CN116393133A - Supported nickel-based catalyst, preparation method and application - Google Patents
Supported nickel-based catalyst, preparation method and application Download PDFInfo
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- CN116393133A CN116393133A CN202310313441.6A CN202310313441A CN116393133A CN 116393133 A CN116393133 A CN 116393133A CN 202310313441 A CN202310313441 A CN 202310313441A CN 116393133 A CN116393133 A CN 116393133A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 239000003054 catalyst Substances 0.000 title claims abstract description 110
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims abstract description 68
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 19
- 229910000943 NiAl Inorganic materials 0.000 claims abstract description 9
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 63
- 239000002243 precursor Substances 0.000 claims description 27
- 238000005984 hydrogenation reaction Methods 0.000 claims description 26
- 229910052742 iron Inorganic materials 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 32
- 238000003756 stirring Methods 0.000 description 20
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 13
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 229920000742 Cotton Polymers 0.000 description 7
- 239000006004 Quartz sand Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 239000010453 quartz Substances 0.000 description 7
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000004445 quantitative analysis Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000007868 Raney catalyst Substances 0.000 description 4
- 229910000564 Raney nickel Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 1
- KBMSFJFLSXLIDJ-UHFFFAOYSA-N 6-aminohexanenitrile Chemical compound NCCCCCC#N KBMSFJFLSXLIDJ-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- NNGAQKAUYDTUQR-UHFFFAOYSA-N cyclohexanimine Chemical compound N=C1CCCCC1 NNGAQKAUYDTUQR-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
-
- 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
- Y02P20/584—Recycling of catalysts
Abstract
The application discloses a supported nickel-based catalyst, a preparation method and application. The supported nickel-based catalyst comprises a carrier and an active component, wherein the active component comprises Fe 2 O 3 And NiAl 2 O 4 The method comprises the steps of carrying out a first treatment on the surface of the The carrier comprises Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The active component accounts for 50-70% of the supported nickel-based catalyst by mass. The supported nickel-based catalyst is used for synthesizing hexamethylenediamine by catalytic hydrogenation of adiponitrile, and has higher reactant conversion rate and target product selectivity.
Description
Technical Field
The application relates to the technical field of catalysts, in particular to a supported nickel-based catalyst, a preparation method and application.
Background
The hydrogenation of adiponitrile to hexamethylenediamine is a complex reaction process, and the reaction system comprises main product hexamethylenediamine, intermediate product 6-aminocapronitrile, byproduct cyclohexylimine, dihexanetriamine and the like. Catalysts for hydrogenation reactions include homogeneous catalysts, heterogeneous acid catalysts, and Ziegler-type catalysts. Patent DE1904613 uses cyclohexane as solvent and triisobutylaluminum and cobalt octoate to prepare Ziegler-type catalyst, and the hexamethylenediamine selectivity reaches 96%. Patent US5726334 uses ruthenium complex RuHCl (H 2 )(PCy 3 ) 2 As a catalyst, the adiponitrile conversion rate reaches 96%. Patents US4429159 and US4491673 use raney nickel as a catalyst to react at lower temperature and pressure conditions, but introduce significant amounts of corrosive materials into the process in order to maintain the activity, selectivity and service life of the catalyst, making separation and purification difficult. The patent CN109647419A prepares the supported nickel-based catalyst modified by the rare earth metal oxide by taking the alumina as a carrier, does not need to add alkali to inhibit the generation of byproducts, and improves the adiponitrile conversion rate and the hexamethylenediamine selectivity of the target product.
Compared with a homogeneous acid catalyst, the heterogeneous acid catalyst has the advantages of simple preparation process, easy separation and recovery from a reaction system and the like. In the current industrial production, a heterogeneous catalyst, namely Raney nickel, is mainly used for preparing hexamethylenediamine by hydrogenating adiponitrile. Raney nickel has high catalytic activity, but is easy to break during stirring due to low mechanical strength, and a large amount of auxiliary alkaline substances (ammonia water, naOH or KOH) are needed to inhibit side reactions. And Raney nickel has active property, is not easy to store, and is easy to generate spontaneous combustion when being contacted with air. Therefore, it is necessary to provide a catalyst with high selectivity and high stability for synthesizing hexamethylenediamine by high-efficiency catalytic hydrogenation.
Disclosure of Invention
The purpose of the application is to provide a supported nickel-based catalyst, a preparation method and application. The supported nickel-based catalyst is used for synthesizing hexamethylenediamine by catalytic hydrogenation of adiponitrile, has higher reactant conversion rate and target product selectivity, and can solve the technical problems.
The embodiment of the application provides a supported nickel-based catalyst, which comprises a carrier and an active component, wherein the nickel-based catalyst comprises Fe 2 O 3 And NiAl 2 O 4 The method comprises the steps of carrying out a first treatment on the surface of the The carrier comprises Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The active component accounts for 50-70% of the weight of the supported nickel-based catalyst.
In some embodiments, the active component has a mass ratio of Ni to Fe of 8:1 to 4:1.
In some embodiments, the carrier is gamma-Al 2 O 3 。
Correspondingly, the embodiment of the application provides a preparation method of the supported nickel-based catalyst, which comprises the following steps:
(S1) preparing a precursor: preparation of Ni-containing alloy 2+ 、Fe 3+ 、Al 3+ Is a precursor solution of (a);
(S2) preparing a precipitant: preparation of the CO-containing products 3 2- Is added to the solution of the precipitant;
(S3) mixing the solutions obtained in the step (S1) and the step (S2), and maintaining the pH to be stable during the mixing process;
(S4) aging the mixed solution obtained in the step (S3) at 50-80 ℃;
and (S5) carrying out suction filtration, drying, roasting and grinding on the mixed solution obtained in the step (S4) to obtain the supported nickel-based catalyst.
In some embodiments of the present invention, in some embodiments,in step (S2), CO 3 2- The concentration is 0.5-1.5 mol/L.
In some embodiments, in step (S3), the pH is 7.0 to 8.5.
In some embodiments, in step (S5), the drying is performed at a temperature of 90 to 110 ℃ for a time of 12 to 24 hours.
In some embodiments, in step (S5), the firing temperature is 500 to 600 ℃ and the firing time is 4 to 6 hours.
In some embodiments, in step (S2), CO 3 2- Derived from one or both of sodium carbonate and potassium carbonate.
Correspondingly, the embodiment of the application provides the application of the supported nickel-based catalyst or the supported nickel-based catalyst prepared by the preparation method in adiponitrile hydrogenation reaction.
Correspondingly, the application also provides a preparation method of hexamethylenediamine, which comprises the following steps:
using a mixed solution of adiponitrile and ethanol as a reaction raw material;
the supported nickel-based catalyst or the supported nickel-based catalyst prepared by the preparation method catalyzes adiponitrile hydrogenation reaction to prepare hexamethylenediamine
In some embodiments, the reaction pressure of the hydrogenation reaction is from 3.0 to 9.0MPa.
In some embodiments, the reaction temperature of the hydrogenation reaction is from 90 to 200 ℃.
The beneficial effects of this application lie in: in contrast to the prior art, the supported nickel-based catalyst of the present application comprises a support and an active component comprising Fe 2 O 3 And NiAl 2 O 4 The method comprises the steps of carrying out a first treatment on the surface of the The carrier comprises Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The active component accounts for 50-70% of the supported nickel-based catalyst by mass. The catalyst takes alumina as a carrier, and iron is added to modify the nickel-based catalyst, so that the obtained catalyst has high mechanical strength and good stability; the catalyst of the application is modified by iron, the specific surface area is increased, and the number of acid sites on the surface of the catalyst is increased, therebyThe hydrogenation activity is improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly introduced below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an X-ray diffraction pattern of supported nickel-based catalysts prepared under different pH conditions in examples 1-4 of the present application.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments herein without making any inventive effort, are intended to be within the scope of the present application. In addition, in the description of the present application, the term "comprising" means "including but not limited to". The terms first, second, third and the like are used merely as labels, and do not impose numerical requirements or on the order of construction. Various embodiments of the present application may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the application; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the ranges, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
To solve the problems of the existing catalysts, embodiments of the present application provideThe supported nickel-based catalyst comprises a carrier and an active component, wherein the active component comprises Fe 2 O 3 And NiAl 2 O 4 The method comprises the steps of carrying out a first treatment on the surface of the The carrier comprises Al 2 O 3 The active component accounts for 50-70% of the weight of the supported nickel-based catalyst.
According to the method, the catalyst is modified by iron, the specific surface area is increased, and the number of acid sites on the surface of the catalyst is increased, so that the hydrogenation activity is improved.
In some embodiments, the nickel-based catalyst comprises 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70% by mass of the supported nickel-based catalyst, or a range of any or any two values.
In some embodiments, the mass ratio of Ni to Fe in the active component is 8:1 to 4:1.
In some embodiments, the alumina as a support is in a crystalline structure, the crystalline form being gamma-Al 2 O 3 。
In some embodiments, the mass ratio of Ni to Fe is any value or range of values of any two values of 8:1, 7:1, 6:1, 5:1, 4:1.
In some embodiments, the present application provides a method of preparing a supported nickel-based catalyst, comprising the steps of:
(S1) preparing a precursor: preparation of Ni-containing alloy 2+ 、Fe 3+ 、Al 3+ Is a precursor solution of (a);
(S2) preparing a precipitant: preparation of the CO-containing products 3 2- Is added to the solution of the precipitant;
(S3) mixing the solutions obtained in the step (S1) and the step (S2), and maintaining the pH to be stable during the mixing process;
(S4) aging the mixed solution obtained in the step (S3) at 50-80 ℃;
and (S5) carrying out suction filtration, drying, roasting and grinding on the mixed solution obtained in the step (S4) to obtain the supported nickel-based catalyst.
In some embodiments, the temperature of aging is any value or a range of values of any two values of 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃.
In some embodiments, in step (S2), CO 3 2- The concentration is 0.5-1.5 mol/L.
In some embodiments, the CO 3 2- The concentration is any value or any two values of 0.5mol/L, 1mol/L and 1.5mol/L.
In some embodiments, in step (S3), the pH is 7.0 to 8.5. In the preparation process of the catalyst, the selectivity of hexamethylenediamine can be further improved by controlling the pH value under the weak alkaline condition.
In some embodiments, the pH is any value or range of values of any two values of 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5.
In some embodiments, in step (S5), the drying temperature is 90-110℃and the drying time is 12-24 hours.
In some embodiments, the drying temperature (c) is any value or range of values of any two values of 90, 95, 100, 105, 110.
In some embodiments, the drying time (h) is: 12. 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or a range of any two values.
In some embodiments, in step (S5), the firing temperature is 500-600℃and the firing time is 4-6 hours.
In some embodiments, the firing temperature (c) is any value or range of values of any two values of 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600.
In some embodiments, the firing time (h) is any value or range of values of 4, 4.5, 5.0, 5.5, 6.0.
In some embodiments, in step (S2), CO 3 2- Derived from one or both of sodium carbonate and potassium carbonate.
In some embodiments, in step (S1), ni (NO) 3 ) 2 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 O、Fe(NO 3 ) 3 ·9H 2 The mixed solution of O is used as a precursor solution.
In some embodiments, in step (S2), na is used 2 CO 3 As a precipitant solution.
In some embodiments, in step (S3), the mixing is performed in the following manner: and (3) respectively filling the solutions obtained in the step (S1) and the step (S2) with a dropping funnel, simultaneously dripping the solutions into a beaker filled with a certain amount of water at a constant dripping speed, heating and stirring the beaker in a water bath, maintaining titration by using a pH meter, and keeping the pH stable until the dripping of the precursor solution is completed.
In some embodiments, in step (S3), the rate of addition of the precursor solution and the precipitant solution is maintained at 1:3 to 1:2.
In some embodiments, in step (S3), the titration process pH is maintained between 7.0 and 8.5.
In some embodiments, in step (S5), the slurry is ground to 40-60 mesh for use.
The embodiment of the application further provides application of the supported nickel-based catalyst or the supported nickel-based catalyst prepared by the preparation method in adiponitrile hydrogenation reaction.
In some embodiments, supported nickel-based catalysts are used to catalyze the hydrogenation of adiponitrile to hexamethylenediamine.
In some embodiments, embodiments of the present application provide a method for preparing hexamethylenediamine, comprising the steps of:
using a mixed solution of adiponitrile and ethanol as a reaction raw material;
the supported nickel-based catalyst or the supported nickel-based catalyst prepared by the preparation method catalyzes adiponitrile hydrogenation reaction to prepare hexamethylenediamine.
In some embodiments, the mass fraction of adiponitrile in the reaction feed is 20-30%, e.g., the mass fraction (%) of adiponitrile is: 20. 25, 30 or a range of any two values.
In some embodiments, the reaction pressure of the hydrogenation reaction is from 3.0 to 9.0MPa. The reaction pressure (MPa) of the hydrogenation reaction is as follows: any value or range of values of 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0.
In some embodiments, the reaction temperature (c) of the hydrogenation reaction is any value or range of values of any two values of 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200.
In some embodiments, hexamethylenediamine is synthesized by the following method:
2mL of the supported nickel-based catalyst is added into a constant temperature section of a fixed bed reactor, quartz sand and quartz cotton are filled at the upper part and the lower part of the catalyst, reaction raw materials are conveyed into the reactor by a advection pump, the flow speed is 0.04-0.12mL/min, 3.0-6.0 MPa hydrogen is introduced, the reaction temperature is set to 90-120 ℃, hexamethylenediamine is prepared by catalytic hydrogenation, and the sampling interval is 2-3 h.
Example 1
At 25 ℃, 150g deionized water was measured to dissolve 11.8373g Ni (NO 3 ) 2 ·6H 2 O、4.3286g Fe(NO 3 ) 3 ·9H 2 O、66.1765g Al(NO 3 ) 3 ·9H 2 O, fully stirring and mixing to obtain a precursor solution; a certain amount of deionized water is measured to dissolve 63.6g of anhydrous Na 2 CO 3 Uniformly mixing to prepare a precipitant solution with the concentration of 1 mol/L; simultaneously dropwise adding a precipitant solution and a precursor solution into a beaker which is pre-filled with a proper amount of deionized water at a water bath heating and stirring temperature of 50 ℃ at a dropping rate of 3:1, keeping the pH at 7.2, aging the solution for 3 hours under the water bath heating and stirring temperature of 50 ℃ after the precursor solution is completely added, carrying out suction filtration, drying the precipitate at 110 ℃ for 12 hours without washing, and roasting the precipitate at 500 ℃ for 6 hours to obtain the iron-modified supported nickel-based catalyst with aluminum oxide as a carrier, wherein the iron-modified nickel-based catalyst contains 20% Ni-5% Fe/Al 2 O 3 -ph7.2, grinding to 40-60 mesh.
In FIG. 1, 20% Ni-5% Fe/Al 2 O 3 X-ray diffraction pattern at pH7.2 shows that the catalyst contains NiAl at the same time 2 O 4 Spinel structure and independent alumina crystal gamma-Al 2 O 3 。
The application of the iron-modified supported nickel-based catalyst with aluminum oxide as a carrier in preparing hexamethylenediamine by hydrogenation of adiponitrile comprises the following steps:
2.5g of 20% Ni-5% Fe/Al are introduced into a fixed bed reactor 2 O 3 And (3) a catalyst with pH of 7.2, wherein quartz cotton and quartz sand are filled at the upper end and the lower end of the catalyst so that the catalyst position falls in a constant temperature zone, the reaction raw material is an ethanol solution with the mass fraction of adiponitrile of 25%, and the raw material solution is conveyed into a reactor by a advection pump, and the flow rate is 0.10mL/min. Introducing 3.0MPa hydrogen, keeping the flow rate of the hydrogen at 32.8mL/min, setting the reaction temperature at 110 ℃, taking a sample at intervals of 2 hours, and carrying out quantitative analysis by using chromatography. Adiponitrile conversion was 99% and hexamethylenediamine selectivity was 80%.
Example 2
At 25 ℃, 150g deionized water was measured to dissolve 11.8373g Ni (NO 3 ) 2 ·6H 2 O、4.3286g Fe(NO 3 ) 3 ·9H 2 O、66.1765g Al(NO 3 ) 3 ·9H 2 O, fully stirring and mixing to obtain a precursor solution; a certain amount of deionized water is measured to dissolve 63.6g of anhydrous Na 2 CO 3 Uniformly mixing to prepare a precipitant solution with the concentration of 1 mol/L; simultaneously dropwise adding a precipitant solution and a precursor solution into a beaker which is pre-filled with a proper amount of deionized water at a water bath heating and stirring temperature of 50 ℃ at a dropping rate of 3:1, keeping the pH at 7.5, aging the solution for 3 hours under the water bath heating and stirring temperature of 50 ℃ after the precursor solution is completely added, carrying out suction filtration, drying the precipitate at 110 ℃ for 12 hours without washing, and roasting at 500 ℃ for 6 hours to obtain the iron-modified supported nickel-based catalyst with aluminum oxide as a carrier, wherein the iron-modified supported nickel-based catalyst is 20% Ni-5% Fe/Al 2 O 3 -ph7.5, grinding for use with 40-60 mesh. In the attached drawing, 20% Ni-5% Fe/Al 2 O 3 X-ray diffraction pattern at pH7.5 shows that the catalyst contains NiAl at the same time 2 O 4 Spinel structure and individual alumina crystals.
The application of the iron-modified supported nickel-based catalyst with aluminum oxide as a carrier in preparing hexamethylenediamine by hydrogenation of adiponitrile comprises the following steps:
2.5g of 20% Ni-5% Fe/Al are introduced into a fixed bed reactor 2 O 3 And (3) a catalyst with pH of 7.5, wherein quartz cotton and quartz sand are filled at the upper end and the lower end of the catalyst so that the catalyst position falls in a constant temperature zone, the reaction raw material is an ethanol solution with the mass fraction of adiponitrile of 25%, and the raw material solution is conveyed into a reactor by a advection pump, and the flow rate is 0.10mL/min. Introducing 3.0MPa hydrogen, keeping the flow rate of the hydrogen at 32.8mL/min, setting the reaction temperature at 110 ℃, taking a sample at intervals of 2 hours, and carrying out quantitative analysis by using chromatography. Adiponitrile conversion was 98% and hexamethylenediamine selectivity was 64%.
Example 3
At 25 ℃, 150g deionized water was measured to dissolve 11.8373g Ni (NO 3 ) 2 ·6H 2 O、4.3286g Fe(NO 3 ) 3 ·9H 2 O、66.1765g Al(NO 3 ) 3 ·9H 2 O, fully stirring and mixing to obtain a precursor solution; a certain amount of deionized water is measured to dissolve 63.6g of anhydrous Na 2 CO 3 Uniformly mixing to prepare a precipitant solution with the concentration of 1mo 1/L; simultaneously dropwise adding a precipitant solution and a precursor solution into a beaker which is pre-filled with a proper amount of deionized water at a water bath heating and stirring temperature of 50 ℃ at a dropping rate of 3:1, keeping the pH at 8.0, aging the solution for 3 hours under the water bath heating and stirring temperature of 50 ℃ after the precursor solution is completely added, carrying out suction filtration, drying the precipitate at 110 ℃ for 12 hours without washing, and roasting at 500 ℃ for 6 hours to obtain the iron-modified supported nickel-based catalyst with aluminum oxide as a carrier, wherein the iron-modified supported nickel-based catalyst is 20% Ni-5% Fe/Al 2 O 3 pH8.0, grinding to 40-60 mesh. In the attached drawing, 20% Ni-5% Fe/Al 2 O 3 X-ray diffraction pattern at pH8.0 shows that the catalyst contains NiAl at the same time 2 O 4 Spinel structure and individual alumina crystals.
The application of the iron-modified supported nickel-based catalyst with aluminum oxide as a carrier in preparing hexamethylenediamine by hydrogenation of adiponitrile comprises the following steps:
2.5g of 20% Ni-5% Fe/Al are introduced into a fixed bed reactor 2 O 3 A catalyst with pH of 8.0, wherein quartz cotton and quartz sand are filled at the upper end and the lower end of the catalystThe catalyst position is located in a constant temperature area, the reaction raw material is ethanol solution with the mass fraction of adiponitrile of 25%, the raw material solution is conveyed into the reactor by a advection pump, and the flow rate is 0.10ml/min. Introducing 3.0MPa hydrogen, keeping the flow rate of the hydrogen at 32.8mL/min, setting the reaction temperature at 110 ℃, taking a sample at intervals of 2 hours, and carrying out quantitative analysis by using chromatography. Adiponitrile conversion was 89% and hexamethylenediamine selectivity was 46%.
Example 4
At 25 ℃, 150g deionized water was measured to dissolve 11.8373g Ni (NO 3 ) 2 ·6H 2 O、4.3286g Fe(NO 3 ) 3 ·9H 2 O、66.1765g Al(NO 3 ) 3 ·9H 2 O, fully stirring and mixing to obtain a precursor solution; a certain amount of deionized water is measured to dissolve 63.6g of anhydrous Na 2 CO 3 Uniformly mixing to prepare a precipitant solution with the concentration of 1 mol/L; simultaneously dropwise adding a precipitant solution and a precursor solution into a beaker which is pre-filled with a proper amount of deionized water at a water bath heating stirring temperature of 50 ℃ at a dropping rate of 3:1, keeping the pH value at 8.5, aging the solution for 3 hours after the precursor solution is completely added under the water bath heating stirring temperature of 50 ℃, carrying out suction filtration, drying the precipitate at 110 ℃ for 12 hours without washing, and roasting at 500 ℃ for 6 hours to obtain the iron-modified supported nickel-based catalyst with aluminum oxide as a carrier, wherein the iron-modified supported nickel-based catalyst is 20% Ni-5% Fe/Al 2 O 3 pH8.5, grinding to 40-60 mesh. In the attached drawing, 20% Ni-5% Fe/Al 2 O 3 X-ray diffraction pattern at pH8.5 shows that the catalyst contains NiAl at the same time 2 O 4 Spinel structure and individual alumina crystals.
The application of the iron-modified supported nickel-based catalyst with aluminum oxide as a carrier in preparing hexamethylenediamine by hydrogenation of adiponitrile comprises the following steps:
2.5g of 20% Ni-5% Fe/Al are introduced into a fixed bed reactor 2 O 3 And (3) filling quartz cotton and quartz sand at the upper end and the lower end of the catalyst to enable the catalyst position to fall in a constant temperature area, wherein the reaction raw material is an ethanol solution with the mass fraction of adiponitrile of 25%, and the raw material solution is conveyed into a reactor by a advection pump, and has the flow rate of 0.10ml/min. Introducing 3.0MPa hydrogen, and hydrogenThe gas flow rate was maintained at 32.8mL/min, the reaction temperature was set at 110℃and samples were taken at 2h intervals and analyzed quantitatively by chromatography. Adiponitrile conversion was 49% and hexamethylenediamine selectivity was 10%.
Example 5
The supported nickel-based catalyst prepared under the neutral condition is used for preparing hexamethylenediamine by hydrogenation of adiponitrile, and the preparation method of the catalyst comprises the following steps:
at 25 ℃, 150g deionized water was measured to dissolve 11.8373g Ni (NO 3 ) 2 ·6H 2 O、4.3286g Fe(NO 3 ) 3 ·9H 2 O、66.1765g Al(NO 3 ) 3 ·9H 2 O, fully stirring and mixing to obtain a precursor solution; a certain amount of deionized water is measured to dissolve 63.6g of anhydrous Na 2 CO 3 Uniformly mixing to prepare a precipitant solution with the concentration of 1 mol/L; simultaneously dropwise adding a precipitant and a precursor into a beaker which is pre-filled with a proper amount of deionized water at a water bath heating stirring temperature of 50 ℃ at a dropping rate of 3:1, keeping the pH at 7.0, aging the solution for 3 hours after the precursor solution is completely added in the water bath heating stirring temperature of 50 ℃, carrying out suction filtration, then carrying out a drying process of the precipitate at 110 ℃ for 12 hours without washing, and roasting at 500 ℃ for 6 hours to obtain the iron-modified supported nickel-based catalyst with aluminum oxide as a carrier, wherein the iron-modified supported nickel-based catalyst is 20% Ni-5% Fe/Al 2 O 3 -ph7.0, grinding to 40-60 mesh.
The application of the supported nickel-based catalyst prepared in the embodiment in preparing hexamethylenediamine by hydrogenation of adiponitrile comprises the following steps:
2.5g of 20% Ni-5% Fe/Al are introduced into a fixed bed reactor 2 O 3 And (3) a catalyst with pH of 7.0, wherein quartz cotton and quartz sand are filled at the upper end and the lower end of the catalyst so that the catalyst position falls in a constant temperature zone, the reaction raw material is an ethanol solution with the mass fraction of adiponitrile of 25%, and the raw material solution is conveyed into a reactor by a advection pump, and the flow rate is 0.12mL/min. Introducing 3.0MPa hydrogen, keeping the flow rate of the hydrogen at 39.4mL/min, setting the reaction temperature at 110 ℃, taking a sample at intervals of 2 hours, and carrying out quantitative analysis by using chromatography. Adiponitrile conversion was 99% and hexamethylenediamine selectivity was 52%.
Example 6
The embodiment is K 2 CO 3 The iron modified supported nickel-based catalyst taking alumina prepared as a precipitator as a carrier is used for preparing hexamethylenediamine by hydrogenation of adiponitrile, and the preparation method of the catalyst comprises the following steps of:
at 25 ℃, 150g deionized water was measured to dissolve 11.8373g Ni (NO 3 ) 2 ·6H 2 O、4.3286g Fe(NO 3 ) 3 ·9H 2 O、66.1765g Al(NO 3 ) 3 ·9H 2 O, fully stirring and mixing to obtain a precursor solution; a certain amount of deionized water is measured to dissolve 82.8g of anhydrous K 2 CO 3 Uniformly mixing to prepare a precipitant solution with the concentration of 1 mol/L; simultaneously dropwise adding a precipitant solution and a precursor solution into a beaker which is pre-filled with a proper amount of deionized water at a water bath heating stirring temperature of 50 ℃ at a dropping rate of 3:1, keeping the pH at 7.2, aging the solution for 3 hours after the precursor solution is completely added under the water bath heating stirring temperature of 50 ℃, carrying out suction filtration, drying the precipitate at 110 ℃ for 12 hours without washing, and roasting at 500 ℃ for 6 hours to obtain the iron-modified supported nickel-based catalyst with aluminum oxide as a carrier, wherein the iron-modified supported nickel-based catalyst is 20% Ni-5% Fe/Al 2 O 3 -K 2 CO 3 Grinding to 40-60 mesh with pH 7.2.
The application of the supported nickel-based catalyst in preparing hexamethylenediamine by hydrogenation of adiponitrile comprises the following steps:
2.5g of 20% Ni-5% Fe/Al are introduced into a fixed bed reactor 2 O 3 And (3) a catalyst with pH of 7.0, wherein quartz cotton and quartz sand are filled at the upper end and the lower end of the catalyst so that the catalyst position falls in a constant temperature zone, the reaction raw material is an ethanol solution with the mass fraction of adiponitrile of 25%, and the raw material solution is conveyed into a reactor by a advection pump, and the flow rate is 0.10mL/min. Introducing 3.0MPa hydrogen, keeping the flow rate of the hydrogen at 32.8mL/min, setting the reaction temperature at 110 ℃, taking a sample at intervals of 2 hours, and carrying out quantitative analysis by using chromatography. Adiponitrile conversion was 66% and hexamethylenediamine selectivity was 8%.
As can be seen from the results of comparative examples 1 and 5 and example 6, the supported nickel-based catalyst prepared in example 1 has a higher selectivity for hexamethylenediamine under the weak alkaline condition, and potassium carbonate is decomposed to form potassium oxide during calcination when it is used as a precipitant, so that the basicity is significantly enhanced, thereby resulting in a significant decrease in adiponitrile conversion and hexamethylenediamine selectivity.
In the foregoing embodiments, the descriptions of the embodiments are emphasized, and for parts of one embodiment that are not described in detail, reference may be made to related descriptions of other embodiments.
The above description is made in detail of a supported nickel-based catalyst, a preparation method and an application provided in the embodiments of the present application, and specific examples are applied herein to illustrate the principles and embodiments of the present application, and the above description of the examples is only used to help understand the method and core ideas of the present application; meanwhile, those skilled in the art will have variations in the specific embodiments and application scope in light of the ideas of the present application, and the present description should not be construed as limiting the present application in view of the above.
Claims (10)
1. A supported nickel-based catalyst, characterized in that the supported nickel-based catalyst comprises a carrier and an active component, the active component comprising Fe 2 O 3 And NiAl 2 O 4 The method comprises the steps of carrying out a first treatment on the surface of the The carrier comprises Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The active component accounts for 50-70% of the weight of the supported nickel-based catalyst.
2. The supported nickel-based catalyst according to claim 1, wherein the mass ratio of Ni to Fe in the active component is 8:1 to 4:1; and/or the number of the groups of groups,
the carrier is gamma-Al 2 O 3 。
3. The method for preparing a supported nickel-based catalyst according to any one of claims 1 to 2, comprising the steps of:
(S1) preparing a precursor: preparation of Ni-containing alloy 2+ 、Fe 3+ 、Al 3+ Is a precursor solution of (a);
(S2) preparing a precipitant: preparation of the CO-containing products 3 2- Is added to the solution of the precipitant;
(S3) mixing the solutions obtained in the step (S1) and the step (S2), and maintaining the pH to be stable during the mixing process;
(S4) aging the mixed solution obtained in the step (S3) at 50-80 ℃;
and (S5) carrying out suction filtration, drying, roasting and grinding on the mixed solution obtained in the step (S4) to obtain the supported nickel-based catalyst.
4. The method for producing a supported nickel-based catalyst according to claim 3, wherein in the step (S2), CO 3 2- The concentration is 0.5-1.5 mol/L.
5. The method for producing a supported nickel-based catalyst according to claim 3, wherein in the step (S3), the pH is 7.0 to 8.5.
6. The method for preparing a supported nickel-based catalyst according to claim 3, wherein in the step (S5), the drying temperature is 90 to 110 ℃ and the drying time is 12 to 24 hours.
7. The method for preparing a supported nickel-based catalyst according to claim 3, wherein in the step (S5), the calcination temperature is 500 to 600 ℃ and the calcination time is 4 to 6 hours.
8. The method for producing a supported nickel-based catalyst according to claim 3, wherein in the step (S2), CO 3 2- Derived from one or both of sodium carbonate and potassium carbonate.
9. Use of a supported nickel-based catalyst according to any one of claims 1-2 or prepared by a preparation method according to any one of claims 3-8 in adiponitrile hydrogenation reactions.
10. The preparation method of hexamethylenediamine is characterized by comprising the following steps of:
taking a mixed solution of adiponitrile and ethanol as a reaction raw material, and introducing hydrogen;
preparing hexamethylenediamine by catalyzing adiponitrile hydrogenation reaction with the supported nickel-based catalyst according to any one of claims 1 to 2 or the supported nickel-based catalyst prepared by the preparation method according to any one of claims 3 to 8; and/or the number of the groups of groups,
the reaction pressure of the hydrogenation reaction is 3.0-9.0 MPa; and/or the number of the groups of groups,
the reaction temperature of the hydrogenation reaction is 90-200 ℃.
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