-dimensional nano-lamellar Ni-M-Al 2 O 3 The catalyst, M, refers to one or both of Cu, ag, au, pd, pt, fe, co, ru, rh, ir other than Ni. By adopting the catalyst, the maleic anhydride conversion rate is close to 100% and the succinic anhydride selectivity is above 98% at the reaction temperature of 40-200 ℃ and the pressure of 1.0-6.0 MPa.
Disclosure of Invention
Aiming at the problem of how to control the generation of byproducts in the process of synthesizing succinic anhydride by hydrogenating maleic anhydride at present, the invention provides a catalyst for producing succinic anhydride by hydrogenating maleic anhydride with high selectivity and a preparation method thereof.
The inventor screens out a catalyst suitable for synthesizing succinic anhydride by selective hydrogenation of maleic anhydride through a large number of experiments. The active component of the catalyst is in an alloy form on the catalyst through the complexing agent, so that the maleic anhydride hydrogenation activity and the succinic anhydride selectivity of the product are effectively improved, and meanwhile, the generation of maleic anhydride hydrogenation byproducts is further reduced by adopting a method of controlling the specific surface area, the surface acid amount and the pore diameter of the catalyst.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the catalyst for producing succinic anhydride by high-selectivity hydrogenation of maleic anhydride consists of an active component and a carrier, wherein the active component is highly dispersed on the carrier in an alloy state through a complexing agent, the dosage of the active component is 1-30wt% of the total weight of the catalyst, and the balance is the carrier;
the specific surface area of the catalyst is 30-200m 2 Per gram, the surface acid amount is 0.01-1.2mmolNH 3 And/g, wherein the average pore diameter is 9-30nm, and pores with the pore diameter of 10-20nm account for 50-80% of the total pore channels of the catalyst.
Further, the active component is at least two of metals Pt, pd, ru, cu, fe, co, ni, zn, mo, and the carrier is any one of alumina, titania, zirconia, silica and activated carbon.
Further, the complexing agent is any one of ammonia water, citric acid and ethylenediamine tetraacetic acid, and the addition amount of the complexing agent is 0.2-3.0 times of the sum of the molar amounts of the active component precursors.
A method for preparing a catalyst for producing succinic anhydride by high-selectivity hydrogenation of maleic anhydride, the method comprising the following steps:
(1) Preparing a mixed solution of soluble precursors of the active components, and adding a complexing agent to form a stable complex;
(2) Placing the carrier in the solution obtained in the step (1), dipping for 3-36h, and continuously stirring during the dipping process to ensure that the active components are distributed on the carrier according to specific structural characteristics;
(3) Drying the sample obtained in the step (2) at 80-150 ℃ for 6-24 hours, wherein the heating rate is 5-20 ℃/h;
(4) Roasting the sample obtained in the step (3) for 3-12 hours at 300-600 ℃;
(5) And (3) reducing the sample obtained in the step (4) in a reducing atmosphere to enable the active components to form an alloy, and then cooling to room temperature, and then, passivating by introducing passivation gas to obtain the required catalyst.
Further, the soluble precursor of the active component in the step (1) is at least two of nitrate, acetate, chloride, sulfate and carbonate.
Further, in the step (5), the temperature increasing program in the reduction step is as follows: raising the temperature from room temperature to 150 ℃ at a heating rate of 10-20 ℃/h, and keeping the temperature constant for 3-12h; raising the temperature to 250-350 ℃ at a heating rate of 10-20 ℃/h, and keeping the temperature constant for 3-12h; raising the temperature to 400-1000 ℃ at a heating rate of 10-20 ℃/h, and keeping the temperature constant for 3-6h.
Further, the reducing atmosphere in the step (5) is H 2 Or H 2 /N 2 Mixture gas, H 2 /N 2 H in the mixed gas 2 The content is 50-100%.
Further, the passivation gas in the step (5) is O 2 /N 2 Mixture gas, O 2 The content is 0.1-10%.
Further, the passivation time in the step (5) is 5-8h.
The application of a catalyst for producing succinic anhydride by high-selectivity hydrogenation of maleic anhydride, wherein the reaction conditions of the catalyst are as follows: under the pressure of 0.5-5.0MPa and hydrogen-oil volume ratio of 100-2000, heating to reaction temperature of 50-250 ℃ at the speed of 0.5-3.0 ℃/min, and controlling maleic anhydride concentration of 5-60% and volume space velocity of 0.5-6.0h -1 Is a feedstock reaction of (a).
The key factors in the preparation process of the catalyst are as follows: firstly, in the preparation process of the catalyst, the complexing agent is used for highly dispersing the active components of the catalyst, and the hydrogenation capacity of the catalyst to carboxyl in succinic anhydride is reduced through alloying of the active components, so that further hydrogenation of succinic anhydride to gamma-butyrolactone and other byproducts are inhibited. Secondly, the maleic anhydride hydrogenation by-product is further reduced by controlling the specific surface area of the catalyst, the surface acid amount and the pore diameter to optimize the combination.
Compared with the prior art, the invention has the following advantages:
the invention adopts a specific catalyst preparation method, utilizes a complexing agent to ensure that the active components of the catalyst are highly dispersed, controls the performance of the catalyst by alloying the active components and controlling the combination of the specific surface area, the surface acid quantity and the pore diameter of the catalyst, inhibits the generation of byproducts such as gamma-butyrolactone and the like, can effectively improve the maleic anhydride hydrogenation activity and the selectivity of the succinic anhydride product, greatly reduces the separation cost of the product, and ensures that the purity of the succinic anhydride meets the polymerization grade requirement.
Detailed Description
The invention is further illustrated, but is not limited, by the following examples.
Example 1
0.47g of nickel nitrate, 0.03g of platinum chloride, and 0.35g of ammonia were weighed into 10mL of deionized water, at which time the amount of ammonia added was 1.93 times the sum of the molar amounts of nickel nitrate and platinum chloride. The solution is stirred uniformly, 9.84g of active carbon carrier is added for impregnation, the mixture is stirred continuously in the impregnation process, the impregnated catalyst is filtered and dried after 3 hours, the temperature is slowly increased to 80 ℃ from the room temperature, the heating rate is 5 ℃/h, and the sample 1 is obtained by constant temperature drying for 24 hours at 80 ℃.
Sample 1 was calcined at 400℃for 5 hours to give sample 2. Sample 2 was taken at a space velocity of 3000h -1 H of (2) 2 Heating from room temperature to 150 ℃ at a speed of 10 ℃/h under the atmosphere, and keeping the temperature constant for 6h; raising the temperature to 250 ℃ at a heating rate of 10 ℃/h, and keeping the temperature constant for 3 hours; raising the temperature to 400 ℃ at a heating rate of 10 ℃/h, and keeping the temperature for 3h. Then at H 2 After the atmosphere had cooled to room temperature, the mixture was cooled to room temperature with O 2 O with a content of 0.1% 2 /N 2 Passivating for 6 hours to finally obtain the catalyst.
The nickel-platinum alloy component of the catalyst is 1.5wt% Ni+0.1wt% Pt, and the carrier active carbon component is 98.4wt%.
1mL of the catalyst was packed in a fixed bed tubular reactor. The catalyst was stirred at a volume space velocity of 1.0h -1 The hydrogen oil volume ratio (calculated as maleic anhydride) was 800, the pressure was 3.0MPa, and the hydrogen oil volume ratio (calculated as maleic anhydride solution) was 2.5Raising the temperature to 80 ℃ in the temperature per minute, and carrying out hydrogenation reaction by taking 10% maleic anhydride/tetrahydrofuran solution as a reaction raw material. The reaction results are shown in Table 1.
Example 2
1.42g of nickel acetate, 0.05g of palladium chloride, and 1.92g of citric acid were weighed out and added to 10mL of deionized water, at which time the amount of citric acid added was 1.20 times the sum of the molar amounts of nickel acetate and palladium chloride. Stirring the solution uniformly, adding 9.5g of titanium oxide carrier for impregnation, stirring continuously during the impregnation process, filtering out and drying the impregnated catalyst after 5 hours, slowly increasing the temperature from room temperature to 100 ℃, keeping the temperature rising rate at 10 ℃/h, and drying at the constant temperature for 8 hours at the temperature of 100 ℃ to obtain a sample 1.
Sample 1 was calcined at 400℃for 5 hours to give sample 2. Sample 2 was taken at a space velocity of 5000h -1 H of (2) 2 /N 2 Mixture of gases, where H 2 Heating from room temperature to 150 ℃ at a speed of 10 ℃/h under the atmosphere with the content of 50%, and keeping the temperature constant for 6 hours; raising the temperature to 250 ℃ at a heating rate of 10 ℃/h, and keeping the temperature constant for 3 hours; raising the temperature to 400 ℃ at a heating rate of 10 ℃/h, and keeping the temperature for 3h. Then at H 2 /N 2 After the atmosphere of the mixture was lowered to room temperature, O was used 2 O with a content of 0.5% 2 /N 2 Passivating for 10 hours to finally obtain the catalyst.
The nickel-palladium alloy component of the catalyst is 4.7wt% Ni+0.3wt% Pd, and the titanium oxide carrier is 95.0wt%.
1mL of the catalyst was packed in a fixed bed tubular reactor. The catalyst was stirred at a volume space velocity of 1.0h -1 The volume ratio of hydrogen to oil (calculated by maleic anhydride) is 500, the pressure is 4.0MPa, the temperature is increased to 90 ℃ at 2.5 ℃/min, and the reaction raw material is 20% maleic anhydride/1, 4-dioxane solution, so as to carry out hydrogenation reaction. The reaction results are shown in Table 1.
Example 3
1.59g of cobalt acetate, 0.58g of zinc nitrate, 0.12g of ruthenium chloride, and 1.02g of ammonia were weighed into 10mL of deionized water, at which time the amount of ammonia added was 0.87 times the sum of the molar amounts of cobalt acetate, zinc nitrate and ruthenium chloride. The solution is stirred uniformly, 9.1g of zirconia carrier is added for impregnation, the mixture is stirred continuously in the impregnation process, the impregnated catalyst is filtered and dried after 10 hours, the temperature is slowly increased to 100 ℃ from the room temperature, the heating rate is 10 ℃/h, and the sample 1 is obtained after the constant temperature drying for 10 hours at 100 ℃.
Sample 1 was calcined at 500℃for 8 hours to give sample 2. Sample 2 was taken at a space velocity of 3000h -1 H of (2) 2 Heating from room temperature to 150 ℃ at a speed of 10 ℃/h under the atmosphere, and keeping the temperature constant for 6h; raising the temperature to 250 ℃ at a heating rate of 10 ℃/h, and keeping the temperature constant for 3 hours; raising the temperature to 400 ℃ at a heating rate of 10 ℃/h, and keeping the temperature for 3h. Then at H 2 After the atmosphere had cooled to room temperature, the mixture was cooled down to room temperature with O 2 O with a content of 1.0% 2 /N 2 Passivating for 10 hours to finally obtain the catalyst.
The cobalt-zinc-ruthenium alloy component of the obtained catalyst is 8.0wt% Co+2wt% Zn+0.6wt% Ru, and the carrier zirconia is 89.4wt%.
1mL of the catalyst was packed in a fixed bed tubular reactor. The catalyst was stirred at a volume space velocity of 1.5h -1 The volume ratio of hydrogen to oil (calculated as maleic anhydride) is 800, the pressure is 3.0MPa, the temperature is raised to 100 ℃ at 2.5 ℃/min, and 20% maleic anhydride/tetrahydrofuran solution is used as the reaction raw material for hydrogenation reaction. The reaction results are shown in Table 1.
Example 4
2.49g of nickel nitrate, 0.39g of copper carbonate, 0.57g of molybdenum chloride, and 1.36g of ammonia were weighed into 10mL of deionized water, at which time the amount of ammonia added was 0.99 times the sum of the molar amounts of nickel nitrate, copper carbonate and molybdenum chloride. Stirring the solution uniformly, adding 8.8g of alumina carrier for impregnation, stirring continuously during the impregnation process, filtering out and drying the impregnated catalyst after 15 hours, slowly raising the temperature from room temperature to 120 ℃, wherein the temperature raising rate is 10 ℃/h, and drying at the constant temperature for 10 hours at the temperature of 120 ℃ to obtain a sample 1.
Sample 1 was calcined at 500℃for 5 hours to give sample 2. Sample 2 was taken at a space velocity of 3000h -1 H of (2) 2 Heating from room temperature to 150 ℃ at a speed of 10 ℃/h under the atmosphere, and keeping the temperature constant for 6h; raising the temperature to 250 ℃ at a heating rate of 10 ℃/h, and keeping the temperature constant for 3 hours; raising the temperature to 400 ℃ at a heating rate of 10 ℃/h, and keeping the temperature for 3h. Then at H 2 After the atmosphere had cooled to room temperature, the mixture was cooled down to room temperature with O 2 At a content of 1.5%O 2 /N 2 Passivating for 5 hours to finally obtain the catalyst.
The nickel-copper-molybdenum alloy component of the obtained catalyst comprises 8.0wt% of Ni+1.9wt% of Cu+3.4wt% of Mo, and the alumina carrier comprises 86.7wt%.
1mL of the catalyst was packed in a fixed bed tubular reactor. The catalyst was stirred at a volume space velocity of 0.5h -1 The volume ratio of hydrogen to oil (calculated by maleic anhydride) is 1000, the pressure is 5.0MPa, the temperature is increased to 120 ℃ at 2.5 ℃/min, and 50% maleic anhydride/tetrahydrofuran solution is used as the reaction raw material for hydrogenation reaction. The reaction results are shown in Table 1.
Example 5
3.88g of cobalt nitrate, 0.14g of platinum chloride, 2.92g of ethylenediamine tetraacetic acid was weighed out and added to 10mL of deionized water, at which time the amount of ethylenediamine tetraacetic acid added was 0.46 times the sum of the molar amounts of cobalt nitrate and platinum chloride. The solution is stirred uniformly, 8.7g of alumina carrier is added for impregnation, the stirring is continued during the impregnation process, the impregnated catalyst is filtered and dried after 20 hours, the temperature is slowly increased to 120 ℃ from the room temperature, the heating rate is 10 ℃/h, and the sample 1 is obtained after the constant temperature drying for 15 hours at 100 ℃.
Sample 1 was calcined at 500℃for 5 hours to give sample 2. Sample 2 was taken at a space velocity of 3000h -1 H of (2) 2 Heating from room temperature to 150 ℃ at a speed of 10 ℃/h under the atmosphere, and keeping the temperature constant for 6h; raising the temperature to 250 ℃ at a heating rate of 10 ℃/h, and keeping the temperature constant for 3 hours; raising the temperature to 400 ℃ at a heating rate of 10 ℃/h, and keeping the temperature for 3h. Then at H 2 After the atmosphere had cooled to room temperature, the mixture was cooled down to room temperature with O 2 O with a content of 1.0% 2 /N 2 Passivating for 8 hours to finally obtain the catalyst.
The cobalt-platinum alloy component of the obtained catalyst is 12.5wt% Co+0.8wt% Pt, and the alumina content of the carrier is 86.7wt%.
1mL of the catalyst was packed in a fixed bed tubular reactor. The catalyst was stirred at a volume space velocity of 1.2h -1 The volume ratio of hydrogen to oil (calculated as maleic anhydride) is 800, the pressure is 3.0MPa, the temperature is increased to 150 ℃ at 2.5 ℃/min, and 10% maleic anhydride/tetrahydrofuran solution is used as the reaction raw material for hydrogenation reaction.The reaction results are shown in Table 1.
Example 6
4.05g of nickel nitrate, 0.07g of palladium chloride, 0.23g of ferric sulfate, 1.36g of ammonia water were weighed out and added to 10mL of deionized water, at which time the addition amount of ammonia water was 0.86 times the sum of the molar amounts of nickel nitrate, palladium chloride and ferric sulfate. The solution is stirred uniformly, 8.5g of alumina carrier is added for impregnation, the stirring is continued during the impregnation process, the impregnated catalyst is filtered out and dried after 18 hours, the temperature is slowly increased to 120 ℃ from the room temperature, the heating rate is 10 ℃/h, and the sample 1 is obtained after the constant temperature drying for 15 hours at 100 ℃.
Sample 1 was calcined at 500℃for 5 hours to give sample 2. Sample 2 was taken at a space velocity of 3000h -1 H of (2) 2 Heating from room temperature to 150 ℃ at a speed of 10 ℃/h under the atmosphere, and keeping the temperature constant for 6h; raising the temperature to 250 ℃ at a heating rate of 10 ℃/h, and keeping the temperature constant for 3 hours; raising the temperature to 400 ℃ at a heating rate of 10 ℃/h, and keeping the temperature for 3h. Then at H 2 After the atmosphere had cooled to room temperature, the mixture was cooled down to room temperature with O 2 O with a content of 0.8% 2 /N 2 Passivating for 8 hours to finally obtain the catalyst.
The nickel-palladium-iron alloy of the catalyst contains 13.0wt% Ni+0.4wt% Pd+0.6wt% Fe and 86.0wt% carrier alumina.
1mL of the catalyst was packed in a fixed bed tubular reactor. The catalyst was stirred at a volume space velocity of 2.0h -1 The volume ratio of hydrogen to oil (calculated by maleic anhydride) is 1000, the pressure is 3.0MPa, the temperature is increased to 170 ℃ at 2.5 ℃/min, and 30% maleic anhydride/1, 4-dioxane solution is used as the reaction raw material for hydrogenation reaction. The reaction results are shown in Table 1.
Example 7
3.11g of nickel nitrate, 1.24g of cobalt nitrate, 0.25g of copper sulfate, and 1.36g of ammonia were weighed into 10mL of deionized water, at which time the amount of ammonia added was 0.79 times the sum of the molar amounts of nickel nitrate, cobalt nitrate, and copper sulfate. Stirring the solution uniformly, adding 8.5g of active carbon carrier for impregnation, stirring continuously during the impregnation process, filtering out and drying the impregnated catalyst after 18 hours, slowly raising the temperature from room temperature to 120 ℃, keeping the temperature raising rate at 10 ℃/h, and drying at the constant temperature at 100 ℃ for 15 hours to obtain a sample 1.
Sample 1 was calcined at 500℃for 5 hours to give sample 2. Sample 2 was taken at a space velocity of 3000h -1 H of (2) 2 Heating from room temperature to 150 ℃ at a speed of 10 ℃/h under the atmosphere, and keeping the temperature constant for 6h; raising the temperature to 250 ℃ at a heating rate of 10 ℃/h, and keeping the temperature constant for 3 hours; raising the temperature to 400 ℃ at a heating rate of 10 ℃/h, and keeping the temperature for 3h. Then at H 2 After the atmosphere had cooled to room temperature, the mixture was cooled down to room temperature with O 2 O with a content of 1.0% 2 /N 2 Passivating for 8 hours to finally obtain the catalyst.
The nickel-cobalt-copper alloy component of the catalyst is 10.0wt% Ni+4wt% Co+1wt% Cu, and the carrier active carbon component is 85.0wt%.
1mL of the catalyst was packed in a fixed bed tubular reactor. The catalyst was stirred at a volume space velocity of 0.8h -1 The volume ratio of hydrogen to oil (calculated by maleic anhydride) is 1000, the pressure is 3.0MPa, the temperature is increased to 190 ℃ at 2.5 ℃/min, and 8% maleic anhydride/tetrahydrofuran solution is used as the reaction raw material for hydrogenation reaction. The reaction results are shown in Table 1.
Example 8
4.36g of nickel nitrate, 0.03g of platinum chloride, 1.86g of ferric sulfate, 0.58g of zinc nitrate, 2.92g of ethylenediamine tetraacetic acid were weighed out and added to 10mL of deionized water, at which time the amount of ethylenediamine tetraacetic acid added was 0.32 times the sum of the molar amounts of nickel nitrate, platinum chloride, ferric sulfate and zinc nitrate. Stirring the solution uniformly, adding 7.9g of alumina carrier for impregnation, stirring continuously during the impregnation process, filtering out and drying the impregnated catalyst after 25 hours, slowly raising the temperature from room temperature to 120 ℃, keeping the temperature raising rate at 10 ℃/h, and drying at the constant temperature for 15 hours at 100 ℃ to obtain a sample 1.
Sample 1 was calcined at 500℃for 5 hours to give sample 2. Sample 2 was taken at a space velocity of 3000h -1 H of (2) 2 Heating from room temperature to 150 ℃ at a speed of 10 ℃/h under the atmosphere, and keeping the temperature constant for 6h; raising the temperature to 250 ℃ at a heating rate of 10 ℃/h, and keeping the temperature constant for 3 hours; raising the temperature to 400 ℃ at a heating rate of 10 ℃/h, and keeping the temperature for 3h. Then at H 2 After the atmosphere had cooled to room temperature, the mixture was cooled down to room temperature with O 2 O with a content of 1.0% 2 /N 2 Passivating for 8 hours to finally obtain the catalyst.
The nickel-platinum-iron-zinc alloy component of the obtained catalyst comprises 14.0wt% of Ni+1.7wt% of Pt+5.2wt% of Fe+0.8wt% of Zn, and the alumina carrier comprises 78.3wt%.
1mL of the catalyst was packed in a fixed bed tubular reactor. The catalyst was stirred at a volume space velocity of 2.0h -1 The volume ratio of hydrogen to oil (calculated as maleic anhydride) is 500, the pressure is 3.0MPa, the temperature is increased to 210 ℃ at 2.5 ℃/min, and 10% maleic anhydride/tetrahydrofuran solution is used as the reaction raw material for hydrogenation reaction. The reaction results are shown in Table 1.
Example 9
7.47g of nickel nitrate, 0.03g of palladium chloride, 0.45g of copper sulfate and 2.92g of ethylenediamine tetraacetic acid were weighed out and added to 10mL of deionized water, at which time the amount of ethylenediamine tetraacetic acid added was 0.22 times the sum of the molar amounts of nickel nitrate, palladium chloride and copper sulfate. Stirring the solution uniformly, adding 7.4g of alumina carrier for impregnation, stirring continuously during the impregnation process, filtering out and drying the impregnated catalyst after 25 hours, slowly raising the temperature from room temperature to 120 ℃, keeping the temperature raising rate at 10 ℃/h, and drying at the constant temperature for 15 hours at 100 ℃ to obtain a sample 1.
Sample 1 was calcined at 500℃for 5 hours to give sample 2. Sample 2 was taken at a space velocity of 3000h -1 H of (2) 2 Heating from room temperature to 150 ℃ at a speed of 10 ℃/h under the atmosphere, and keeping the temperature constant for 6h; raising the temperature to 250 ℃ at a heating rate of 10 ℃/h, and keeping the temperature constant for 3 hours; raising the temperature to 400 ℃ at a heating rate of 10 ℃/h, and keeping the temperature for 3h. Then at H 2 After the atmosphere had cooled to room temperature, the mixture was cooled down to room temperature with O 2 O with a content of 1.5% 2 /N 2 Passivating for 8 hours to finally obtain the catalyst.
The nickel-palladium-copper alloy component of the obtained catalyst comprises 24.0wt% Ni+1.8wt% Pd+1.8wt% Cu, and the alumina carrier comprises 72.4wt%.
1mL of the catalyst was packed in a fixed bed tubular reactor. The catalyst was stirred at a volume space velocity of 2.5h -1 The volume ratio of hydrogen to oil (calculated as maleic anhydride) is 1000, the pressure is 3.0MPa, the temperature is increased to 240 ℃ at 2.5 ℃/min, and 15% maleic anhydride/tetrahydrofuran solution is used as the reaction raw material for hydrogenation reaction. The reaction results are shown in Table 1.
TABLE 1 catalyst characterization and reaction results
What is not described in detail in the present specification belongs to the prior art known to those skilled in the art. While the foregoing describes illustrative embodiments of the present invention to facilitate an understanding of the present invention by those skilled in the art, it should be understood that the present invention is not limited to the scope of the embodiments, but is to be construed as protected by the accompanying claims insofar as various changes are within the spirit and scope of the present invention as defined and defined by the appended claims.

Claims (10)

1. The catalyst for producing succinic anhydride by high-selectivity hydrogenation of maleic anhydride is characterized by comprising an active component and a carrier, wherein the active component is highly dispersed on the carrier in an alloy state through a complexing agent, the dosage of the active component is 1-30wt% of the total weight of the catalyst, and the balance is the carrier;
the specific surface area of the catalyst is 30-200m 2 Per gram, the surface acid amount is 0.01-1.2mmolNH 3 And/g, wherein the average pore diameter is 9-30nm, and pores with the pore diameter of 10-20nm account for 50-80% of the total pore channels of the catalyst.
2. The catalyst for the high-selectivity hydrogenation of maleic anhydride to succinic anhydride according to claim 1, wherein the active component is at least two of metals Pt, pd, ru, cu, fe, co, ni, zn, mo, and the carrier is any one of alumina, titania, zirconia, silica and activated carbon.
3. The catalyst for producing succinic anhydride by high-selectivity hydrogenation of maleic anhydride according to claim 1, wherein the complexing agent is any one of ammonia water, citric acid and ethylenediamine tetraacetic acid, and the addition amount of the complexing agent is 0.2-3.0 times of the sum of the molar amounts of the active component precursors.
4. A method for preparing a catalyst for the highly selective hydrogenation of maleic anhydride to succinic anhydride according to any one of claims 1 to 3, wherein the preparation method comprises the steps of:
(1) Preparing a mixed solution of soluble precursors of the active components, and adding a complexing agent to form a stable complex;
(2) Placing the carrier in the solution obtained in the step (1), dipping for 3-36h, and continuously stirring during the dipping process to ensure that the active components are distributed on the carrier according to specific structural characteristics;
(3) Drying the sample obtained in the step (2) at 80-150 ℃ for 6-24 hours, wherein the heating rate is 5-20 ℃/h;
(4) Roasting the sample obtained in the step (3) for 3-12 hours at 300-600 ℃;
(5) And (3) reducing the sample obtained in the step (4) in a reducing atmosphere to enable the active components to form an alloy, and then cooling to room temperature, and then, passivating by introducing passivation gas to obtain the required catalyst.
5. The method for preparing a catalyst according to claim 4, wherein the soluble precursor of the active ingredient in the step (1) is at least two of nitrate, acetate, chloride, sulfate and carbonate.
6. The method for preparing a catalyst according to claim 4, wherein the reducing step in step (5) is performed by a temperature-increasing program of: raising the temperature from room temperature to 150 ℃ at a heating rate of 10-20 ℃/h, and keeping the temperature constant for 3-12h; raising the temperature to 250-350 ℃ at a heating rate of 10-20 ℃/h, and keeping the temperature constant for 3-12h; raising the temperature to 400-1000 ℃ at a heating rate of 10-20 ℃/h, and keeping the temperature constant for 3-6h.
7. The method for preparing a catalyst according to claim 4, wherein the reducing atmosphere in the step (5) is H 2 Or H 2 /N 2 Mixture gas, H 2 /N 2 H in the mixed gas 2 The content is 50-100%.
8. The method for preparing a catalyst according to claim 4, wherein the passivation gas in the step (5) is O 2 /N 2 Mixture gas, O 2 The content is 0.1-10%.
9. The method for preparing a catalyst according to claim 4, wherein the passivation time in the step (5) is 5 to 8 hours.
10. Use of a catalyst for the production of succinic anhydride by highly selective hydrogenation of maleic anhydride according to any one of claims 1 to 3, wherein the catalyst reaction conditions are: under the pressure of 0.5-5.0MPa and hydrogen-oil volume ratio of 100-2000, heating to reaction temperature of 50-250 ℃ at the speed of 0.5-3.0 ℃/min, and controlling maleic anhydride concentration of 5-60% and volume space velocity of 0.5-6.0h -1 Is a feedstock reaction of (a).
CN202310298987.9A 2023-03-24 2023-03-24 Catalyst for producing succinic anhydride by maleic anhydride high-selectivity hydrogenation and preparation thereof Pending CN116474790A (en)

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