CN116589363B - Preparation method of catalyst for preparing 1, 3-cyclohexanediamine by hydrogenating m-xylylenediamine in micro-packed bed - Google Patents
Preparation method of catalyst for preparing 1, 3-cyclohexanediamine by hydrogenating m-xylylenediamine in micro-packed bed Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 121
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 title claims abstract description 38
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 29
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000012018 catalyst precursor Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052596 spinel Inorganic materials 0.000 claims description 12
- 239000011029 spinel Substances 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229910020068 MgAl Inorganic materials 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 24
- 238000000034 method Methods 0.000 abstract description 15
- 150000001412 amines Chemical class 0.000 abstract description 7
- 238000007086 side reaction Methods 0.000 abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 abstract description 4
- 229910021529 ammonia Inorganic materials 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 8
- 150000004982 aromatic amines Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 241000219782 Sesbania Species 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000009615 deamination Effects 0.000 description 3
- 238000006481 deamination reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- -1 alicyclic amine Chemical class 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical group NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001448 anilines Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- AVKNGPAMCBSNSO-UHFFFAOYSA-N cyclohexylmethanamine Chemical compound NCC1CCCCC1 AVKNGPAMCBSNSO-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical group CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/70—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines
- C07C209/72—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines by reduction of six-membered aromatic rings
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- 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 invention relates to a preparation method of a catalyst for preparing 1, 3-cyclohexanediamine by hydrogenating m-xylylenediamine in a micro-packed bed, which comprises the following steps: preparing a catalyst carrier; preparation of LiOH-modified Ru/MgO.Al 2O3 monometal catalyst 1, 3-cyclohexanedimethanamine was prepared by hydrogenation in a micro packed bed reactor. The hydrogenation is selected in the micro-packed bed reactor to prepare the 1, 3-cyclohexanediamine, so that the progress of side reactions such as demethanization and the like can be inhibited, the yield and the selectivity of target products are improved, and the temperature in the reactor can be more accurate; in addition, the reaction pressure and the molar ratio of the hydrogen and the amine are lower, the equipment requirement is low, the hydrogen circulation amount is small, so the energy consumption of production operation can be lower, the catalyst structure and the synergistic effect of the catalyst are adopted to ensure that the catalytic activity is high, the participation of ammonia or other organic amines in the reaction is not needed, the method is economical and environment-friendly, the side reaction can be effectively reduced, and the catalytic efficiency is improved.
Description
Technical Field
The application relates to the field of catalysts, in particular to a preparation method of a catalyst for preparing 1, 3-cyclohexanediamine by hydrogenating m-xylylenediamine in a micro-packed bed.
Background
1, 3-Cyclohexanediamine is a desired alicyclic amine product, also known as 1, 3-aminomethylcyclohexane or 1, 3-bis (aminomethyl) cyclohexane, and is known by the english name 1,3-cyclohexanebis (methylamine). The 1, 3-cyclohexanediamine has the advantages of low unsaturation degree, low viscosity, higher reaction activity, strong chemical resistance, good curing effect and the like, so the 1, 3-cyclohexanediamine is the most commonly used amine curing agent. In particular, after m-xylylenediamine is included as a toxic chemical, 1, 3-xylylenediamine is used as a substitute therefor, and the demand in the field of epoxy resins is rapidly increasing. Meanwhile, the 1, 3-cyclohexanediamine is used as an important intermediate in fine chemical industry and organic chemical industry, and can be widely used for synthesizing polyurethane intermediates, composite materials, stone materials and the like.
The key to the process route for preparing 1, 3-cyclohexanediamine by selective hydrogenation of m-xylylenediamine is a good catalytic system. In recent years, few studies have been made on the reaction of m-xylylenediamine for preparing 1, 3-cyclohexanediamine by selective hydrogenation, and many reports have been made on catalytic systems of aromatic amines in which amino groups such as hydrogenated aniline, m-phenylenediamine and o-methylaniline are directly connected to benzene rings; because of the compatibility of the hydrogenation reaction of aromatic amine compounds, the research on catalysts for hydrogenation reaction of aromatic amines can be referred to each other.
The existing aromatic amine chemical hydrogenation catalytic system can be mainly divided into a noble metal catalytic system, a Ni-based catalytic system and the like. Researchers at home and abroad use VIII group transition metal as the active component of the catalyst, which comprises the following components: ni, co, ru, rh, pd and Pt, a supported catalyst was studied, and a reaction for preparing cyclohexylamine by selective hydrogenation of aromatic amine was carried out using a kettle reactor. The use of Ru, rh, pd, pt and other noble metals as active center components of the catalyst in aromatic amine hydrogenation is a main aromatic amine hydrogenation catalyst system. In the aromatic amine hydrogenation reaction, the noble metal catalyst shows good catalytic activity, and can efficiently realize selective hydrogenation of benzene rings. According to the current state of research of noble metal catalysts, it is mainly classified into single-component metal catalysts and double-component metal catalysts. The existing process route for preparing the 1, 3-cyclohexanediamine by the selective hydrogenation of the m-xylylenediamine mostly adopts a reaction kettle preparation process, and has the defects of low selectivity, higher deamination and deamination byproducts, poor catalyst stability, high dosage, difficult separation and the like, so that the methods have a plurality of problems in the process of realizing batch industrial production.
In addition, in the hydrogenation reaction of m-xylylenediamine, because each substance in the catalytic system usually has a plurality of hydrogenation active sites, the main reaction is carried out and simultaneously the secondary reaction of de-methylamine or deamination occurs, so that the m-xylylenediamine or a target product is subjected to deep hydrogenation, and the selectivity and the yield of the target product 1, 3-cyclohexanedimethylamine are reduced.
At present, for the reaction process of preparing 1, 3-cyclohexanediamine by the selective hydrogenation of m-xylylenediamine, some progress is made in the research of a reaction catalytic system thereof, but the following disadvantages still exist: (1) The occurrence of side reactions such as demethanization and the like in a reaction system cannot be effectively inhibited; (2) The report of the technological conditions of the micro-packed bed hydrogenation reaction is less; (3) stability studies of the catalyst still need improvement; (4) The catalyst prepared by a precipitation method and the like has high cost, long period and difficult operation.
Disclosure of Invention
Aiming at the defects of the prior researches, the invention provides a preparation method of a catalyst for preparing 1, 3-cyclohexanediamine by hydrogenating m-xylylenediamine in a micro-packed bed.
The invention provides a preparation method of a catalyst for preparing 1, 3-cyclohexanediamine by hydrogenating m-xylylenediamine in a micro-packed bed, which comprises the following steps:
S1, preparing a catalyst carrier MgO.Al 2O3:
Uniformly mixing MgAl 2O4 powder, aluminum hydroxide dry gel and sesbania powder, dripping dilute nitric acid, extruding and molding to obtain a magnesia-alumina spinel carrier, placing the magnesia-alumina spinel carrier in a muffle furnace, calcining for 4 hours at 500 ℃, and removing impurities possibly existing as far as possible to obtain a catalyst carrier MgO.Al 2O3;
S2, preparing a LiOH modified Ru/MgO.Al 2O3 single-metal catalyst:
S21, weighing a certain amount of RuCl 3·H2 O, and dissolving in 100mL of deionized water;
S22, after stirring for 30min, adding the catalyst carrier MgO.Al 2O3 prepared in the step S1 into the solution, and then continuously stirring for 12h;
s23, centrifugally separating the obtained mixed solution by a centrifugal machine, washing by deionized water and ethanol in sequence, and vacuum drying for 12 hours at 350 ℃ to obtain a catalyst precursor;
s24, calcining the obtained catalyst precursor in a muffle furnace at 643 ℃ for 5 hours, and reducing the calcined catalyst in a mixed gas of H 2/N2 in a tubular furnace at 500 ℃ for 6 hours to obtain a reduced catalyst sample which is marked as 5 Ru/MgO.Al 2O3;
s25, accurately weighing a certain amount of 5 Ru/MgO.Al 2O3 catalyst and dissolving in 100mL of deionized water;
s26, adding metered lithium hydroxide into the solution after stirring for 30min, and then continuing stirring for 24h;
S27, centrifugally separating the obtained mixed solution by a centrifugal machine, washing by deionized water and ethanol in sequence, and vacuum drying for 12 hours at 350 ℃ to obtain a catalyst sample, which is marked as 5 Ru-xLi/MgO.Al 2O3.
S3, preparing 1, 3-cyclohexanediamine:
Adding 0.5g of 5 Ru-xLi/MgO.Al 2O3 catalyst into a micro-packed bed reactor, and carrying out hydrogenation reaction under the conditions of 3-8 MPa of reaction pressure, 120-140 ℃ of reaction temperature, 0.3-0.4 h -1 of liquid space velocity and 20-30 of hydrogen-amine molar ratio to obtain 1, 3-cyclohexanediamine.
According to the preparation method of the catalyst for preparing the 1, 3-cyclohexanediamine by hydrogenating the m-xylylenediamine in the micro-packed bed, disclosed by the invention, the ruthenium-based bimetallic catalyst with proper pore diameter structure, excellent catalytic performance and good stability can be prepared, the m-xylylenediamine is used as a raw material, and the 1, 3-cyclohexanediamine is prepared by selecting hydrogenation in the micro-packed bed reactor, so that the progress of side reactions such as demethanization can be inhibited, the yield and selectivity of target products can be improved, and the temperature in the reactor can be more accurate; in addition, the reaction pressure and the molar ratio of the hydrogen and the amine are lower, the equipment requirement is low, the hydrogen circulation amount is small, so the energy consumption of production operation can be lower, the catalyst structure and the synergistic effect of the catalyst are adopted to ensure that the catalytic activity is high, the participation of ammonia or other organic amines in the reaction is not needed, the method is economical and environment-friendly, the side reaction can be effectively reduced, and the catalytic efficiency is improved.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
The invention provides a preparation method of a catalyst for preparing 1, 3-cyclohexanediamine by hydrogenating m-xylylenediamine in a micro-packed bed, which comprises the following steps:
S1, preparing a catalyst carrier MgO.Al 2O3:
Mixing MgAl 2O4 powder, aluminum hydroxide dry gel and sesbania powder uniformly, dripping dilute nitric acid, extruding and molding to obtain magnesia-alumina spinel carrier, placing the magnesia-alumina spinel carrier in a muffle furnace, calcining for 4h at 500 ℃, and removing impurities possibly existing as far as possible to obtain the catalyst carrier MgO.Al 2O3.
Wherein, mgAl 2O4 powder with larger area, aluminum hydroxide dry glue and sesbania powder are reasonably mixed and extruded to form, so that more active components can appear on the carrier, and the catalytic activity of the subsequent catalyst is increased. In addition, the muffle furnace is calcined at a proper temperature to remove impurities as much as possible, so that the quality of the prepared catalyst carrier is ensured.
S2, preparing the LiOH modified Ru/MgO.Al 2O3 single metal catalyst.
S21, weighing a certain amount of RuCl 3·H2 O and dissolving in 100mL of deionized water.
The proper deionized water is selected to avoid the interference of impurities on the catalyst precursor, so that the purity of the reaction is ensured; the addition of RuCl 3·H2 O can provide the catalytic metal required for the subsequent metal catalyst.
S22, after stirring for 30min, adding the catalyst carrier MgO.Al 2O3 prepared in the step S1 into the solution, and then continuously stirring for 12h.
Wherein, stirring for 30min is helpful for fully mixing RuCl 3·H2 O and the carrier, and improves the activity and stability of the catalyst. Through stirring for 12 hours, ruCl 3·H2 O can be more evenly distributed on the surface of the carrier, and the catalytic efficiency of the catalyst is enhanced.
S23, centrifugally separating the obtained mixed solution by a centrifugal machine, washing by deionized water and ethanol in sequence, and vacuum drying for 12 hours at 350 ℃ to obtain the catalyst precursor.
Wherein, the centrifugal separation of the centrifugal machine can effectively remove unreacted substances and other impurities, and improve the purity of the catalyst. The unreacted substances and impurities on the surface of the catalyst can be removed by washing with deionized water and ethanol in sequence, so that the stability and activity of the catalyst are ensured. After the catalyst is dried for 12 hours at 350 ℃ in vacuum, the catalyst can reach a better drying degree, and the subsequent calcination treatment is facilitated.
S24, calcining the obtained catalyst precursor in a muffle furnace at 643 ℃ for 5 hours, and reducing the calcined catalyst in a mixed gas of H 2/N2 in a tubular furnace at 500 ℃ for 6 hours to obtain a reduced catalyst sample which is marked as 5 Ru/MgO.Al 2O3.
Wherein, the high temperature calcination in the muffle furnace can promote the formation of the catalyst crystal structure and the adjustment of the metal quantum size, thereby further improving the performance of the catalyst. After reduction in the mixed gas of H 2/N2, the metal catalyst can be more uniformly distributed on the surface of the carrier, so that the catalytic activity is enhanced.
S25, accurately weighing a certain amount of 5 Ru/MgO.Al 2O3 catalyst and dissolving in 100mL of deionized water.
Wherein, the proper deionized water is selected to avoid the interference of the catalyst by impurities and ensure the purity of the reaction.
S26, after stirring for 30min, adding metered lithium hydroxide into the solution, and then stirring for 24 hours.
Wherein, stirring for 30min is helpful for fully mixing the 5 Ru/MgO.Al 2O3 catalyst and lithium hydroxide, and improves the activity and stability of the catalyst. After 24 hours of stirring, lithium hydroxide can be more evenly distributed on the surface of the catalyst, and the catalytic efficiency is enhanced.
S27, centrifugally separating the obtained mixed solution by a centrifugal machine, washing by deionized water and ethanol in sequence, and vacuum drying for 12 hours at 350 ℃ to obtain a catalyst sample, which is marked as 5 Ru-xLi/MgO.Al 2O3.
Wherein, the centrifugal separation of the centrifugal machine can effectively remove unreacted substances and other impurities, and improve the purity of the catalyst. The unreacted substances and impurities on the surface of the catalyst can be removed by washing with deionized water and ethanol in sequence, so that the stability and activity of the catalyst are ensured. After the catalyst is dried for 12 hours at 350 ℃ in vacuum, the catalyst can reach a better drying degree, and the subsequent calcination treatment is facilitated. 5 Ru-xLi/MgO.Al 2O3 is the final catalyst sample prepared in step S2. Wherein 5 represents the mass fraction of Ru metal in the catalyst and x represents the amount of LiOH modification in the catalyst. The catalyst has good catalytic performance in the subsequent 1, 3-cyclohexanediamine hydrogenation reaction, and can effectively promote the reaction.
S3, preparing 1, 3-cyclohexanediamine by hydrogenation in a micro-packed bed reactor:
Adding 0.5g of 5 Ru-xLi/MgO.Al 2O3 catalyst into a micro-packed bed reactor, and carrying out hydrogenation reaction under the conditions of 3-8 MPa of reaction pressure, 120-140 ℃ of reaction temperature, 0.3-0.4 h -1 of liquid space velocity and 20-30 of hydrogen-amine molar ratio to obtain 1, 3-cyclohexanediamine.
Wherein, the 5 Ru-xLi/MgO.Al 2O3 catalyst can effectively catalyze the synthesis reaction of the 1,3 cyclohexanediamine. The micro-packed bed reactor is helpful to improve the reaction efficiency and the purity of the product under the proper conditions of reaction pressure, reaction temperature and liquid space velocity.
Example 1
The preparation method of the catalyst for preparing the 1, 3-cyclohexanediamine by hydrogenating the m-xylylenediamine in the micro-packed bed comprises the following steps:
S1, preparing a catalyst carrier MgO.Al 2O3:
Uniformly mixing MgAl 2O4 powder, aluminum hydroxide dry gel and sesbania powder, dripping dilute nitric acid, extruding and molding to obtain a magnesia-alumina spinel carrier, placing the magnesia-alumina spinel carrier in a muffle furnace, calcining for 4 hours at 500 ℃, and removing impurities possibly existing as far as possible to obtain a catalyst carrier MgO.Al 2O3;
S2, preparing a LiOH modified Ru/MgO.Al 2O3 single-metal catalyst:
S21, weighing a certain amount of RuCl 3·H2 O, and dissolving in 100mL of deionized water;
S22, after stirring for 30min, adding the catalyst carrier MgO.Al 2O3 prepared in the step S1 into the solution, and then continuously stirring for 12h;
s23, centrifugally separating the obtained mixed solution by a centrifugal machine, washing by deionized water and ethanol in sequence, and vacuum drying for 12 hours at 350 ℃ to obtain a catalyst precursor;
s24, calcining the obtained catalyst precursor in a muffle furnace at 643 ℃ for 5 hours, and reducing the calcined catalyst in a mixed gas of H 2/N2 in a tubular furnace at 500 ℃ for 6 hours to obtain a reduced catalyst sample which is marked as 5 Ru/MgO.Al 2O3;
s25, accurately weighing a certain amount of 5 Ru/MgO.Al 2O3 catalyst and dissolving in 100mL of deionized water;
s26, adding metered lithium hydroxide into the solution after stirring for 30min, and then continuing stirring for 24h;
S27, centrifugally separating the obtained mixed solution by a centrifugal machine, washing by deionized water and ethanol in sequence, and vacuum drying for 12 hours at 350 ℃ to obtain a catalyst sample, which is marked as 5 Ru-xLi/MgO.Al 2O3.
S3, preparing 1, 3-cyclohexanediamine:
Adding 0.5g of 5 Ru-xLi/MgO.Al 2O3 catalyst into a micro-packed bed reactor, and carrying out hydrogenation reaction under the conditions of reaction pressure of 3MPa, reaction temperature of 130 ℃, liquid space velocity of 0.3h -1 and hydrogen-amine molar ratio of 20 to obtain 1, 3-cyclohexanediamine.
Example 2
The preparation method of the catalyst for preparing the 1, 3-cyclohexanediamine by hydrogenating the m-xylylenediamine in the micro-packed bed comprises the following steps:
S1, preparing a catalyst carrier MgO.Al 2O3:
Uniformly mixing MgAl 2O4 powder, aluminum hydroxide dry gel and sesbania powder, dripping dilute nitric acid, extruding and molding to obtain a magnesia-alumina spinel carrier, placing the magnesia-alumina spinel carrier in a muffle furnace, calcining for 4 hours at 500 ℃, and removing impurities possibly existing as far as possible to obtain a catalyst carrier MgO.Al 2O3;
S2, preparing a LiOH modified Ru/MgO.Al 2O3 single-metal catalyst:
S21, weighing a certain amount of RuCl 3·H2 O, and dissolving in 100mL of deionized water;
S22, after stirring for 30min, adding the catalyst carrier MgO.Al 2O3 prepared in the step S1 into the solution, and then continuously stirring for 12h;
s23, centrifugally separating the obtained mixed solution by a centrifugal machine, washing by deionized water and ethanol in sequence, and vacuum drying for 12 hours at 350 ℃ to obtain a catalyst precursor;
s24, calcining the obtained catalyst precursor in a muffle furnace at 643 ℃ for 5 hours, and reducing the calcined catalyst in a mixed gas of H 2/N2 in a tubular furnace at 500 ℃ for 6 hours to obtain a reduced catalyst sample which is marked as 5 Ru/MgO.Al 2O3;
s25, accurately weighing a certain amount of 5 Ru/MgO.Al 2O3 catalyst and dissolving in 100mL of deionized water;
s26, adding metered lithium hydroxide into the solution after stirring for 30min, and then continuing stirring for 24h;
S27, centrifugally separating the obtained mixed solution by a centrifugal machine, washing by deionized water and ethanol in sequence, and vacuum drying for 12 hours at 350 ℃ to obtain a catalyst sample, which is marked as 5 Ru-xLi/MgO.Al 2O3.
S3, preparing 1, 3-cyclohexanediamine:
Adding 0.5g of 5 Ru-xLi/MgO.Al 2O3 catalyst into a micro-packed bed reactor, and carrying out hydrogenation reaction under the conditions of reaction pressure of 5MPa, reaction temperature of 120 ℃, liquid space velocity of 0.3h -1 and hydrogen-amine molar ratio of 20 to obtain 1, 3-cyclohexanediamine.
Example 3
The preparation method of the catalyst for preparing the 1, 3-cyclohexanediamine by hydrogenating the m-xylylenediamine in the micro-packed bed comprises the following steps:
S1, preparing a catalyst carrier MgO.Al 2O3:
Uniformly mixing MgAl 2O4 powder, aluminum hydroxide dry gel and sesbania powder, dripping dilute nitric acid, extruding and molding to obtain a magnesia-alumina spinel carrier, placing the magnesia-alumina spinel carrier in a muffle furnace, calcining for 4 hours at 500 ℃, and removing impurities possibly existing as far as possible to obtain a catalyst carrier MgO.Al 2O3;
S2, preparing a LiOH modified Ru/MgO.Al 2O3 single-metal catalyst:
S21, weighing a certain amount of RuCl 3·H2 O, and dissolving in 100mL of deionized water;
S22, after stirring for 30min, adding the catalyst carrier MgO.Al 2O3 prepared in the step S1 into the solution, and then continuously stirring for 12h;
s23, centrifugally separating the obtained mixed solution by a centrifugal machine, washing by deionized water and ethanol in sequence, and vacuum drying for 12 hours at 350 ℃ to obtain a catalyst precursor;
s24, calcining the obtained catalyst precursor in a muffle furnace at 643 ℃ for 5 hours, and reducing the calcined catalyst in a mixed gas of H 2/N2 in a tubular furnace at 500 ℃ for 6 hours to obtain a reduced catalyst sample which is marked as 5 Ru/MgO.Al 2O3;
s25, accurately weighing a certain amount of 5 Ru/MgO.Al 2O3 catalyst and dissolving in 100mL of deionized water;
s26, adding metered lithium hydroxide into the solution after stirring for 30min, and then continuing stirring for 24h;
S27, centrifugally separating the obtained mixed solution by a centrifugal machine, washing by deionized water and ethanol in sequence, and vacuum drying for 12 hours at 350 ℃ to obtain a catalyst sample, which is marked as 5 Ru-xLi/MgO.Al 2O3.
S3, preparing 1, 3-cyclohexanediamine:
Adding 0.5g of 5 Ru-xLi/MgO.Al 2O3 catalyst into a micro-packed bed reactor, and carrying out hydrogenation reaction under the conditions of reaction pressure of 8MPa, reaction temperature of 140 ℃, liquid space velocity of 0.4h -1 and hydrogen-amine molar ratio of 30 to obtain 1, 3-cyclohexanediamine.
Compared with the prior art, the method has the following advantages: 1) The operation is simple: the catalyst can be prepared by simple steps such as dipping, drying and the like, and the operation difficulty is low. 2) The preparation period is short: the time of many steps in the method is relatively short, such as stirring time, drying time and the like, so that the preparation period of the catalyst can be greatly shortened. 3) The catalytic activity is high: the method can prepare the LiOH modified Ru/MgO.Al 2O3 catalyst with higher catalytic activity. 4) The application range is wide: the method is simple and convenient to operate, can be used under the condition of a conventional laboratory, and has a wide application range. 5) The cost is low: compared with other methods such as precipitation method, the method has the advantages of less equipment and reagent articles and low cost.
According to the preparation method of the catalyst for preparing the 1, 3-cyclohexanediamine by hydrogenating the m-xylylenediamine in the micro-packed bed, disclosed by the invention, the ruthenium-based bimetallic catalyst with proper pore diameter structure, excellent catalytic performance and good stability can be prepared, the m-xylylenediamine is used as a raw material, and the 1, 3-cyclohexanediamine is prepared by selecting hydrogenation in the micro-packed bed reactor, so that the progress of side reactions such as demethanization can be inhibited, the yield and selectivity of target products can be improved, and the temperature in the reactor can be more accurate; in addition, the reaction pressure and the molar ratio of the hydrogen and the amine are lower, the equipment requirement is low, the hydrogen circulation amount is small, so the energy consumption of production operation can be lower, the catalyst structure and the synergistic effect of the catalyst are adopted to ensure that the catalytic activity is high, the participation of ammonia or other organic amines in the reaction is not needed, the method is economical and environment-friendly, the side reaction can be effectively reduced, and the catalytic efficiency is improved.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution, and the present invention is intended to be covered in the scope of the present invention.
Claims (1)
1. The preparation method of the catalyst for preparing the 1, 3-cyclohexanediamine by hydrogenating the m-xylylenediamine in the micro-packed bed is characterized by comprising the following steps of:
S1, preparing a catalyst carrier MgO.Al 2O3:
Uniformly mixing MgAl 2O4 powder, aluminum hydroxide dry gel and sesbania powder, dripping dilute nitric acid, extruding to form a magnesia-alumina spinel carrier, and calcining the magnesia-alumina spinel carrier in a muffle furnace at 500 ℃ for 4 hours to obtain a catalyst carrier MgO-Al 2O3;
S2, preparing a LiOH modified Ru/MgO.Al 2O3 single metal catalyst, namely a 5 Ru-xLi/MgO.Al 2O3 catalyst:
S21, weighing a certain amount of RuCl 3·H2 O, and dissolving in 100mL of deionized water;
S22, stirring for 30min, adding the catalyst carrier MgO.Al 2O3 prepared in the step S1 into the solution, and then continuously stirring for 12h;
s23, centrifugally separating the obtained mixed solution by a centrifugal machine, washing by deionized water and ethanol in sequence, and vacuum drying for 12 hours at 350 ℃ to obtain a catalyst precursor;
s24, calcining the obtained catalyst precursor in a muffle furnace at 643 ℃ for 5 hours, and reducing the calcined catalyst in a mixed gas of H 2/N2 in a tubular furnace at 500 ℃ for 6 hours to obtain a reduced catalyst sample which is marked as 5 Ru/MgO.Al 2O3;
s25, accurately weighing a certain amount of 5 Ru/MgO.Al 2O3 catalyst and dissolving in 100mL of deionized water;
s26, adding metered lithium hydroxide into the solution after stirring for 30min, and then continuing stirring for 24h;
S27, centrifugally separating the obtained mixed solution by a centrifugal machine, washing the mixed solution by deionized water and ethanol in sequence, and vacuum drying the mixed solution at 350 ℃ for 12 hours to obtain a catalyst sample, which is marked as 5 Ru-xLi/MgO.Al 2O3;
S3, preparing 1, 3-cyclohexanediamine by hydrogenation in a micro-packed bed reactor:
adding 0.5g of 5 Ru-xLi/MgO.Al 2O3 catalyst into a micro-packed bed reactor, and carrying out hydrogenation reaction under the conditions of reaction pressure of 3-8 MPa, reaction temperature of 120-140 ℃, liquid space velocity of 0.3-0.4 h -1 and hydrogen-amine molar ratio of 20-30 to obtain 1, 3-cyclohexanediamine.
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