CN117358235A - Catalyst for preparing MACM by continuous hydrogenation and preparation method and application thereof - Google Patents
Catalyst for preparing MACM by continuous hydrogenation and preparation method and application thereof Download PDFInfo
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- CN117358235A CN117358235A CN202310966335.8A CN202310966335A CN117358235A CN 117358235 A CN117358235 A CN 117358235A CN 202310966335 A CN202310966335 A CN 202310966335A CN 117358235 A CN117358235 A CN 117358235A
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- metal
- metal oxide
- macm
- mdt
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 72
- 239000002184 metal Substances 0.000 claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 37
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 35
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 14
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- -1 lanthanide metal oxide Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims 1
- 239000006227 byproduct Substances 0.000 abstract description 14
- 230000009615 deamination Effects 0.000 abstract description 13
- 238000006481 deamination reaction Methods 0.000 abstract description 13
- 239000000047 product Substances 0.000 abstract description 11
- 239000000539 dimer Substances 0.000 abstract description 6
- 239000007791 liquid phase Substances 0.000 abstract description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 description 37
- 238000007792 addition Methods 0.000 description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 239000011572 manganese Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000008213 purified water Substances 0.000 description 6
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 2
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012527 feed solution Substances 0.000 description 2
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical group O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 229920000805 Polyaspartic acid Polymers 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910000311 lanthanide oxide Inorganic materials 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 108010064470 polyaspartate Proteins 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
- B01J23/38—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
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
-
- 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
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6522—Chromium
-
- 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
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6525—Molybdenum
-
- 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
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6567—Rhenium
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst for preparing MACM by continuous hydrogenation and a preparation method and application thereof, belonging to the technical field of liquid phase catalytic hydrogenation. The catalyst disclosed by the invention comprises an active component serving as a carrier and loaded on the carrier, wherein the carrier comprises silicon dioxide and a metal oxide auxiliary agent M2, and the active component comprises ruthenium and a metal auxiliary agent M1; the metal auxiliary agent M1 comprises any one of Mo, re, cr and Mn; the metal oxide promoter M2 is an alkaline earth metal oxide. The catalyst can effectively inhibit the generation of byproducts such as hydrogenated dimer, deamination product and the like during the reaction in a fixed bed reactor, meanwhile, the catalyst can ensure that the MDT conversion rate of the raw material reaches more than 99.7 percent, the selectivity of the MACM product reaches more than 97.5 percent, the content of the first isomer in the MACM product is less than or equal to 26 percent by weight, the service life is long, and the catalyst can stably run for more than 2500 hours.
Description
Technical Field
The invention belongs to the technical field of liquid phase catalytic hydrogenation, and particularly relates to a catalyst for preparing MACM (MACM) through continuous hydrogenation, a preparation method and application thereof.
Background
3,3 '-dimethyl-4, 4' -diaminodicyclohexylmethane (MACM) is widely used as a chain extender and auxiliary agent for epoxy resin curing agents, epoxy paint curing agents (such as ship paint, heavy-duty paint, etc.), epoxy composite material curing agents (such as wind blade curing agents, wind mold material curing agents, etc.), synthetic Polyurethane (PU), polyurea spray elastomer (SPUA), etc.; it can also be used for synthesizing polyaspartic acid ester, polyamide (PA), etc. Polyurethane synthesized by MACM has the elasticity of rubber, the strength of plastic and excellent processing performance, and has the incomparable advantages of other materials in the aspects of sound insulation, heat resistance, wear resistance, oil resistance, elasticity and the like. The synthesized polyamide has the characteristics of no toxicity and light weight, and simultaneously has excellent mechanical strength, better wear resistance and corrosion resistance. In recent years, MACM has been rapidly expanding in application at home and abroad, and MACM with excellent productivity has significant industrial and commercial value.
In the prior art, 3 '-dimethyl-4, 4' -diaminophenylmethane (MDT) is mostly adopted for hydrogenation to prepare 3,3 '-dimethyl-4, 4' -diaminodicyclohexylmethane (MACM), and the reaction has the technical difficulties that (one) and byproducts are more: the method is mainly characterized by comprising two types, 1) the generated intermediate imine is very active, is very easy to generate condensation reaction with a product MACM to generate a hydrogenated dimer, 2) amino is easy to be deaminated in the process of generating cyclohexane by benzene ring hydrogenation, and an amino byproduct is obtained; and secondly, the catalyst is easy to agglomerate and deactivate, and the service life of the catalyst is short. The prior art adopts an intermittent kettle type hydrogenation process to obtain MACM, the kettle type hydrogenation process has low production efficiency and high labor intensity, and the yield and the selectivity of the reaction are reduced in the continuous hydrogenation process of liquid phase catalysis along with the continuous expansion of the dosage of MACM, so that the design of a catalyst suitable for the continuous hydrogenation of the liquid phase catalysis is urgently needed, and the continuous production process of MACM is developed.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a catalyst for preparing MACM by continuous hydrogenation, a preparation method and application thereof, and the catalyst can effectively improve the activity of the catalyst and the service life of the catalyst, can effectively improve the yield of continuous hydrogenation reaction of liquid phase catalysis, and can effectively inhibit the generation of byproducts such as hydrogenated dimer, deamination product and the like by modifying and loading metal auxiliary agent M1 on carrier silicon dioxide and adopting ruthenium modified by metal oxide auxiliary agent M2 as an active component.
The invention is realized by adopting the following technical scheme:
in a first aspect, the present invention provides a catalyst for preparing MACM, comprising a support, an active component supported on the support, a metal promoter M1 and a metal oxide promoter M2, the support comprising silica, the active component comprising ruthenium.
Further, the metal auxiliary M1 comprises at least one of Mo, re, cr and Mn; preferably, the metal auxiliary M1 is Mn.
Further, the metal oxide auxiliary agent M2 is alkaline earth metal oxide or lanthanide oxide; preferably, the metal oxide auxiliary M2 comprises CaO, baO, mgO, la 2 O 3 And at least one of SrO, more preferably, the alkaline earth metal oxide comprises CaO or BaO; most preferably, the alkaline earth metal oxide is CaO.
Further, the mass fraction of ruthenium is 0.5 to 10wt% based on the total mass of the catalyst; the mass fraction of the metal auxiliary agent M1 is 0.5-5wt%; the mass fraction of the metal oxide auxiliary agent M2 is 5.0-20.0 wt% and the balance is silicon dioxide.
In a second aspect, the present invention also provides a method for preparing the catalyst for continuous hydrogenation preparation of MACM, comprising the steps of:
step S1: the precursor of the metal oxide auxiliary agent M2 is immersed on silicon dioxide in an equal volume, and is dried and roasted to obtain M2-SiO 2 ；
Step S2: mixing active component ruthenium precursor and metal auxiliary agent M1 precursor, and soaking in M2-SiO in equal volume 2 And (3) sequentially carrying out precipitation, drying and reduction to obtain the catalyst.
Further, the precursor of the metal oxide additive M2 is nitrate of the corresponding metal.
Further, the precursor of the active component ruthenium is ruthenium trichloride;
further, the precursor of the metal auxiliary M1 is XCl of the corresponding metal 2 、X(NO 3 ) 3 、H 2 XO 4 Or NH 4 XO 4 Wherein X is a corresponding metal element in the metal auxiliary M1.
Further, in step S1, the immersion time is 12 to 36 hours.
In step S1, the drying temperature is 110-140 ℃ and the drying time is 4-16 h.
In step S1, the roasting temperature is 350-500 ℃ and the roasting time is 2-8 h.
Further, in step S2, the immersion time is 12 to 36 hours.
Further, the precipitant comprises at least one of NaOH, ammonia water, sodium carbonate and sodium bicarbonate; more preferably, the precipitant comprises NaOH or sodium carbonate; most preferably, the precipitant is sodium carbonate.
Further, what is said isThe reducing agent is formaldehyde, naBH 4 At least one of hydrazine hydrate and hydrogen. More preferably, the reducing agent is formaldehyde or hydrazine hydrate; most preferably, the reducing agent is formaldehyde.
In a third aspect, the invention provides an application of the catalyst or the catalyst prepared by the method in preparing MACM by continuous hydrogenation.
In a fourth aspect, the present invention provides a method for preparing MACM by continuous hydrogenation of MDT, comprising the steps of:
MDT is added into a reaction solvent to obtain a raw material liquid;
and (3) reacting the raw material liquid with a fixed bed reactor containing the catalyst or the catalyst prepared by the preparation method to obtain MACM.
Further, the reaction solvent is THF.
Further, the hydrogenation pressure of the fixed bed reactor is 2.0-10.0 MPa; more preferably, the hydrogenation pressure of the fixed bed reactor is 2.0-5.0 MPa; most preferably, the hydrogenation pressure of the fixed bed reactor is 3.0MPa.
Further, the reaction temperature is 110-220 ℃; more preferably, the reaction temperature is 150-170 ℃; most preferably the reaction temperature is 160 ℃.
Further, the space velocity of the feeding mass of MDT is 0.1 to 1.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the More preferably, the MDT has a feed mass space velocity of 0.1 to 0.3h -1 The method comprises the steps of carrying out a first treatment on the surface of the Most preferably, the MDT has a feed mass space velocity of 0.2h -1 。
Further, the molar ratio of the hydrogen to the MDT is 10.0-80.0; more preferably, the molar ratio of hydrogen to MDT is 30.0.
Further, the MDT accounts for 10 to 60 weight percent of the reaction liquid; more preferably, the MDT accounts for 20-40 wt% of the reaction liquid; most preferably 15wt%.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, ru is loaded on the surface of the silicon dioxide carrier as an active component, and alkaline earth metal oxide auxiliary agent M2 is added to modify the carrier, so that the generation of byproducts such as hydrogenated dimer and the like can be effectively inhibited when MACM is prepared by continuous hydrogenation; meanwhile, the supported metal auxiliary agent M1 modifies the electronic state of the active component ruthenium, and forms an alloy or a bimetallic catalyst with the active component metal Ru, so that the generation of deamination byproducts is inhibited.
(2) Through strictly controlling the loading amounts of active components and two metal assistants, the catalyst prepared by the invention can ensure that the conversion rate of the MDT of the raw material reaches more than 99.7 percent, the selectivity of the MACM product reaches more than 97.5 percent, the content of the first isomer in the MACM product is less than or equal to 26 percent by weight, the service life of the catalyst is long, and the catalyst can stably run for more than 2500 hours.
Detailed Description
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
For the purposes of this specification and the appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, as used in the specification and the appended claims, are to be understood as being modified in all instances by the term "about". Furthermore, all ranges disclosed herein are inclusive of the endpoints and independently combinable.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below.
Examples 1-13 are process examples for preparing the catalyst.
Example 1
Preparing a catalyst:
22.8g of calcium nitrate tetrahydrate is weighed, dissolved in 12.0g of purified water, and 30.0g of dried SiO 2 Immersing the carrier in the solution for carrying out isovolumetric immersion for 24 hours;
soaking SiO 2 Drying the carrier at 120 ℃ for 6 hours and roasting the carrier at 450 ℃ for 4 hours to obtain CaO-SiO 2 A carrier;
weighing 0.98g of ruthenium trichloride solid and 0.83g of manganese chloride solid, dissolving in 30.0g of purified water to obtain a preparation solution, and mixing the CaO-SiO 2 Immersing the carrier in the preparation solution, and carrying out isovolumetric immersion for 24 hours;
CaO-SiO after impregnation 2 Drying the carrier at 120 ℃ for 6 hours, then putting the carrier into a 10% sodium carbonate solution, stirring, precipitating, adding formaldehyde for reduction, finally filtering and washing until no chloride ions exist in the filtrate, and continuously drying at 120 ℃ for 6 hours to obtain the catalyst 1.
In the catalyst 1, the theoretical loading of the active component metal Ru is 1.0%, the theoretical loading of the metal Mn serving as the metal auxiliary M1 is 1.0%, and the theoretical loading of the CaO serving as the metal oxide auxiliary M2 is 15.0% according to the total mass of the catalyst.
Example 2
Unlike example 1, the metal oxide promoter M2 was BaO, the precursor of which was barium nitrate, 9.25g of barium nitrate was weighed, dissolved in 23.0g of purified water, and 30.0g of dried SiO 2 The support was immersed in the above solution for an equal volume impregnation for 24 hours. The rest conditions were the same, to prepare catalyst 2.
According to the total mass of the catalyst, the theoretical loading of the active component metal Ru in the catalyst 2 is 1.0%, the theoretical loading of the metal Mn serving as the metal auxiliary M1 is 1.0%, and the theoretical loading of the BaO serving as the metal oxide auxiliary M2 is 15.0%.
Example 3
Unlike example 1, mgO is used as the metal oxide additive M2, the precursor is magnesium nitrate hexahydrate, 34.5g of magnesium nitrate hexahydrate is weighed, 25.0g of purified water is used for dissolution, and 30.0g of dried SiO 2 Immersing the carrier in the solutionSoaking in the solution for 24h, spin-drying excessive water, and preparing the catalyst 3 under the same conditions.
According to the total mass of the catalyst, the theoretical loading of the active component metal Ru in the catalyst 3 is 1.0%, the theoretical loading of the metal Mn serving as the metal auxiliary M1 is 1.0%, and the theoretical loading of MgO serving as the metal oxide auxiliary M2 is 15.0%.
Example 4
Unlike example 1, la was used as the metal oxide auxiliary M2 2 O 3 The precursor is lanthanum nitrate hexahydrate, 7.21g of lanthanum nitrate hexahydrate is weighed, 25.0g of purified water is used for dissolving, and 30.0g of dried SiO 2 The carrier was immersed in the above solution for an equal volume impregnation for 24 hours under the same conditions to prepare catalyst 4.
Based on the total mass of the catalyst, the theoretical loading of the active component metal Ru in the catalyst 4 is 1.0 percent, the theoretical loading of the metal Mn serving as the metal auxiliary M1 is 1.0 percent, and the La serving as the metal oxide auxiliary M2 is 1.0 percent 2 O 3 Is 15.0%.
Example 5
Unlike example 1, the metal oxide additive M2 was SrO, the precursor of which was strontium nitrate, 11.08g of strontium nitrate was weighed, dissolved in 21.0g of purified water, and 30.0g of dried SiO 2 The support was immersed in the above solution for an equal volume impregnation for 24 hours. The rest of the conditions were the same, to prepare catalyst 5.
According to the total mass of the catalyst, the theoretical loading of the active component metal Ru in the catalyst 5 is 1.0%, the theoretical loading of the metal Mn serving as the metal auxiliary M1 is 1.0%, and the theoretical loading of the SrO serving as the metal oxide auxiliary M2 is 15.0%.
Example 6
Unlike example 1, the metal auxiliary M1 is Re, and its precursor is NH 4 ReO 4 The amount of the catalyst added in the second impregnation was 0.53g, and the other conditions were the same, to thereby prepare a catalyst 6.
According to the total mass of the catalyst, the theoretical loading of the active component metal Ru in the catalyst 6 is 1.0%, the theoretical loading of the metal Re serving as the metal auxiliary agent M1 is 1.0%, and the theoretical loading of the CaO serving as the metal oxide auxiliary agent M2 is 15.0%.
Example 7
Unlike example 1, the metal auxiliary M1 is Mo, the precursor of which is H 2 MoO 4 The amount of the catalyst added in the second impregnation was 0.55g, and the other conditions were the same, to thereby obtain catalyst 7.
According to the total mass of the catalyst, the theoretical loading of the active component metal Ru in the catalyst 7 is 1.0%, the theoretical loading of the metal Mo serving as the metal auxiliary agent M1 is 1.0%, and the theoretical loading of the CaO serving as the metal oxide auxiliary agent M2 is 15.0%.
Example 8
In contrast to example 1, the metal auxiliary M1 is Cr, the precursor of which is Cr (NO 3 ) 3 The amount of the catalyst added in the second impregnation step was 1.65g, and the other conditions were the same, to prepare a catalyst 8.
According to the total mass of the catalyst, the theoretical loading of the active component metal Ru in the catalyst 8 is 1.0%, the theoretical loading of the metal Cr serving as the metal auxiliary agent M1 is 1.0%, and the theoretical loading of the CaO serving as the metal oxide auxiliary agent M2 is 15.0%.
Example 9
Different from example 1, the precipitants in this example were 10% NaOH, 10% ammonia water and 10% sodium bicarbonate, respectively, and the other conditions were the same, to prepare catalysts 9-11.
According to the total mass of the catalyst, the theoretical loading of active component metal Ru in the catalyst 9-11 is 1.0%, the theoretical loading of metal Cr serving as a metal auxiliary agent M1 is 1.0%, and the theoretical loading of CaO serving as a metal oxide auxiliary agent M2 is 15.0%.
Example 10
In the present embodiment, naBH was used as the reducing agent, unlike in example 1 4 The hydrazine hydrate and the hydrogen are the same in other conditions, and the catalyst 12-14 is prepared.
According to the total mass of the catalyst, the theoretical loading of active component metal Ru in the catalyst 12-14 is 1.0%, the theoretical loading of metal Cr serving as a metal auxiliary agent M1 is 1.0%, and the theoretical loading of CaO serving as a metal oxide auxiliary agent M2 is 15.0%.
Example 11
Unlike example 1, the theoretical loading of metal Mn as metal promoter M1 was 0, 0.5%, 2.0%, 3.0% and 5.0%, corresponding to MnCl 2 The amounts of the catalyst added were 0,0.41g,1.65g,2.55g and 4.28g, respectively, and the other conditions were the same, to prepare catalysts 15 to 19.
Example 12
Unlike example 1, the theoretical loadings of metal CaO as metal oxide co-agent M2 were 0, 5.0%, 10.0% and 20.0%, and the corresponding calcium nitrate tetrahydrate additions were 0,6.80g,14.5g and 31.9g, respectively, with the remaining conditions being the same, to prepare catalysts 20 to 23.
Example 13
Unlike example 1, the theoretical loading of metallic ruthenium as an active component was 0.2%, 5.0% and 10%, and the corresponding addition amounts of ruthenium trichloride were 0.49g,5.02g and 10.8g, respectively, with the other conditions being the same, to prepare catalysts 24 to 26.
Comparative example 1
Unlike example 1, the catalyst 27 was prepared without adding the metal oxide auxiliary M2 and the metal auxiliary M1 under the same conditions. In the catalyst 27, the theoretical loading of the active component metal Ru in the catalyst 27 was 1.0%.
Test example 1
Reaction equation for preparing MACM by MDT hydrogenation:
this test example 10.0g of a catalyst, which was prepared according to examples 1 to 13 and comparative example 1, was packed in a 13mm reaction tube of a fixed bed reactor, MDT was dissolved in tetrahydrofuran solvent to obtain 15wt% of a feed solution of MDT, and the feed solution of MDT was pumped into the fixed bed reactor by a feed pumpAnd (3) reacting. Wherein the reaction temperature is 160 ℃, the reaction pressure is 3.0MPa, and the feeding mass space velocity of MDT is 0.2h -1 The molar ratio of hydrogen to MDT was 30.0, tested to give MDT conversion, MACM selectivity, deamination product selectivity and MACM first isomer ratio, and the results are presented in Table 1.
Wherein, MDT conversion (%) = (MDT addition amount (mol) -reaction end MDT measurement amount (mol))/MDT addition amount (mol). Times.100%;
MACM Selectivity (%) = reaction end MACM measurement amount (mol)/(MDT addition amount (mol) -reaction end MDT measurement amount (mol)). Times.100%;
deamination product selectivity (%) = reaction end deamination product measurement (mol)/(MDT addition amount (mol) -reaction end MDT measurement (mol)) ×100%;
MACM first isomer ratio (%) = end of reaction MACM first isomer measurement (mol)/end of reaction MACM measurement (mol) ×100%.
Wherein, the first isomer of MACM has the structural formula:
TABLE 1 screening of MACM catalyst for MDT hydrogenation
As can be seen from catalysts 1 to 5 and catalyst 20 in Table 1, the alkaline earth metal oxide as metal oxide promoter M2 significantly improved the selectivity of MACM during the continuous hydrogenation of MDT in a fixed bed reactor, and the MDT conversion and MACM selectivity were better than those obtained by adding several other metal promoters when CaO was used as metal oxide promoter M2.
As can be seen from catalysts 1, 6-8 and 15 in Table 1, mn is preferably used as the metal promoter M1, and the addition of the metal promoter M1 is effective in improving the selectivity of MACM; and compared with the metal oxide auxiliary agent M2, the metal auxiliary agent M1 can also obviously inhibit the generation of deamination byproducts, which is probably because the metal auxiliary agent M1 can modify the electronic state of the metal Ru and provide electrons for the metal Ru, inhibit the generation of deamination byproducts and effectively inhibit the sintering and agglomeration of the metal Ru.
As can be seen from catalysts 1, 9-11 in Table 1, the precipitant Na was selected 2 CO 3 The activity of the prepared catalyst is higher than that of the catalyst prepared by selecting other precipitants.
As can be seen from catalysts 1 and 12-14 in Table 1, the catalyst prepared with formaldehyde as the reducing agent was more active than the catalyst prepared with several other reducing agents.
As is clear from the catalysts 1, 15 to 19 in Table 1, the addition of Mn was effective in suppressing the formation of deamination by-products, but the addition amount of Mn had an optimum value of 1.0wt%. When the addition amount is low, the deamination by-product cannot be effectively inhibited; when the addition amount is too high, the catalyst activity is inhibited, resulting in a decrease in MDT conversion.
As is clear from the catalysts 1 and 20 to 23 in Table 1, the addition of CaO effectively suppresses the formation of polymers such as hydrogenated dimers and improves the MACM selectivity, but the addition amount of CaO is 15.0% by weight, and the addition amount of CaO is relatively low, and the formation of polymers such as hydrogenated dimers cannot be effectively suppressed, and the addition amount is too high, and the SiO may be blocked 2 The channels may lead to reduced catalyst activity and thus reduced MDT conversion.
As is clear from the catalysts 1, 24 to 26 in Table 1, the loading of ruthenium in the active component had an optimum value of 1.0wt%, and the lower loading of ruthenium resulted in a decrease in catalyst activity and thus in MDT conversion.
In comparison with catalysts 1, 15, 20 and 27 in table 1, the alkaline earth metal oxide CaO and the metal auxiliary Mn may all function to inhibit both polymer formation and deamination by-product formation, in contrast to the alkaline earth metal oxide auxiliary M2, which is a metal oxide auxiliary, which primarily functions to inhibit polymer formation, and the metal auxiliary M1, which primarily functions to inhibit deamination by-product formation.
Examples 14-25 are optimization of the reaction process conditions for the continuous hydrogenation of MDT to MACM in a fixed bed reactor for the catalyst prepared according to example 1. See table 2 for details.
TABLE 2 influence of reaction conditions on MACM Performance by MDT hydrogenation
As can be seen from a comparison of examples 14 to 18 in Table 2, the reaction temperature for MDT hydrogenation is better at 160℃and when the reaction temperature is as low as 150℃or even 110℃the MDT is not partially available for reaction, the reaction is not complete, and thus the hydrogenation effect is poor; and when the reaction temperature is as high as 170 ℃ and above, the byproducts are more due to the overhigh temperature.
As can be seen from examples 14, 19-22 in Table 2, the hydrogenation pressure is more than 3.0MPa, the hydrogenation effect is better, the MDT conversion rate is more than 99.6%, the MACM selectivity is more than 97.4%, and the first isomer ratio is 24.5-25.3%.
As can be seen from examples 14, 23-25 of Table 2, the MDT feed mass space velocity affects the MDT conversion and the MDT feed mass space velocity is at 0.2h -1 Preferably, the method comprises the steps of.
Test example 2
Preparation of MACM by continuous hydrogenation of MDT in a fixed bed reactor according to the reaction process conditions of example 14 the lifetime of catalyst 1 was evaluated experimentally and the evaluation results are shown in Table 3.
TABLE 3 evaluation of MACM catalyst lifetime by MDT hydrogenation
Note that: the starting temperature is increased by 5 ℃ in 2000 hours
As can be seen from the data in Table 3, the reaction time was 10 to 1000 hours, the MDT conversion was substantially stable, the MACM selectivity was gradually increased, and the deamination by-product was decreased. Catalyst 1 had good stability, after 2500h, MDT conversion remained at 99.6%, MACM selectivity as high as 97.9%, first isomer ratio 24.5%. Meanwhile, the catalyst has no obvious deactivation phenomenon after stably running for more than 2500 hours, which proves that the catalyst has good industrial application prospect when being used for preparing MACM by MDT hydrogenation in a fixed bed reactor.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and variations could be made by those skilled in the art without departing from the technical principles of the present invention, and such modifications and variations should also be regarded as being within the scope of the invention.
Claims (10)
1. A catalyst for preparing MACM, comprising a support, an active component supported on the support, a metal promoter M1 and a metal oxide promoter M2, the support comprising silica, the active component comprising ruthenium.
2. The catalyst according to claim 1, wherein the metal auxiliary M1 comprises at least one of Mo, re, cr and Mn;
and/or the metal oxide auxiliary M2 is an alkaline earth metal oxide or a lanthanide metal oxide, the alkaline earth metal oxide is preferably MgO, caO, baO, srO and the lanthanide metal oxide is selected from La 2 O 3 At least one of them.
3. The catalyst according to claim 1, wherein the mass fraction of ruthenium is 0.5 to 10wt% based on the total mass of the catalyst; the mass fraction of the metal auxiliary agent M1 is 0.5-5wt%; the mass fraction of the metal oxide auxiliary agent M2 is 5.0-20.0 wt% and the balance is silicon dioxide.
4. A process for the preparation of a catalyst as claimed in any one of claims 1 to 3, comprising the steps of:
step S1: the precursor of the metal oxide auxiliary agent M2 is immersed on silicon dioxide in an equal volume, and is dried and roasted to obtain M2-SiO 2 ；
Step S2: mixing active component ruthenium precursor and metal auxiliary agent M1 precursor, and soaking in M2-SiO in equal volume 2 And (3) sequentially carrying out precipitation, drying and reduction to obtain the catalyst.
5. The preparation method according to claim 4, wherein the precursor of the metal oxide additive M2 is a nitrate of the metal in the metal oxide additive M2;
and/or the precursor of the active component ruthenium is ruthenium trichloride;
and/or the precursor of the metal auxiliary agent M1 is XCl 2 、X(NO 3 ) 3 、H 2 XO 4 Or NH 4 XO 4 Wherein X is a metal element in the metal auxiliary M1.
6. The method according to claim 4, wherein in the step S1, the dipping time is 12 to 36 hours;
and/or the drying temperature is 110-140 ℃ and the drying time is 4-16 h;
and/or the roasting temperature is 350-500 ℃ and the roasting time is 2-8 h.
7. The method according to claim 4-6, wherein in step S2, the dipping time is 12-36 hours;
and/or the precipitant comprises at least one of NaOH, ammonia water, sodium carbonate and sodium bicarbonate;
and/or the reducing agent is formaldehyde, naBH 4 At least one of hydrazine hydrate and hydrogen.
8. Use of a catalyst according to any one of claims 1-3 or a catalyst prepared according to the preparation method of any one of claims 4-7 in the continuous hydrogenation of MDT to prepare MACM.
9. A method for preparing MACM by MDT continuous hydrogenation, which is characterized by comprising the following steps:
MDT is added into a reaction solvent to obtain a raw material liquid;
contacting the raw material liquid with a catalyst containing any one of the catalysts of claims 1-3 or a catalyst prepared by the preparation method of any one of claims 4-7, and reacting to obtain MACM.
10. The method for preparing MACM by continuous hydrogenation of MDT according to claim 9, wherein the reaction solvent is THF;
and/or the reaction adopts a fixed bed reactor, and the hydrogenation pressure is 2.0-10.0 MPa;
and/or the reaction temperature is 110-220 ℃;
and/or MDT feed mass space velocity of 0.1-1.0 h -1 ；
And/or the molar ratio of hydrogen to MDT is 10.0-80.0;
and/or the MDT accounts for 10-60 wt%, preferably 20-40 wt% of the reaction liquid.
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| CN116037138A (en) * | 2022-12-28 | 2023-05-02 | 西安理工大学 | Double-site single-atom catalyst, preparation method and application |
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