CN106622220B - Hydrogenation catalyst, preparation method and application - Google Patents
Hydrogenation catalyst, preparation method and application Download PDFInfo
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- CN106622220B CN106622220B CN201610970790.5A CN201610970790A CN106622220B CN 106622220 B CN106622220 B CN 106622220B CN 201610970790 A CN201610970790 A CN 201610970790A CN 106622220 B CN106622220 B CN 106622220B
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- Prior art keywords
- hydrotalcite
- dimethyl
- catalyst
- hydrogenation catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 9
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 20
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 20
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 5
- WLLURKMCNUGIRG-UHFFFAOYSA-N alumane;cerium Chemical compound [AlH3].[Ce] WLLURKMCNUGIRG-UHFFFAOYSA-N 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 7
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 claims description 2
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 claims description 2
- 229910001051 Magnalium Inorganic materials 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- -1 methyl - Chemical class 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims 1
- 235000012222 talc Nutrition 0.000 claims 1
- 239000000454 talc Substances 0.000 claims 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 13
- 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 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical group [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 abstract 1
- 238000001914 filtration Methods 0.000 description 22
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 15
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- 238000003483 aging Methods 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- QANIADJLTJYOFI-UHFFFAOYSA-K aluminum;magnesium;carbonate;hydroxide;hydrate Chemical compound O.[OH-].[Mg+2].[Al+3].[O-]C([O-])=O QANIADJLTJYOFI-UHFFFAOYSA-K 0.000 description 7
- SWCIQHXIXUMHKA-UHFFFAOYSA-N aluminum;trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SWCIQHXIXUMHKA-UHFFFAOYSA-N 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- ZATZOOLBPDMARD-UHFFFAOYSA-N magnesium;hydrate Chemical compound O.[Mg] ZATZOOLBPDMARD-UHFFFAOYSA-N 0.000 description 5
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000004962 Polyamide-imide Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- CQGVSILDZJUINE-UHFFFAOYSA-N cerium;hydrate Chemical compound O.[Ce] CQGVSILDZJUINE-UHFFFAOYSA-N 0.000 description 2
- 229920002312 polyamide-imide Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 108010088350 Lactate Dehydrogenase 5 Proteins 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 108010087599 lactate dehydrogenase 1 Proteins 0.000 description 1
- 108010088076 lactate dehydrogenase 2 Proteins 0.000 description 1
- 108010088074 lactate dehydrogenase 3 Proteins 0.000 description 1
- 108010088351 lactate dehydrogenase 4 Proteins 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000069 nitrogen hydride Chemical group 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000009466 transformation Effects 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a hydrogenation catalyst, a preparation method and application thereof, in particular to a hydrogenation catalyst for synthesizing 3,3 '-dimethyl-4, 4' -diaminodicyclohexylmethane, a preparation method and application thereof, and belongs to the technical field of chemistry. The catalyst consists of a carrier hydrotalcite and an active component ruthenium, wherein the hydrotalcite is magnesium aluminum or cerium aluminum layered double hydroxide. The catalyst has good catalytic activity and high selectivity, is particularly suitable for catalytic hydrogenation reaction for synthesizing 3,3 '-dimethyl-4, 4' -diaminodicyclohexyl methane, effectively reduces reaction temperature and pressure, can obtain higher stereoisomer content of the product, has low requirements on equipment, and has good industrial application prospect.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst, preparation method and application more particularly to a kind of 3,3 '-diformazans of synthesis
Hydrogenation catalyst, preparation method and the application of 4,4 '-diamino-dicyclohexyl methane of base-, belong to technical field of chemistry.
Background technique
3,3 '-dimethyl -4,4 '-diamino-dicyclohexyl methane (MACM) are widely used in as a kind of important intermediate
The synthesis of polyamide and polyimides, the polyamide or polyimide material of synthesis have excellent calorifics, mechanics and optics
Performance is applied to aerospace industry, wind-power electricity generation and defence and military etc..Meanwhile MACM can make as a kind of alicyclic diamine
For polyurethane chain extender and epoxy curing agent.The elasticity of the existing rubber of polyurethane of MACM synthesis, and have the intensity of plastics
With excellent processing performance, especially sound insulation, heat-insulated, wear-resisting, oil resistant, in terms of have other synthetic materials incomparable
Advantage；Its polyamide synthesized has nontoxic, light, excellent mechanical strength, wearability and preferable corrosion resistance；It is applied to
Epoxy resin has a series of excellent properties such as cohesiveness is strong, electrical insulating property is excellent, chemical property is stable and processing performance is good.
In recent years, the application of MACM at home and abroad expands rapidly, and the good MACM of production performance has great industrial value and business
Value, and MACM stereoisomer ratio largely influences application range and downstream product performance.
Currently, the related patents of the production method about MACM are seldom, and industrially produced by monopolization.Related patents
As follows: the hydrate and hydrophobic silica that ru oxide is disclosed in patent WO2009090179 obtain oxygen containing ruthenium after adding hydrogen
The suspension of compound is as catalyst, and under the pressure of 200bar, MDT liquid melt hydrogenates in the presence of a catalyst
Reaction, reaction are cooled to 230-240 DEG C and obtain target product.The patent carries out at high temperature and pressure, the high requirements on the equipment,
And reacting under high temperature easily increases the by-product generated, and MACM stereoisomer ratio is not referred to.
It is disclosed in patent US20120289747 in 500mL reaction kettle, using silicon dioxide carried ruthenium as catalyst, with
The tetrahydrofuran solution of 17.7% ortho-aminotoluene is solvent, reacts 2.5h at 75bar hydrogen pressure, 180 DEG C of temperature, obtains
98.15% MACM yield, but MACM stereoisomer ratio is not referred to yet.
It is disclosed in patent WO2010005859 in 300mL reaction kettle, using alumina load ruthenium as catalyst, with methyl
Tetrahydrofuran is solvent, reacts 3h at 70bar hydrogen pressure, 185 DEG C of temperature, obtains 85% MACM yield, and report gas phase
The isomer proportion that chromatography obtains.
MACM product can be obtained using the prior art, but be industrially generally required to the harsher item such as high temperature and pressure
Part has higher requirement to equipment.And the product reacted in small-sized reaction kettle, it is more difficult to obtain high income, while first
The MACM product that isomer proportion is also met the requirements, and the solvent cost used is also relatively high.
Summary of the invention
The purpose of the present invention is in view of the defects existing in the prior art, proposing a kind of 3,3 '-dimethyl -4 of synthesis, 4 '-two
The hydrogenation catalyst of amino bicyclic hexyl methane, preparation method and application.
Present invention firstly provides a kind of synthesis 3,3 '-dimethyl -4,4 '-diamino-dicyclohexyl methane hydrogenation catalysts
Agent, the hydrogenation catalyst are made of active component and carrier, and the active component is the metal Ru that weight content is 3-10%,
The carrier is hydrotalcite, and hydrotalcite weight content is 90-97%.
The hydrotalcite is magnalium or cerium aluminium layered double hydroxide.
The molar ratio of aluminum nitrate and magnesium nitrate or cerous nitrate is 1-3:1 in the hydrotalcite.
The present invention further provides a kind of synthesis 3,3 '-dimethyl -4,4 '-diamino-dicyclohexyl methane hydrogenation catalysts
The preparation method of agent, comprising the following steps:
Step 1: aluminum nitrate and magnesium nitrate or cerous nitrate are dissolved in deionized water, mixed solution A is obtained；
Step 2: weighing alkali compounds is dissolved in configuration alkali compounds aqueous solution B in deionized water；
Step 3: 65 DEG C, keep stirring under conditions of, while be added dropwise mixed solution A and alkali compounds aqueous solution B into
Row co-precipitation, mixture ageing, filtering, drying finally roast 3 hours at 200 DEG C, obtain hydrotalcite supports；
Step 4: hydrotalcite supports to be ground into the powder of 30-50 mesh, it is added into the ruthenium saline solution containing 35-40wt%
Stirring 2-2.5 hours, stands overnight, and filters, and filter cake is washed to neutrality, dries at 120 DEG C, and hydrogen reducing at 200 DEG C is urged
Agent Ru/LDH.
The mixed solution A concentration of the above method is 15-30wt%.
The alkali compounds aqueous solution B is LiOH, NaOH, KOH or NH3·H2One of O, concentration 10-
25wt%.
The present invention further provides a kind of synthesis 3,3 '-dimethyl -4,4 '-diamino-dicyclohexyl methane plus hydrogen is urged
The application of agent is used for 3,3 '-dimethyl -4,4 '-diaminodiphenylmethane hydrogenation synthesizing reactions, and reaction temperature is 160 DEG C, hydrogen
Atmospheric pressure is 8Mpa, and tetrahydrofuran 60mL, 3,3 '-dimethyl -4 5g, 4 '-diamino hexichol first are added in 500ml reaction kettle
Alkane, 0.8g hydrogenation catalyst, reaction time 5h.
Reaction equation is as follows:
3,3 '-dimethyl -4,4 '-diaminodiphenylmethane product isomers shown in formula I:
In above-mentioned application, 3,3 '-dimethyl -4,4 '-diamino-dicyclohexyl methane yields >=97%, 3,3 '-diformazans
Base -4,4 '-diaminodiphenylmethane product assay >=30wt%.
The beneficial effects of the invention are as follows easy preparations, and catalytic activity is good, and selectivity is high, MACM high income, particularly suitable for synthesis
3,3 '-dimethyl -4, the catalytic hydrogenation reaction of 4 '-diamino-dicyclohexyl methanes are effectively reduced reaction temperature and pressure, are not necessarily to
Addition auxiliary agent can obtain the product of higher proportion isomers shown in formula I, and production cost is low, and there is good industrialization to answer
Use prospect.
Specific embodiment
Embodiment 1
37.5g ANN aluminium nitrate nonahydrate and bis- nitric hydrate magnesium of 55.3g are dissolved in 500g deionized water, it is molten to be made into mixing
Liquid A.Configure 15wt% lithium hydroxide aqueous solution B.Under being kept stirring at 65 DEG C, into four-hole boiling flask simultaneously be added dropwise solution A and
Solution B is co-precipitated, mixture ageing, filtering, filtration cakes torrefaction, is roasted 3 hours at 200 DEG C, is ground, obtain hydrotalcite
Support powder.It takes 5g hydrotalcite powder to be added in the aqueous solution of 0.6g ruthenic chloride (ruthenium content 37wt%) to stir 2 hours, it is quiet
Filtering overnight is set, filter cake is washed with deionized water to neutrality, dry, hydrogen reducing at 200 DEG C.Obtain catalyst Ru/LDH-1.
Embodiment 2
37.5g ANN aluminium nitrate nonahydrate and bis- nitric hydrate magnesium of 36.9g are dissolved in 400g deionized water, mixed solution is made into
A.Configure 10wt% lithium hydroxide aqueous solution B.Under keeping stirring at 65 DEG C, solution A and molten is added dropwise simultaneously into four-hole boiling flask
Liquid B is co-precipitated, mixture ageing, filtering, filtration cakes torrefaction, is roasted 3 hours, is ground at 200 DEG C, and hydrotalcite load is obtained
Body powder.It takes 5g hydrotalcite powder to be added in the aqueous solution of 0.6g ruthenic chloride (ruthenium content 37wt%) to stir 2 hours, stand
Overnight, filtering, filter cake is washed with deionized water to neutrality, dry, hydrogen reducing at 200 DEG C.Obtain catalyst Ru/LDH-2.
Embodiment 3
37.5g ANN aluminium nitrate nonahydrate and bis- nitric hydrate magnesium of 55.3g are dissolved in 400g deionized water, mixed solution is made into
A.Configure 20wt% sodium hydrate aqueous solution B.Under keeping stirring at 65 DEG C, solution A and molten is added dropwise simultaneously into four-hole boiling flask
Liquid B is co-precipitated, mixture ageing, filtering, filtration cakes torrefaction, is roasted 3 hours, is ground at 200 DEG C, and hydrotalcite load is obtained
Body powder.It takes 5g hydrotalcite powder to be added in the aqueous solution of 0.6g ruthenic chloride (ruthenium content 37wt%) to stir 2 hours, stand
Overnight, filtering, filter cake is washed with deionized water to neutrality, dry, hydrogen reducing at 200 DEG C.Obtain catalyst Ru/LDH-3.
Embodiment 4
37.5g ANN aluminium nitrate nonahydrate and bis- nitric hydrate magnesium of 55.3g are dissolved in 350g deionized water, mixed solution is made into
A.Configure 20wt% potassium hydroxide aqueous solution B.Under keeping stirring at 65 DEG C, solution A and molten is added dropwise simultaneously into four-hole boiling flask
Liquid B is co-precipitated, mixture ageing, filtering, filtration cakes torrefaction, is roasted 3 hours, is ground at 200 DEG C, and hydrotalcite load is obtained
Body powder.It takes 5g hydrotalcite powder to be added in the aqueous solution of 1.2g ruthenic chloride (ruthenium content 37wt%) to stir 2 hours, stand
Overnight, filtering, filter cake is washed with deionized water to neutrality, dry, hydrogen reducing at 200 DEG C.Obtain catalyst Ru/LDH-4.
Embodiment 5
37.5g ANN aluminium nitrate nonahydrate and six nitric hydrate cerium of 43.4g are dissolved in 450g deionized water, mixed solution is made into
A.Configure 15wt% lithium hydroxide aqueous solution B.Under keeping stirring at 65 DEG C, solution A and molten is added dropwise simultaneously into four-hole boiling flask
Liquid B is co-precipitated, mixture ageing, filtering, filtration cakes torrefaction, is roasted 3 hours, is ground at 200 DEG C, and hydrotalcite load is obtained
Body powder.It takes 5g hydrotalcite powder to be added in the aqueous solution of 0.6g ruthenic chloride (ruthenium content 37wt%) to stir 2 hours, stand
Overnight, filtering, filter cake is washed with deionized water to neutrality, dry, hydrogen reducing at 200 DEG C.Obtain catalyst Ru/LDH-5.
Embodiment 6
37.5g ANN aluminium nitrate nonahydrate and bis- nitric hydrate magnesium of 55.3g are dissolved in 500g deionized water, mixed solution is made into
A.Configure 10wt% ammonia spirit B.Under being kept stirring at 65 DEG C, solution A is added dropwise simultaneously into four-hole boiling flask and solution B carries out
It is co-precipitated, mixture ageing, filtering, filtration cakes torrefaction, is roasted 3 hours at 200 DEG C, grind, obtain hydrotalcite supports powder.
It takes 5g hydrotalcite powder to be added in the aqueous solution of 0.84g ruthenic chloride (ruthenium content 37wt%) to stir 2 hours, stand overnight,
Filtering, filter cake is washed with deionized water to neutrality, dry, hydrogen reducing at 200 DEG C.Obtain catalyst Ru/LDH-6.
Embodiment 7
37.5g ANN aluminium nitrate nonahydrate and six nitric hydrate cerium of 43.4g are dissolved in 500g deionized water, mixed solution is made into
A.Configure 10wt% lithium hydroxide solution B.Under keeping stirring at 65 DEG C, solution A and solution B is added dropwise simultaneously into four-hole boiling flask
It is co-precipitated, mixture ageing, filtering, filtration cakes torrefaction, is roasted 3 hours at 200 DEG C, grind, obtain hydrotalcite supports
Powder.It takes 5g hydrotalcite powder to be added in the aqueous solution of 0.36g ruthenic chloride (ruthenium content 37wt%) to stir 2 hours, stand
Overnight, filtering, filter cake is washed with deionized water to neutrality, dry, hydrogen reducing at 200 DEG C.Obtain catalyst Ru/LDH-7.
Hydrotalcite supported ruthenium catalyst made from embodiment 1 to 7 the method for embodiment is used for 3,3 '-dimethyl -4,
4 '-diaminodiphenylmethane (MDT) hydrogenation synthesis, 3,3 '-dimethyl -4,4 '-diamino-dicyclohexyl methanes (MACM) reaction,
Test its catalyst performance.Specific reaction condition are as follows: temperature be 160 DEG C, Hydrogen Vapor Pressure be 8MPa under conditions of, in 500mL
Solvents tetrahydrofurane 60mL, 3,3 '-dimethyl -4 of 5g raw material, 4 '-diaminodiphenylmethane, 0.8g catalysis are added in reaction kettle
Agent, reaction time 5h.
Catalyst performance test result is as follows table:
As it can be seen that the catalyst being prepared by above embodiments is synthesizing 3,3 '-dimethyl -4,4 '-diamino, two hexamethylene
In the reaction of methylmethane, MACM high income can obtain the production of higher proportion isomers shown in formula I without adding auxiliary agent
Product have higher commercial price and value, are conducive to further synthesize downstream product.
In addition to above-mentioned implementation, the present invention can also have other embodiments.It is all to be formed using equivalent substitution or equivalent transformation
Technical solution, fall within the scope of protection required by the present invention.
Claims (1)
1. a kind of 3,3 '-dimethyl -4 of synthesis, the application of the hydrogenation catalyst of 4 '-diamino-dicyclohexyl methanes, described plus hydrogen
Catalyst is made of active component and carrier, and the active component is the metal Ru that weight content is 3-10%, and the carrier is water
Talcum, hydrotalcite weight content are 90-97%;The hydrogenation catalyst is used for 3,3 '-dimethyl -4,4 '-diamino hexichol first
Alkane hydrogenation synthesizing reaction, reaction temperature are 160 DEG C, and tetrahydrofuran is added in 500ml reaction kettle in Hydrogen Vapor Pressure 8Mpa
3,3 '-dimethyl -4 60mL, 5g, 4 '-diaminodiphenylmethane, 0.8g hydrogenation catalyst, reaction time 5h;3,3 '-two
4,4 '-diamino-dicyclohexyl methane yield >=97%, 3 of methyl -, 3 '-dimethyl -4,4 '-diaminodiphenylmethane products contain
Amount >=30wt%;The hydrotalcite is magnalium or cerium aluminum hydrotalcite;Aluminum nitrate and magnesium nitrate or cerous nitrate rubs in the hydrotalcite
You are than being 1-3:1.
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| CN102030657A (en) * | 2010-11-25 | 2011-04-27 | 浙江台州清泉医药化工有限公司 | Synthesizing method of 3,3'-dimethyl-4,4'-diamido-dicyclohexyl methane |
| CN102627569A (en) * | 2012-03-01 | 2012-08-08 | 江苏清泉化学有限公司 | Method for synthesizing 3,3'-dimethyl-4,4'-diamino dicyclohexyl methane |
| CN105921155A (en) * | 2016-05-16 | 2016-09-07 | 北京化工大学 | High-dispersion supported ruthenium dioxide catalyst and preparing method thereof |
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| CN102627569A (en) * | 2012-03-01 | 2012-08-08 | 江苏清泉化学有限公司 | Method for synthesizing 3,3'-dimethyl-4,4'-diamino dicyclohexyl methane |
| CN105921155A (en) * | 2016-05-16 | 2016-09-07 | 北京化工大学 | High-dispersion supported ruthenium dioxide catalyst and preparing method thereof |
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