Preparation method of 2-butene isomerization catalyst
By introducing organic bases and metals into ZSM-22 molecular sieves, a highly efficient 2-butene isomer catalyst was prepared, which solved the problems of insufficient 2-butene conversion and catalyst stability, and achieved the effect of efficient conversion to 1-butene.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- DALIAN INSTITUTE OF CHEMICAL PHYSICS CHINESE ACADEMY OF SCIENCES
- Filing Date
- 2024-11-19
- Publication Date
- 2026-05-19
AI Technical Summary
In existing technologies, the conversion rate of 2-butene and the selectivity of 1-butene are low, and the catalyst stability is insufficient, resulting in inadequate utilization of C4 resources.
By introducing an organic base and loading cobalt or nickel into ZSM-22 molecular sieves, a highly efficient 2-butene isomer catalyst was prepared by adjusting the acid strength and pore size distribution, thereby improving the 2-butene conversion rate and catalyst stability.
The catalyst achieved efficient conversion of 2-butene to 1-butene, exhibiting excellent catalytic performance and stability. The catalyst preparation method is simple and the raw materials are inexpensive.
Abstract
Description
Technical Field
[0001] This application relates to a method for preparing a 2-butene isomeric catalyst, which belongs to the field of chemical engineering. Background Technology
[0002] n-Butene, as an important basic chemical raw material, is mainly used to manufacture butadiene, and secondarily to manufacture methyl ethyl ketone, sec-butanol, epoxide, and butene polymers and copolymers. Isobutylene is mainly used to manufacture butyl rubber, polyisobutylene rubber, and various plastics.
[0003] Traditional production methods include the oligomerization of ethylene with a nickel catalyst to produce long-chain α-olefins, partially generating n-butene; and the disproportionation of propylene to produce ethylene and 2-butene, both of which are of low purity. Similarly, the C4 fraction obtained from catalytic cracking contains approximately 13% 1-butene, 12% cis-2-butene, and 13% trans-2-butene; the cracked C4 fraction contains approximately 14% 1-butene, 5% cis-2-butene, and 6% trans-2-butene.
[0004] To make more rational use of C4 resources, research on the isomerization of 2-butene to 1-butene has received widespread attention. Patent CN102649674 A discloses alkali metal-supported ZSM molecular sieves, which exhibit high selectivity for 1-butene, but their conversion rate remains low. Therefore, developing highly efficient catalysts for 2-butene double bond isomerization remains a pressing issue. Summary of the Invention
[0005] This application improves the conversion and stability of 2-butene by introducing metal atoms into the molecular sieve framework, thereby modulating its acid strength and improving pore size distribution. In view of the problems existing in the prior art, the purpose of this invention is to provide a method for preparing a 2-butene isomer catalyst that exhibits excellent catalytic performance and stability in the catalytic reaction of 2-butene isomerization directly to 1-butene. To achieve the above objective, a metal is introduced into an organic base-modified ZSM-22 molecular sieve, which improves the catalytic performance of 2-olefin double bond isomerization and increases the catalyst's stability.
[0006] According to one aspect of this application, a method for preparing a 2-butene isomer catalyst is provided, characterized in that...
[0007] Includes the following steps:
[0008] 2-Butene is reacted with a catalyst to yield 1-butene;
[0009] The catalyst is composed of active metal and organic base modified ZSM-22 molecular sieve.
[0010] The catalyst contains 0.5 to 5 wt% active metal.
[0011] The active metal is one or both of cobalt and nickel.
[0012] The organic base modified ZSM-22 molecular sieve is obtained through the following steps:
[0013] ZSM-22 molecular sieve was impregnated in an organic alkali solution, washed, dried (I), and calcined (I) to obtain organic alkali modified ZSM-22 molecular sieve.
[0014] The organic base in the organic base solution is selected from one of triethylamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide;
[0015] The concentration of the organic base solution is 0.05–2 mol / L;
[0016] The volume ratio of the ZSM-22 molecular sieve to the organic alkali solution is 1:5 to 20;
[0017] The silicon-to-aluminum ratio of the ZSM-22 molecular sieve is 50 to 200.
[0018] The impregnation temperature is 150–170°C;
[0019] The soaking time is 6-8 hours;
[0020] The temperature of the drying process I is 100–120°C;
[0021] The drying time for step I is 6–12 hours;
[0022] The temperature of the calcination I is 550–650°C;
[0023] The roasting time for the first stage is 6 to 8 hours.
[0024] The catalyst is obtained through the following steps:
[0025] The catalyst was obtained by mixing organic base-modified ZSM-22 molecular sieve and metal salt solution, followed by aging, drying (II), and calcination (II).
[0026] The metal salt in the metal salt solution is selected from at least one of Co(NO3)2·6H2O and Ni(NO3)2·6H2O;
[0027] The concentration of the metal salt solution is 0.005–0.025 g / ml;
[0028] The mass ratio of the organic base modified ZSM-22 molecular sieve to the metal salt is 4 to 15:1.
[0029] The aging time is 1 to 12 hours;
[0030] The temperature of the drying II process is 100–120°C;
[0031] The drying time for step II is 6–12 hours;
[0032] The temperature of the second calcination is 500–600°C;
[0033] The roasting time is 4 to 8 hours.
[0034] The catalyst is activated;
[0035] The activation atmosphere is a nitrogen atmosphere;
[0036] The activation temperature is 400–500°C;
[0037] The activation time is 2 to 5 hours.
[0038] Optionally, the catalyst is obtained through the following steps:
[0039] a) Take ZSM-22 molecular sieve, add it to an organic base solution, put it into a crystallizer, and place it in an oven at 140-170℃ for 5-15 hours;
[0040] b) Centrifuge, filter, wash, dry, and calcine at 550℃-650℃ for 6-8 hours to obtain organic alkali modified ZSM-22 molecular sieve.
[0041] The catalyst is prepared as follows:
[0042] a) Prepare a solution containing a certain amount of active metal salt;
[0043] b) A certain mass of organic base-modified ZSM-22 molecular sieve is added to a);
[0044] c) After aging for a certain period of time, the catalyst is dried and calcined to obtain the active metal-organic base modified ZSM-22 molecular sieve catalyst.
[0045] The feed space velocity of the 2-butene is 10–25 h⁻¹. -1 ;
[0046] The reaction temperature is 200–400°C;
[0047] The reaction pressure is 0.1–3 MPa.
[0048] The beneficial effects that this application can produce include:
[0049] 1) This invention introduces metal into ZSM-22 molecular sieve modified with organic base to prepare a catalyst for the isomerization of 2-butene to 1-butene. The catalyst has high 2-butene conversion rate, 1-butene selectivity and catalyst stability.
[0050] 2) The catalyst preparation method provided by this invention is simple and efficient, and the raw materials are inexpensive and of stable quality. Detailed Implementation
[0051] The present invention will be described in detail below with reference to the embodiments, but the scope of protection of the present invention is not limited to the following embodiments.
[0052] Example 1
[0053] Preparation and application of modified ZSM-22 (silicon-to-aluminum ratio 100) catalyst
[0054] Add 0.505 g of triethylamine and 100 g of deionized water to a beaker and stir well to prepare a 0.05 mol·L⁻¹ solution. -1 The solution was prepared by adding 10g of ZSM-22 (silicon-to-aluminum ratio 100) molecular sieve to the above solution, transferring it to a crystallizer, and placing it in an oven at 150℃ for 6 hours. The white solid was washed with water until neutral, dried at 100℃ overnight, and calcined at 550℃ for 8 hours to obtain the modified ZSM-22 (silicon-to-aluminum ratio 100) molecular sieve.
[0055] 1g of the prepared catalyst was loaded into a fixed-bed reactor, and the temperature was increased to 450℃ at a rate of 10℃ / min with 50ml / min N2, and activated for 4h. The reactor was then activated at 380℃, 0.5MPa, and a space velocity of 10h⁻¹. -1 The reaction was carried out under the specified conditions. The results are listed in Table 1.
[0056] Example 2
[0057] Preparation and application of modified ZSM-22 (silicon-to-aluminum ratio 150) catalyst
[0058] Configure 1.5 mol·L -1 A tetrapropylammonium hydroxide solution was prepared; 10g of ZSM-22 (silicon-to-aluminum ratio 150) molecular sieve was added to the above solution, transferred to a crystallizer, and placed in an oven at 170℃ for 8 hours; the white solid was taken out, washed with water until neutral, dried at 100℃ overnight, and calcined at 600℃ for 6 hours to obtain the modified ZSM-22 (silicon-to-aluminum ratio 150) molecular sieve.
[0059] 1g of the prepared catalyst was loaded into a fixed-bed reactor, and the temperature was increased to 450℃ at a rate of 10℃ / min with 50ml / min N2, and activated for 4h. The reactor was then activated at 380℃, 1MPa pressure, and a space velocity of 10h⁻¹. -1 The reaction was carried out under the specified conditions. The results are listed in Table 1.
[0060] Example 3
[0061] Preparation and application of Co / ZSM-22 (silicon-to-aluminum ratio 100) catalyst
[0062] Add 0.505 g of triethylamine and 100 g of deionized water to a beaker and stir well to prepare a 0.05 mol·L⁻¹ solution. -1 The solution was prepared by adding 5g of ZSM-22 (silicon-to-aluminum ratio 100) molecular sieve to the above solution, transferring it to a crystallizer, and placing it in an oven at 150℃ for 6 hours. The white solid was washed with water until neutral, dried at 100℃ overnight, and calcined at 550℃ for 8 hours to obtain the modified ZSM-22 (silicon-to-aluminum ratio 100) molecular sieve.
[0063] 0.1g of Co(NO3)2·6H2O was added to 20mL of deionized water and stirred to dissolve. Then, 1g of modified ZSM-22 (silicon-to-aluminum ratio 100) molecular sieve was added to it. After aging for a certain period of time, it was dried, ground, and calcined in a muffle furnace at 550℃ for 6h to obtain Co / ZSM-22 (silicon-to-aluminum ratio 100) molecular sieve.
[0064] 1g of the prepared catalyst was loaded into a fixed-bed reactor, and the temperature was increased to 450℃ at a rate of 10℃ / min with 50ml / min N2, and activated for 4h. The reactor was then activated at 400℃, 0.2MPa, and a space velocity of 15h⁻¹. -1 The reaction was carried out under the specified conditions. The results are listed in Table 1.
[0065] Example 4
[0066] Preparation and application of Ni / ZSM-22 (silicon-to-aluminum ratio 150) catalyst
[0067] Prepare 1 mol·L -1 A tetrapropylammonium hydroxide solution was prepared; 10g of ZSM-22 (silicon-to-aluminum ratio 150) molecular sieve was added to the above solution, transferred to a crystallizer, and placed in an oven at 170℃ for 8 hours; the white solid was taken out, washed with water until neutral, dried at 100℃ overnight, and calcined at 600℃ for 6 hours to obtain the modified ZSM-22 (silicon-to-aluminum ratio 150) molecular sieve.
[0068] 0.12g Ni(NO3)2·6H2O was added to 20mL of deionized water and stirred to dissolve. Then, 1g of modified ZSM-22 (silicon-to-aluminum ratio 150) molecular sieve was added to it. After aging for a certain period of time, drying, grinding, and calcining in a muffle furnace at 550℃ for 6h, Ni / ZSM-22 (silicon-to-aluminum ratio 150) molecular sieve was obtained.
[0069] 1g of the prepared catalyst was loaded into a fixed-bed reactor, and the temperature was increased to 450℃ at a rate of 10℃ / min with 50ml / min N2, and activated for 4h. The reactor was then activated at 400℃, 0.2MPa, and a space velocity of 15h⁻¹. -1 The reaction was carried out under the specified conditions. The results are listed in Table 1.
[0070] Example 5
[0071] Preparation and application of Co / ZSM-22 (silicon-to-aluminum ratio 150) catalyst
[0072] Prepare 2 mol·L -1 A tetrabutylammonium hydroxide solution was prepared; 15g of ZSM-22 (silicon-to-aluminum ratio 150) molecular sieve was added to the above solution, transferred to a crystallizer, and placed in an oven at 170℃ for 8h; the white solid was taken out, washed with water until neutral, dried at 100℃ overnight, and calcined at 550℃ for 6h to obtain the modified ZSM-22 (silicon-to-aluminum ratio 150) molecular sieve.
[0073] 0.5g of Co(NO3)2·6H2O was added to 20mL of deionized water and stirred to dissolve. Then, 5g of modified ZSM-22 (silicon-to-aluminum ratio 150) molecular sieve was added to it. After aging for a certain period of time, it was dried, ground, and calcined in a muffle furnace at 550℃ for 8h to obtain Co / ZSM-22 (silicon-to-aluminum ratio 150) molecular sieve.
[0074] 1g of the prepared catalyst was loaded into a fixed-bed reactor, and the temperature was increased to 450℃ at a rate of 10℃ / min with 50ml / min N2, and activated for 4h. The reactor was then activated at 350℃, 0.2MPa, and a space velocity of 10h⁻¹. -1 The reaction was carried out under the specified conditions. The results are listed in Table 1.
[0075] Comparative Example 1
[0076] Application of ZSM-22 (silicon-to-aluminum ratio 100) catalyst
[0077] 1g of the prepared catalyst was loaded into a fixed-bed reactor, and the temperature was increased to 500℃ at a rate of 10℃ / min with 50ml / min N2, and activated for 4h. The reactor was then activated at 380℃, 0.1MPa, and a space velocity of 15h⁻¹. -1 The reaction was carried out under the specified conditions. The results are listed in Table 1.
[0078] Comparative Example 2
[0079] Application of ZSM-22 (silicon-to-aluminum ratio 150) catalyst
[0080] 1g of the prepared catalyst was loaded into a fixed-bed reactor, and the temperature was increased to 500℃ at a rate of 10℃ / min with 50ml / min N2, and activated for 4h. The reactor was then activated at 400℃, 0.5MPa, and a space velocity of 10h⁻¹. -1 The reaction was carried out under the specified conditions. The results are listed in Table 1.
[0081] Table 1. Experimental results for catalyst activity evaluation
[0082] Example 2-Butene conversion rate / % 1-Butene selectivity / % Lifespan / h Example 1 25.9 80.1 6000 Example 2 26.3 82.2 6000 Example 3 37.9 98.4 7000 Example 4 35.6 98 8000 Example 5 34.3 97.8 7500 Comparative Example 1 25.2 50.5 1000 Comparative Example 2 27.6 46.7 1200
[0083] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.
Claims
1. A method for preparing a 2-butene isomer catalyst, characterized in that, Includes the following steps: 2-Butene is reacted with a catalyst to yield 1-butene; The catalyst is composed of active metal and organic base modified ZSM-22 molecular sieve.
2. The method according to claim 1, characterized in that, The catalyst contains 0.5 to 5 wt% active metal. The active metal is one or both of cobalt and nickel.
3. The method according to claim 1, characterized in that, The organic base modified ZSM-22 molecular sieve is obtained through the following steps: ZSM-22 molecular sieve was impregnated in an organic alkali solution, washed, dried (I), and calcined (I) to obtain organic alkali modified ZSM-22 molecular sieve.
4. The method according to claim 3, characterized in that, The organic base in the organic base solution is selected from one of triethylamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide; The concentration of the organic base solution is 0.05–2 mol / L; The volume ratio of the ZSM-22 molecular sieve to the organic alkali solution is 1:5 to 20; The silicon-to-aluminum ratio of the ZSM-22 molecular sieve is 50 to 200.
5. The method according to claim 3, characterized in that, The impregnation temperature is 150–170°C; The soaking time is 6-8 hours; The temperature of the drying process I is 100–120°C; The drying time for step I is 6–12 hours; The temperature of the calcination I is 550–650°C; The roasting time for the first stage is 6 to 8 hours.
6. The method according to claim 1, characterized in that, The catalyst is obtained through the following steps: The catalyst was obtained by mixing organic base-modified ZSM-22 molecular sieve and metal salt solution, followed by aging, drying (II), and calcination (II).
7. The method according to claim 6, characterized in that, The metal salt in the metal salt solution is selected from at least one of Co(NO3)2·6H2O and Ni(NO3)2·6H2O; The concentration of the metal salt solution is 0.005–0.025 g / ml; The mass ratio of the organic base modified ZSM-22 molecular sieve to the metal salt is 4 to 15:
1.
8. The method according to claim 6, characterized in that, The aging time is 1 to 12 hours; The temperature of the drying II process is 100–120°C; The drying time for step II is 6–12 hours; The temperature of the second calcination is 500–600°C; The roasting time is 4 to 8 hours.
9. The method according to claim 1, characterized in that, The catalyst is activated; The activation atmosphere is a nitrogen atmosphere; The activation temperature is 400–500°C; The activation time is 2 to 5 hours.
10. The method according to claim 1, characterized in that, The feed space velocity of the 2-butene is 10–25 h⁻¹. -1 ; The reaction temperature is 200–400°C; The reaction pressure is 0.1–3 MPa.