CN111054388B - Nickel-based carbon four-fraction selective hydrogenation catalyst and preparation method thereof - Google Patents

Nickel-based carbon four-fraction selective hydrogenation catalyst and preparation method thereof Download PDF

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CN111054388B
CN111054388B CN201811202634.XA CN201811202634A CN111054388B CN 111054388 B CN111054388 B CN 111054388B CN 201811202634 A CN201811202634 A CN 201811202634A CN 111054388 B CN111054388 B CN 111054388B
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nickel
pseudo
boehmite
roasting
selective hydrogenation
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CN111054388A (en
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姜建波
齐焕东
薛红霞
白志敏
王昊
赵庆鲁
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China Petroleum and Chemical Corp
Qilu Petrochemical Co of Sinopec
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Qilu Petrochemical Co of Sinopec
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/892—Nickel and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
    • C07C5/05—Partial hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

A nickel-based carbon four-fraction selective hydrogenation catalyst and a preparation method thereof, belonging to the technical field of hydrogenation catalysts. The method is characterized in that: the preparation method takes magnesium aluminate spinel as a carrier and Ni-Ag as an active component, and comprises the following preparation steps: heating a magnesium acetate solution, a pseudo-boehmite slurry and ethylene glycol to 55-65 ℃, preserving heat and stirring to obtain slurry, drying the slurry and roasting to obtain a magnesia-alumina spinel material; mixing the magnesia-alumina spinel material with pseudo-boehmite, crushing, and soaking in nickel nitrate and silver nitrate; and roasting the impregnated material to obtain the catalyst. The method utilizes the advantage that the quality of the magnesia-alumina spinel material is improved, improves the performance of the catalyst, can greatly reduce the cost of the catalyst, and has lower isomerization activity of 1-butene.

Description

Nickel-based carbon four-fraction selective hydrogenation catalyst and preparation method thereof
Technical Field
A nickel-based carbon four-fraction selective hydrogenation catalyst and a preparation method thereof, belonging to the technical field of hydrogenation catalysts.
Background
The C-C fraction is a mixture of a plurality of alkanes, alkenes, alkadienes and alkynes containing four carbon atoms, mainly comes from refinery gas generated in the petroleum refining process and byproducts in the process of ethylene preparation by cracking petroleum hydrocarbons, and the cracking C-C fraction contains saturated hydrocarbons and unsaturated hydrocarbons such as n-butane, isobutane, 1-butene, trans-2-butene, cis-2-butene, isobutene, 1,2-butadiene, 1,3-butadiene, methylacetylene, ethylacetylene and vinylacetylene, and is mainly used for industrially producing 1,3-butadiene, isobutene and 1-butene.
The 1-butene is an important chemical raw material, is mainly used for copolymerizing monomers of Linear Low Density Polyethylene (LLDPE) and producing poly-1-butene plastics, and can be used as a main raw material for producing chemical products with high added values, such as sec-butyl alcohol, methyl ethyl ketone and the like; the oligomerization of 1-butene can produce C eight-C and C twelve-C alpha olefins, which are excellent raw materials for preparing the surfactant. Has wide application in the fields of petrochemical industry, fine chemical industry, medicine, pesticide and the like.
In the method for producing the butene by using the cracking carbon IV, one method is to directly carry out selective hydrogenation on the cracking carbon IV, and hydrogenate 1,2-butadiene, 1,3-butadiene, methylacetylene, ethylacetylene and vinylacetylene in the cracking carbon IV to generate monoolefin such as 1-butene, trans-2-butene, cis-2-butene and the like, and simultaneously avoid further hydrogenation of the monoolefin to generate alkane; another method is to separate 1,3-butadiene from cracked C4 to obtain the residual by-product mainly containing C tetraolefin and C tetramonoolefin, which is called C tetraraffinate, usually containing about 1.0wt% of 1,3-butadiene, and the butadiene is removed by selective hydrogenation. The catalyst for preparing butylene by selective hydrogenation of carbon four applied to the current industrial production comprises Pd/Al 2 O 3 Catalyst and Pd-Ag/Al 2 O 3 A bimetallic catalyst.
The patent US4409410 discloses a catalyst for preparing 1-butene by selective hydrogenation of 1,3-butadiene in a carbon-four mixed gas and a preparation method thereof, wherein the catalyst is prepared by adopting an impregnation method, contains palladium-silver bimetallic and takes alumina as a carrier, and is used for selective hydrogenation of 1,3-butadiene in the carbon-four mixed gas. The patent states that the bimetallic catalyst containing 0.3wt% Pd and 0.3wt% Ag has a lower loss of 1-butene than the Pd alone (0.3 wt%) catalyst. Patent CN1236333 discloses a selective hydrogenation catalyst containing palladium and at least one element selected from tin and lead for use in a process for selective hydrogenation of unsaturated diolefins to monoolefins, mainly for use in the hydrogenation of butadiene to 1-butene, which teaches that a catalyst containing 0.3wt% pd and 0.99wt% pb can increase the hydrogenation rate of butadiene by at least 1.5 times the hydrogenation rate of 1-butene. Patent 102240547 discloses a carbon four selective hydrogenation catalyst, its preparation method and application, the catalyst adopts ionizing radiation method to reduce active metal Pd and adjuvant metal on the surface of alumina carrier. The patent states that the metal particles prepared by ionizing radiation have average diameters of less than 10nm and have the advantage of not requiring prior reduction with hydrogen, and that butadiene selectivity with this type of catalyst is 83%.
In the prior art, 1-butene is generally lost in the process of 1,3-butadiene selective hydrogenation to prepare 1-butene, which is mainly caused by the generation of butane and the isomerization of 1-butene to 2-butene, so that the development of a catalyst which can hydrogenate 1,3-butadiene to form 1-butene and can prevent excessive hydrogenation to butane and isomerization reaction is very important. Most hydrogenation catalysts are supported metal catalysts, wherein a commonly used active component is noble metal palladium. Due to the expensive price and scarcity of palladium metal, the development of a non-noble metal catalyst has higher strategic significance; in addition, the acidity of the alumina carrier can greatly improve the generation of green oil in the diene hydrogenation reaction process, and in actual production, people often adopt the method of reducing the acidity of the alumina carrier by improving the roasting temperature of the carrier to realize the inhibition of the generation of the green oil. However, the consequence of increasing the calcination temperature is not only a decrease in the specific surface of the alumina support but also a limitation of the crystalline phase of the alumina.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: overcomes the defects of the prior art, and provides a nickel-based C four-fraction selective hydrogenation catalyst which has low catalyst cost and lower 1-butene isomerization activity and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows: the nickel-based carbon four-fraction selective hydrogenation catalyst comprises a carrier and active components, and is characterized in that: the carrier is magnesium aluminate spinel, the active component is Ni-Ag, and the content of nickel in the catalyst is 19-25 wt% calculated by NiO. The catalyst takes Ni-Ag as an active component and takes magnesia-alumina spinel material as a carrier, and has lower cost under the condition of ensuring better selectivity and hydrogenation efficiency of the catalyst.
The preparation method of the nickel-based carbon four-fraction selective hydrogenation catalyst is characterized by comprising the following preparation steps:
1) Adding pseudo-boehmite powder into water to prepare pseudo-boehmite water slurry; dissolving magnesium acetate in water to prepare a magnesium acetate solution;
2) Heating a magnesium acetate solution, pseudo-boehmite water slurry and ethylene glycol to 55-65 ℃, preserving heat and stirring to obtain slurry, wherein the magnesium acetate and Al in the pseudo-boehmite 2 O 3 In a molar ratio of 1:1 to 1.2; the amount of the ethylene glycol is 6-8% of the mass of the magnesium acetate;
3) Pouring the slurry obtained in the step 2), drying at 115-125 ℃ for 22-26h, and roasting to obtain a magnesium aluminate spinel material;
4) Taking the magnesia alumina spinel material obtained in the step 3), adding pseudo-boehmite as an auxiliary agent, mixing and crushing into 160-mesh powder, wherein the mass of the pseudo-boehmite is Al 2 O 3 Meter, magnesia-alumina spinel material and Al 2 O 3 The mass ratio is 2 to 3;
5) Preparing a mixed solution of nickel nitrate and silver nitrate, mixing the powder obtained in the step 4) with the mixed solution, and then soaking; the molar ratio of nickel nitrate to silver nitrate in the mixed solution is 40 to 100;
6) Adding an extrusion-assisting pore-forming agent into the impregnated material, extruding the material into strips, airing the strips, and roasting the strips for 8 hours at the temperature of 300-350 ℃ to obtain the catalyst.
The invention provides a preparation method of a catalyst for preparing 1-butene by 1,3-butadiene in four-carbon fraction through selective hydrogenation, wherein a nickel-based non-noble metal catalyst is prepared by adopting an improved magnesia-alumina spinel material as a main carrier component, and the magnesia-alumina spinel is used as a composite oxide, has the advantages of two oxides of magnesia and alumina, has a stable structure and does not have the advantages of the two oxides, so that magnesium-aluminum powder with a magnesia-alumina spinel phase is an excellent carrier component. The catalyst adopts the improved magnesia-alumina spinel material as the main carrier component and pseudoboehmite as the auxiliary agent, and the effect is optimal when the proportion of the two is within the range of the invention. The method has the advantages of improving the quality of the magnesia-alumina spinel material, improving the performance of the catalyst, greatly reducing the cost of the catalyst and having lower isomerization activity of 1-butene.
Preferably, the mass ratio of water to magnesium acetate in preparing the magnesium acetate solution in the step 1) is 100:30 to 40.
Preferably, the mass ratio of water to the pseudo-boehmite powder in the preparation of the pseudo-boehmite slurry in the step 1) is 100:50 to 60.
The concentration of the preferred solution or water slurry is enough to react at a more appropriate rate, the obtained magnesium aluminate spinel structure is more stable, and the prepared catalyst active component is more uniformly distributed.
Preferably, the heating in the step 2) is carried out to 58-62 ℃, and the stirring time is 2h. The optimized reaction conditions can better ensure the performance of the obtained magnesia-alumina spinel.
Preferably, the drying temperature in the step 3) is 118-122 ℃, and the drying time is 23.5-24.5 h. The magnesia-alumina spinel material formed under the preferable drying condition has more uniform surface gaps and is more suitable to be used as a carrier.
Preferably, the roasting temperature of the roasting in the step 3) is 540-560 ℃; the temperature rise process during roasting comprises the following steps: the temperature rise rate is 297 ℃/h-303 ℃/h in the stage from the normal temperature to 315 ℃; the temperature rise rate in the stage from 315 ℃ to 415 ℃ is 97 ℃/h to 103 ℃/h; the heating rate is 297 ℃/h to 303 ℃/h in the stage from 410 ℃ to the roasting temperature, and then the constant temperature is kept for 2.8 to 3.2 hours at the roasting temperature.
The magnesium aluminate spinel material property with the best performance can be obtained through the optimized heating process and the constant temperature, the environment of the material is rapidly changed by rapidly heating in the heating process, the stress effect is enhanced, then the heating rate is reduced to control the material form transformation rate, finally the temperature is rapidly raised to the roasting temperature, after the temperature is kept for a certain time, the obtained magnesium aluminate spinel material property structure is more stable, the magnesium aluminate spinel material structure is used as a carrier, has a higher contact surface after carrying an active component, and can improve the catalytic efficiency of the catalyst.
Preferably, the magnesia alumina spinel material and Al in the step 4) 2 O 3 The mass ratio is 2.4 to 2.6. The preferred amount of adjuvant is more effective.
Preferably, the molar ratio of the nickel nitrate to the silver nitrate in the mixed solution in the step 5) is 60 to 80. The preferable proportion of the nickel and the silver can achieve a better catalytic effect.
Preferably, in step 6), the extrusion-assisted pore-forming agent is one or a mixture of two or more of nitric acid, citric acid, kapok, lignocellulose, graphite or sesbania powder.
Compared with the prior art, the invention has the following beneficial effects: the invention provides a preparation method of a catalyst for preparing 1-butene by selectively hydrogenating 1,3-butadiene in four-carbon fraction, which adopts an improved magnesia-alumina spinel material as a main carrier and adds pseudo-boehmite as an auxiliary agent to prepare a Ni-Ag series non-noble metal catalyst. The method has the advantages of improving the quality of the magnesia-alumina spinel material, improving the performance of the catalyst, greatly reducing the cost of the catalyst and having lower isomerization activity of 1-butene.
Detailed Description
The invention is further illustrated by the following specific examples, of which example 1 is the best mode of practice.
Example 1
1) Adding pseudo-boehmite powder into water to prepare pseudo-boehmite water slurry; dissolving magnesium acetate in water to prepare a magnesium acetate solution; the mass ratio of water to magnesium acetate is 100:35; the mass ratio of water to the pseudo-boehmite powder is 100:55;
2) Heating magnesium acetate solution, pseudo-boehmite water slurry and ethylene glycol to 60 ℃, preserving heat and stirring for 2 hours to prepare slurry, wherein the magnesium acetate and Al in the pseudo-boehmite 2 O 3 In a molar ratio of 1:1.1; the amount of the ethylene glycol is 7 percent of the mass of the magnesium acetate;
3) Pouring the slurry obtained in the step 2), drying at 120 ℃ for 24h, and roasting at the roasting temperature of 550 ℃ after drying; the temperature rise process during roasting comprises the following steps: the temperature rise rate is 300 ℃/h in the stage from normal temperature to 315 ℃; the temperature rise rate is 100 ℃/h in the stage from 315 ℃ to 415 ℃; the temperature rise rate is 300 ℃/h in the stage from 410 ℃ to the roasting temperature, and then the temperature is kept constant for 3 hours at the roasting temperature; obtaining a magnesia-alumina spinel material;
4) Taking the magnesia alumina spinel material obtained in the step 3), adding pseudo-boehmite as an auxiliary agent, mixing and crushing into 160-mesh powder, namely pseudo-boehmiteThe mass of the stone is Al 2 O 3 Meter, magnesia-alumina spinel feedstock and Al 2 O 3 The mass ratio is 2.5;
5) Preparing a mixed solution of nickel nitrate and silver nitrate, mixing the powder obtained in the step 4) with the mixed solution, and kneading the mixture for 20min by using a kneading machine; the molar ratio of the nickel nitrate to the silver nitrate in the mixed solution is 70;
6) Adding a proper amount of citric acid aqueous solution and a proper amount of sesbania powder into the soaked materials, continuously kneading for 5 minutes, taking out and extruding strips. After air drying, roasting at 330 ℃ for 8H to obtain a catalyst finished product H-1.
Example 2
1) Adding pseudo-boehmite powder into water to prepare pseudo-boehmite water slurry; dissolving magnesium acetate in water to prepare a magnesium acetate solution; the mass ratio of water to magnesium acetate is 100:33; the mass ratio of water to the pseudo-boehmite powder is 100:58;
2) Heating magnesium acetate solution, pseudo-boehmite water slurry and ethylene glycol to 62 ℃, preserving heat and stirring for 2 hours to prepare slurry, wherein the magnesium acetate and Al in the pseudo-boehmite 2 O 3 In a molar ratio of 1:1.1; the amount of the ethylene glycol is 6.5 percent of the mass of the magnesium acetate;
3) Pouring out the slurry in the step 2), drying at 122 ℃ for 23.5h, and roasting at the roasting temperature of 555 ℃ after drying; the temperature rise process during roasting comprises the following steps: the temperature rise rate is 300 ℃/h in the stage from normal temperature to 315 ℃; the temperature rise rate is 100 ℃/h in the stage from 315 ℃ to 415 ℃; the temperature rise rate is 300 ℃/h in the stage from 410 ℃ to the roasting temperature, and then the temperature is kept constant for 3.2 hours at the roasting temperature; obtaining a magnesia-alumina spinel material;
4) Taking the magnesia alumina spinel material obtained in the step 3), adding pseudo-boehmite as an auxiliary agent, mixing and crushing into 160-mesh powder, wherein the mass of the pseudo-boehmite is Al 2 O 3 Meter, magnesia-alumina spinel feedstock and Al 2 O 3 The mass ratio is 2.6;
5) Preparing a mixed solution of nickel nitrate and silver nitrate, mixing the powder obtained in the step 4) with the mixed solution, and kneading the mixture for 20min by using a kneading machine; the molar ratio of the nickel nitrate to the silver nitrate in the mixed solution is 80;
6) Adding a proper amount of nitric acid solution into the soaked materials, continuously kneading a proper amount of sesbania powder and kapok for 5 minutes, and taking out and extruding strips. After air drying, roasting at 320 ℃ for 8H to obtain the catalyst finished product H-2.
Example 3
1) Adding pseudo-boehmite powder into water to prepare pseudo-boehmite water slurry; dissolving magnesium acetate in water to prepare a magnesium acetate solution; the mass ratio of water to magnesium acetate is 100:38; the mass ratio of water to the pseudo-boehmite powder is 100:53;
2) Heating magnesium acetate solution, pseudo-boehmite water slurry and ethylene glycol to 58 ℃, preserving heat and stirring for 2 hours to prepare slurry, wherein the magnesium acetate and Al in the pseudo-boehmite 2 O 3 In a molar ratio of 1:1; the amount of the ethylene glycol is 7.5 percent of the mass of the magnesium acetate;
3) Pouring out the slurry obtained in the step 2), drying for 24.5 hours at 118 ℃, and roasting at 545 ℃ after drying; the temperature rise process during roasting comprises the following steps: the temperature rise rate is 300 ℃/h in the stage from normal temperature to 315 ℃; the temperature rise rate in the stage from 315 ℃ to 415 ℃ is 98 ℃/h; the temperature rise rate is 300 ℃/h in the stage from 410 ℃ to the roasting temperature, and then the temperature is kept constant for 2.9 hours at the roasting temperature; obtaining a magnesia-alumina spinel material;
4) Taking the magnesia alumina spinel material obtained in the step 3), adding pseudo-boehmite as an auxiliary agent, mixing and crushing into 160-mesh powder, wherein the mass of the pseudo-boehmite is Al 2 O 3 Meter, magnesia-alumina spinel material and Al 2 O 3 The mass ratio is 2.4;
5) Preparing a mixed solution of nickel nitrate and silver nitrate, mixing the powder obtained in the step 4) with the mixed solution, and kneading the mixture for 20min by using a kneading machine; the molar ratio of the nickel nitrate to the silver nitrate in the mixed solution is 60;
6) Adding a proper amount of nitric acid solution into the soaked materials, continuously kneading a proper amount of sesbania powder and kapok for 5 minutes, and taking out and extruding strips. After air drying, roasting for 8 hours at 340 ℃ to obtain the catalyst finished product H-3.
Example 4
1) Adding pseudo-boehmite powder into water to prepare pseudo-boehmite water slurry; dissolving magnesium acetate in water to prepare a magnesium acetate solution; the mass ratio of water to magnesium acetate is 100:30, of a nitrogen-containing gas; the mass ratio of water to the pseudo-boehmite powder is 100:60;
2) Heating magnesium acetate solution, pseudo-boehmite water slurry and ethylene glycol to 55 ℃, preserving heat and stirring for 2 hours to prepare slurry, wherein the magnesium acetate and Al in the pseudo-boehmite 2 O 3 In a molar ratio of 1:1; the amount of the ethylene glycol is 6 percent of the mass of the magnesium acetate;
3) Pouring the slurry obtained in the step 2), drying at 115 ℃ for 26h, and roasting at 540 ℃ after drying; the temperature rise process during roasting comprises the following steps: the temperature rise rate is 297 ℃/h in the stage from the normal temperature to 315 ℃; the temperature rise rate in the stage from 315 ℃ to 415 ℃ is 97 ℃/h; the temperature rise rate is 297 ℃/h in the stage from 410 ℃ to the roasting temperature, and then the temperature is kept constant for 2.8 hours at the roasting temperature; obtaining a magnesia-alumina spinel material;
4) Taking the magnesia alumina spinel material obtained in the step 3), adding pseudo-boehmite as an auxiliary agent, mixing and crushing into 160-mesh powder, wherein the mass of the pseudo-boehmite is Al 2 O 3 Meter, magnesia-alumina spinel feedstock and Al 2 O 3 The mass ratio is 3:1;
5) Preparing a mixed solution of nickel nitrate and silver nitrate, mixing the powder obtained in the step 4) with the mixed solution, and kneading the mixture for 20min by using a kneading machine; the molar ratio of the nickel nitrate to the silver nitrate in the mixed solution is 40;
6) Adding a proper amount of nitric acid solution into the soaked materials, continuously kneading a proper amount of sesbania powder and kapok for 5 minutes, and taking out and extruding strips. After air drying, roasting at 350 ℃ for 8H to obtain the catalyst finished product H-4.
Example 5
1) Adding pseudo-boehmite powder into water to prepare pseudo-boehmite water slurry; dissolving magnesium acetate in water to prepare a magnesium acetate solution; the mass ratio of water to magnesium acetate is 100:40; the mass ratio of water to the pseudo-boehmite powder is 100:50;
2) Heating magnesium acetate solution, pseudo-boehmite water slurry and ethylene glycol to 65 ℃, preserving heat and stirring for 2 hours to prepare slurry, wherein the magnesium acetate and Al in the pseudo-boehmite 2 O 3 In a molar ratio of 1: 1.2; the amount of the ethylene glycol is 8 percent of the mass of the magnesium acetate;
3) Pouring out the slurry obtained in the step 2), drying 22 h at 125 ℃, and roasting at the roasting temperature of 560 ℃ after drying; the temperature rise process during roasting comprises the following steps: the temperature rise rate is 303 ℃/h in the stage from normal temperature to 315 ℃; the temperature rise rate is 103 ℃/h in the stage from 315 ℃ to 415 ℃; the temperature rise rate is 303 ℃/h from 410 ℃ to the roasting temperature, and then the temperature is kept constant for 3.2 hours at the roasting temperature; obtaining a magnesia-alumina spinel material;
4) Taking the magnesia alumina spinel material obtained in the step 3), adding pseudo-boehmite as an auxiliary agent, mixing and crushing into 160-mesh powder, wherein the mass of the pseudo-boehmite is Al 2 O 3 Meter, magnesia-alumina spinel material and Al 2 O 3 The mass ratio is 2:1;
5) Preparing a mixed solution of nickel nitrate and silver nitrate, mixing the powder obtained in the step 4) with the mixed solution, and kneading the mixture for 20min by using a kneading machine; the molar ratio of the nickel nitrate to the silver nitrate in the mixed solution is 100;
6) Adding a proper amount of nitric acid solution and a proper amount of sesbania powder into the soaked materials, continuously kneading for 5 minutes, and taking out and extruding strips. After air drying, roasting at 300 ℃ for 8H to obtain a catalyst finished product H-5.
Example 6
1) Adding pseudo-boehmite powder into water to prepare pseudo-boehmite water slurry; dissolving magnesium acetate in water to prepare a magnesium acetate solution; the mass ratio of water to magnesium acetate is 100:38; the mass ratio of water to the pseudo-boehmite powder is 100:53;
2) Heating magnesium acetate solution, pseudo-boehmite water slurry and ethylene glycol to 58 ℃, preserving heat and stirring for 2 hours to prepare slurry, wherein the magnesium acetate and Al in the pseudo-boehmite 2 O 3 In a molar ratio of 1:1; the amount of the ethylene glycol is 7.5 percent of the mass of the magnesium acetate;
3) Pouring the slurry obtained in the step 2), drying at 118 ℃ for 24.5h, and roasting at 545 ℃ after drying; the temperature rise process during roasting comprises the following steps: the heating rate is 300 ℃/h in the stage from the normal temperature to the roasting temperature; then keeping the temperature constant at the roasting temperature for 2.9 hours; obtaining a magnesia-alumina spinel material;
4) Taking the magnesia-alumina spinel material obtained in the step 3), and adding pseudo-boehmiteAs an auxiliary agent, the raw materials are mixed and crushed into 160 meshes of powder, and the quality of the pseudo-boehmite is Al 2 O 3 Meter, magnesia-alumina spinel material and Al 2 O 3 The mass ratio is 2.4;
5) Preparing a mixed solution of nickel nitrate and silver nitrate, mixing the powder obtained in the step 4) with the mixed solution, and kneading the mixture for 20min by using a kneading machine; the molar ratio of the nickel nitrate to the silver nitrate in the mixed solution is 60;
6) Adding a proper amount of nitric acid solution into the soaked materials, continuously kneading a proper amount of sesbania powder and kapok for 5 minutes, taking out and extruding. After air drying, roasting for 8H at 340 ℃ to obtain the catalyst finished product H-6.
Comparative example 1
Comparative catalyst J-1 was prepared according to the protocol of example 5 which gave the best results in the catalyst examples published in Chinese patent CN 106582625A.
The catalysts H-1 to H5 prepared in examples and comparative example J-1 were evaluated, and the results are shown in Table 2.
In the present invention, the hydrogenation rate of butadiene, the loss rate of butene and the isomerization rate of 1-butene are used to represent the reactivity of the catalyst. The first two indices are used to indicate the selective hydrogenation performance of the catalyst and the third index is used to indicate the isomerization performance of the catalyst. The method for calculating the butadiene hydrogenation rate, the butene loss rate and the 1-butene isomerization rate comprises the following steps:
Figure 921047DEST_PATH_IMAGE001
catalyst evaluation conditions: the reaction temperature is 50 ℃, the reaction pressure is 2.0MPa, and the liquid air speed is 10h -1 Hydrogen/butadiene molar ratio 1.5.
The composition of the C4 feedstock used for the evaluation is shown in table 1. The evaluation results are shown in Table 2
TABLE 1 composition of C4 feedstock
Figure DEST_PATH_IMAGE002
。
TABLE 2 evaluation results
Figure 307029DEST_PATH_IMAGE003
。
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.

Claims (9)

1. A nickel series carbon four-fraction selective hydrogenation catalyst comprises a carrier and an active component, and is characterized in that: the carrier is magnesium aluminate spinel, the active component is Ni-Ag, the content of nickel in the catalyst is 19-25 wt% calculated by NiO;
the preparation method of the nickel-based carbon four-fraction selective hydrogenation catalyst comprises the following steps:
1) Adding pseudo-boehmite powder into water to prepare pseudo-boehmite water slurry; dissolving magnesium acetate in water to prepare a magnesium acetate solution;
2) Heating a magnesium acetate solution, a pseudo-boehmite water slurry and ethylene glycol to 55-65 ℃, preserving heat and stirring to obtain slurry, wherein the magnesium acetate and Al in the pseudo-boehmite 2 O 3 In a molar ratio of 1:1 to 1.2; the amount of the ethylene glycol is 6-8% of the mass of the magnesium acetate;
3) Pouring the slurry obtained in the step 2), drying at 115-125 ℃ for 22-26h, and roasting to obtain a magnesium aluminate spinel material;
4) Taking the magnesia alumina spinel material obtained in the step 3), adding pseudo-boehmite as an auxiliary agent, mixing and crushing into 160-mesh powder, wherein the mass of the pseudo-boehmite is Al 2 O 3 Meter, magnesia-alumina spinel material and Al 2 O 3 The mass ratio is 2 to 3;
5) Preparing a mixed solution of nickel nitrate and silver nitrate, mixing the powder obtained in the step 4) with the mixed solution, and then soaking; the molar ratio of the nickel nitrate to the silver nitrate in the mixed solution is 40-100;
6) Adding an extrusion-assisting pore-forming agent into the impregnated material, extruding the material into strips, airing the strips, and roasting the strips for 8 hours at the temperature of 300-350 ℃ to obtain the catalyst.
2. The nickel-based carbon four-fraction selective hydrogenation catalyst according to claim 1, wherein: the mass ratio of water to magnesium acetate in the preparation of the magnesium acetate solution in the step 1) is 100:30 to 40.
3. The nickel-based carbon four-fraction selective hydrogenation catalyst according to claim 1, wherein: step 1) preparing the pseudo-boehmite water slurry, wherein the mass ratio of water to the pseudo-boehmite powder is 100:50 to 60.
4. The nickel-based carbon four-fraction selective hydrogenation catalyst according to claim 1, wherein: in the step 2), the temperature is heated to 58-62 ℃, and the stirring time is 2h.
5. The nickel-based carbon four-fraction selective hydrogenation catalyst according to claim 1, characterized in that: the drying temperature of the drying in the step 3) is 118-122 ℃, and the drying time is 23.5-24.5 h.
6. The nickel-based carbon four-fraction selective hydrogenation catalyst according to claim 1, wherein: the roasting temperature of the roasting in the step 3) is 540-560 ℃; the temperature rise process during roasting comprises the following steps: the temperature rise rate is 297 ℃/h-303 ℃/h in the stage from the normal temperature to 315 ℃; the temperature rise rate in the stage from 315 ℃ to 415 ℃ is 97 ℃/h to 103 ℃/h; the temperature rise rate is 297 ℃/h-303 ℃/h in the stage from 410 ℃ to the roasting temperature, and then the constant temperature is kept for 2.8-3.2 hours at the roasting temperature.
7. The nickel-based carbon four-fraction selective hydrogenation catalyst according to claim 1, characterized in that: the magnesia alumina spinel material and Al in the step 4) 2 O 3 The mass ratio is 2.4 to 2.6.
8. The nickel-based carbon four-fraction selective hydrogenation catalyst according to claim 1, characterized in that: the molar ratio of the nickel nitrate to the silver nitrate in the mixed solution in the step 5) is 60 to 80.
9. The nickel-based carbon four-fraction selective hydrogenation catalyst according to claim 1, wherein: in the step 6), the extrusion-assisted pore-forming agent is one or a mixture of more than two of nitric acid, citric acid, kapok, lignocellulose, graphite or sesbania powder.
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