CN106622220A - Hydrogenation catalyst, preparation method and application - Google Patents
Hydrogenation catalyst, preparation method and application Download PDFInfo
- Publication number
- CN106622220A CN106622220A CN201610970790.5A CN201610970790A CN106622220A CN 106622220 A CN106622220 A CN 106622220A CN 201610970790 A CN201610970790 A CN 201610970790A CN 106622220 A CN106622220 A CN 106622220A
- Authority
- CN
- China
- Prior art keywords
- hydrogenation catalyst
- dimethyl
- brucite
- hydrogenation
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 14
- 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 9
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 9
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 9
- WLLURKMCNUGIRG-UHFFFAOYSA-N alumane;cerium Chemical compound [AlH3].[Ce] WLLURKMCNUGIRG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052599 brucite Inorganic materials 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 9
- 238000003483 aging Methods 0.000 claims description 9
- 239000012065 filter cake Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 7
- 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 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001051 Magnalium Inorganic materials 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 238000003556 assay Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910000069 nitrogen hydride Chemical group 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 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 7
- 230000002194 synthesizing effect Effects 0.000 abstract description 5
- 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
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- -1 alicyclic diamine Chemical class 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 150000003841 chloride salts Chemical class 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- ZATZOOLBPDMARD-UHFFFAOYSA-N magnesium;hydrate Chemical compound O.[Mg] ZATZOOLBPDMARD-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- DLYLVPHSKJVGLG-UHFFFAOYSA-N 4-(cyclohexylmethyl)cyclohexane-1,1-diamine Chemical compound C1CC(N)(N)CCC1CC1CCCCC1 DLYLVPHSKJVGLG-UHFFFAOYSA-N 0.000 description 2
- 239000004962 Polyamide-imide Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000000034 method Methods 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
- 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 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 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
- 150000001335 aliphatic alkanes Chemical class 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 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
- 230000000694 effects Effects 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
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 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
- 239000000725 suspension Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000009466 transformation Effects 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, its preparation method and application, more particularly to a kind of synthesis 3,3 '-diformazan
Base -4, the hydrogenation catalyst of 4 '-diamino-dicyclohexyl methane, its preparation method and application, belong to technical field of chemistry.
Background technology
3,3 '-dimethyl -4,4 '-diamino-dicyclohexyl methane (MACM) is widely used in as a kind of important intermediate
The synthesis of polyamide and polyimides, the polyamide or polyimide material of its synthesis have excellent calorifics, mechanics and optics
Performance, is applied to the aspects such as aerospace industry, wind-power electricity generation and defence and military.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, there is the intensity of plastics again
With excellent processing characteristics, especially there are other synthetic materials incomparable at the aspect such as sound insulation, heat-insulated, wear-resisting, oil resistant, elasticity
Advantage;The polyamide of its synthesis has nontoxic, light weight, excellent mechanical strength, wearability and preferable corrosion resistance;It is applied to
Epoxy resin has that cohesiveness is strong, electrical insulating property is excellent, stable chemical nature and a series of excellent properties such as processing characteristics is good.
In recent years, MACM applications at home and abroad expand rapidly, and the good MACM of production performance has great industrial value and business
Value, and MACM stereoisomers ratio affects to a great extent range of application and downstream product performance.
At present, it is little with regard to the Patents of the production method of MACM, and industrially by monopolization production.Patents
It is as follows:The hydrate and hydrophobic silica that ru oxide is disclosed in patent WO2009090179 obtains oxygen containing ruthenium after hydrogenation
Used as catalyst, under the pressure of 200bar, MDT liquid melts are hydrogenated in the presence of a catalyst the suspension of compound
Reaction, reaction is cooled to 230-240 DEG C and obtains target product.The patent is carried out at high temperature and pressure, higher to equipment requirements,
And reacting under high temperature easily increases the by-product of generation, and for MACM stereoisomer ratios are not referred to.
Disclose in patent US20120289747 in 500mL reactors, with silicon dioxide carried ruthenium as catalyst, with
The tetrahydrofuran solution of 17.7% ortho-aminotoluene is solvent, and at 75bar hydrogen pressures, 180 DEG C of temperature 2.5h is reacted, and is obtained
98.15% MACM yields, but do not refer to MACM stereoisomer ratios yet.
Disclose in patent WO2010005859 in 300mL reactors, with alumina load ruthenium as catalyst, with methyl
Tetrahydrofuran is solvent, and at 70bar hydrogen pressures, 185 DEG C of temperature 3h is reacted, and obtains 85% MACM yields, and reports gas phase
The isomer proportion that chromatography is obtained.
MACM products can be obtained using prior art, but be industrially typically required to the harsher bar such as High Temperature High Pressure
Part, there is higher requirement to equipment.And the product obtained in small-sized reaction kettle for reaction, it is more difficult to high income is obtained, while first
Isomer proportion also meets the MACM products of requirement, and the solvent cost for using is also of a relatively high.
The content of the invention
The purpose of the present invention is to be directed to the defect that prior art is present, a kind of synthesis 3 of proposition, 3 '-dimethyl -4,4 '-two
Hydrogenation catalyst, the preparation method and application of amino bicyclic hexyl methane.
Present invention firstly provides a kind of synthesis 3,3 '-dimethyl -4,4 ' hydrogenation catalyst of-diamino-dicyclohexyl methane
Agent, the hydrogenation catalyst is made up of active component and carrier, and the active component is the metal Ru that weight content is 3-10%,
The carrier is brucite, and brucite weight content is 90-97%.
The brucite is magnalium or cerium aluminum layered double hydroxide.
Aluminum nitrate and the mol ratio of magnesium nitrate or cerous nitrate are 1-3 in the brucite:1.
The present invention further provides a kind of synthesis 3,3 '-dimethyl -4,4 ' hydrogenation catalyst of-diamino-dicyclohexyl methane
The preparation method of agent, comprises the following steps:
Step one, aluminum nitrate and magnesium nitrate or cerous nitrate are dissolved in deionized water, obtain mixed solution A;
Step 2, weigh alkali compoundss and be dissolved in deionized water configuration alkali compoundss aqueous solution B;
Step 3,65 DEG C, do not stop stirring under conditions of, while Deca mixed solution A and alkali compoundss aqueous solution B enter
Row co-precipitation, mixture ageing, filtration, drying, finally roasting 3 hours at 200 DEG C, obtain hydrotalcite supports;
Step 4, the powder that hydrotalcite supports are ground to form 30-50 mesh, add into the ruthenium saline solution containing 35-40wt%
Stirring 2-2.5 hours, stand overnight, and filter, and filter cake is washed to neutrality, are dried at 120 DEG C, and hydrogen reducing at 200 DEG C is urged
Agent Ru/LDH.
The mixed solution A concentration of said method is 15-30wt%.
The alkali compoundss aqueous solution B is LiOH, NaOH, KOH or NH3·H2One kind in O, concentration is 10-
25wt%.
The present invention further provides a kind of synthesis 3,3 '-dimethyl -4,4 ' hydrogenation of-diamino-dicyclohexyl methane urges
The application of agent, for 3,3 '-dimethyl -4,4 '-MDA hydrogenation synthesizing reaction, reaction temperature is 160 DEG C, hydrogen
Atmospheric pressure is 8Mpa, and tetrahydrofuran 60mL, 5g 3,3 '-dimethyl -4,4 '-diaminourea hexichol first are added in 500ml reactors
Alkane, 0.8g hydrogenation catalysts, the response time is 5h.
Reaction equation is as follows:
3,3 '-dimethyl -4,4 '-MDA product isomer shown in formula I:
In above-mentioned application, 3,3 '-dimethyl -4,4 '-diamino-dicyclohexyl methane yield >=97%, 3,3 '-diformazan
Base -4,4 '-MDA product assay >=30wt%.
The invention has the beneficial effects as follows easily preparing, catalysis activity is good, and selectivity is high, MACM high incomes, is particularly suited for synthesis
3,3 '-dimethyl -4, the catalytic hydrogenation reaction of 4 '-diamino-dicyclohexyl methane effectively reduces reaction temperature and pressure, without the need for
Addition auxiliary agent is just obtained the product of higher proportion isomer shown in formula I, and low production cost should with good industrialization
Use prospect.
Specific embodiment
Embodiment 1
37.5g ANN aluminium nitrate nonahydrates and the nitric hydrate magnesium of 55.3g bis- are dissolved in 500g deionized waters, mixing is made into molten
Liquid A.Configuration 15wt% lithium hydroxide aqueous solution B.Under not stopping stirring at 65 DEG C, in four-hole boiling flask simultaneously Deca solution A and
Solution B is co-precipitated, mixture ageing, filtration, filtration cakes torrefaction, and roasting 3 hours, grind at 200 DEG C, obtain brucite
Support powder.Take 5g brucite powder and be added to stirring 2 hours in the aqueous solution of 0.6g ruthenic chlorides (ruthenium content is 37wt%), it is quiet
Put overnight, filter, filter cake deionized water is washed till neutrality, be dried, hydrogen reducing at 200 DEG C.Obtain catalyst Ru/LDH-1.
Embodiment 2
37.5g ANN aluminium nitrate nonahydrates and the nitric hydrate magnesium of 36.9g bis- are dissolved in 400g deionized waters, mixed solution is made into
A.Configuration 10wt% lithium hydroxide aqueous solution B.Under not stopping stirring at 65 DEG C, the simultaneously Deca solution A and molten in four-hole boiling flask
Liquid B is co-precipitated, mixture ageing, filtration, filtration cakes torrefaction, and roasting 3 hours, grind at 200 DEG C, obtains brucite load
Body powder.Take 5g brucite powder and be added to stirring 2 hours in the aqueous solution of 0.6g ruthenic chlorides (ruthenium content is 37wt%), stand
Overnight, filter, filter cake deionized water is washed till neutrality, be dried, hydrogen reducing at 200 DEG C.Obtain catalyst Ru/LDH-2.
Embodiment 3
37.5g ANN aluminium nitrate nonahydrates and the nitric hydrate magnesium of 55.3g bis- are dissolved in 400g deionized waters, mixed solution is made into
A.Configuration 20wt% sodium hydrate aqueous solution B.Under not stopping stirring at 65 DEG C, the simultaneously Deca solution A and molten in four-hole boiling flask
Liquid B is co-precipitated, mixture ageing, filtration, filtration cakes torrefaction, and roasting 3 hours, grind at 200 DEG C, obtains brucite load
Body powder.Take 5g brucite powder and be added to stirring 2 hours in the aqueous solution of 0.6g ruthenic chlorides (ruthenium content is 37wt%), stand
Overnight, filter, filter cake deionized water is washed till neutrality, be dried, hydrogen reducing at 200 DEG C.Obtain catalyst Ru/LDH-3.
Embodiment 4
37.5g ANN aluminium nitrate nonahydrates and the nitric hydrate magnesium of 55.3g bis- are dissolved in 350g deionized waters, mixed solution is made into
A.Configuration 20wt% potassium hydroxide aqueous solution B.Under not stopping stirring at 65 DEG C, the simultaneously Deca solution A and molten in four-hole boiling flask
Liquid B is co-precipitated, mixture ageing, filtration, filtration cakes torrefaction, and roasting 3 hours, grind at 200 DEG C, obtains brucite load
Body powder.Take 5g brucite powder and be added to stirring 2 hours in the aqueous solution of 1.2g ruthenic chlorides (ruthenium content is 37wt%), stand
Overnight, filter, filter cake deionized water is washed till neutrality, be dried, hydrogen reducing at 200 DEG C.Obtain catalyst Ru/LDH-4.
Embodiment 5
37.5g ANN aluminium nitrate nonahydrates and the nitric hydrate ceriums of 43.4g six are dissolved in 450g deionized waters, mixed solution is made into
A.Configuration 15wt% lithium hydroxide aqueous solution B.Under not stopping stirring at 65 DEG C, the simultaneously Deca solution A and molten in four-hole boiling flask
Liquid B is co-precipitated, mixture ageing, filtration, filtration cakes torrefaction, and roasting 3 hours, grind at 200 DEG C, obtains brucite load
Body powder.Take 5g brucite powder and be added to stirring 2 hours in the aqueous solution of 0.6g ruthenic chlorides (ruthenium content is 37wt%), stand
Overnight, filter, filter cake deionized water is washed till neutrality, be dried, hydrogen reducing at 200 DEG C.Obtain catalyst Ru/LDH-5.
Embodiment 6
37.5g ANN aluminium nitrate nonahydrates and the nitric hydrate magnesium of 55.3g bis- are dissolved in 500g deionized waters, mixed solution is made into
A.Configuration 10wt% ammonia spirit B.Under not stopping stirring at 65 DEG C, simultaneously Deca solution A and solution B are carried out in four-hole boiling flask
Co-precipitation, mixture ageing, filtration, filtration cakes torrefaction, roasting 3 hours, grind at 200 DEG C, obtain hydrotalcite supports powder.
Take 5g brucite powder and be added to stirring 2 hours in the aqueous solution of 0.84g ruthenic chlorides (ruthenium content is 37wt%), stand overnight,
Filter, filter cake deionized water is washed till neutrality, be dried, hydrogen reducing at 200 DEG C.Obtain catalyst Ru/LDH-6.
Embodiment 7
37.5g ANN aluminium nitrate nonahydrates and the nitric hydrate ceriums of 43.4g six are dissolved in 500g deionized waters, mixed solution is made into
A.Configuration 10wt% lithium hydroxide solution B.Under not stopping stirring at 65 DEG C, in four-hole boiling flask while Deca solution A and solution B
It is co-precipitated, mixture ageing, filtration, filtration cakes torrefaction, roasting 3 hours, grind at 200 DEG C, obtain hydrotalcite supports
Powder.Take 5g brucite powder and be added to stirring 2 hours in the aqueous solution of 0.36g ruthenic chlorides (ruthenium content is 37wt%), stand
Overnight, filter, filter cake deionized water is washed till neutrality, be dried, hydrogen reducing at 200 DEG C.Obtain catalyst Ru/LDH-7.
Brucite supported ruthenium catalyst obtained in embodiment 1 to the methods described of embodiment 7 is used for into 3,3 '-dimethyl -4,
4 '-MDA (MDT) hydrogenation synthesis 3,3 '-dimethyl -4,4 '-diamino-dicyclohexyl methane (MACM) reaction,
Test its catalyst performance.Specifically reaction condition is:It it is 160 DEG C in temperature, Hydrogen Vapor Pressure is under conditions of 8MPa, in 500mL
Solvents tetrahydrofurane 60mL, 5g raw materials 3,3 '-dimethyl -4,4 '-MDA, 0.8g catalysis are added in reactor
Agent, the response time is 5h.
Catalyst performance test result such as following table:
It can be seen that, the catalyst prepared by above example is synthesizing 3,3 '-dimethyl -4, the hexamethylene of 4 '-diaminourea two
In the reaction of methylmethane, MACM high incomes are just obtained the product of higher proportion isomer shown in formula I without the need for adding auxiliary agent
Product, with higher commercial price and value, are conducive to further synthesizing downstream product.
In addition to above-mentioned enforcement, the present invention can also have other embodiment.All employing equivalents or equivalent transformation are formed
Technical scheme, all fall within the protection domain of application claims.
Claims (8)
1. a kind of hydrogenation catalyst, the hydrogenation catalyst is made up of active component and carrier, it is characterised in that:The activearm
It is divided into the metal Ru that weight content is 3-10%, the carrier is brucite, and brucite weight content is 90-97%.
2. hydrogenation catalyst according to claim 1, it is characterised in that:The brucite is magnalium or cerium aluminum hydrotalcite.
3. hydrogenation catalyst according to claim 2, it is characterised in that:Aluminum nitrate and magnesium nitrate or nitre in the brucite
The mol ratio of sour cerium is 1-3:1.
4. a kind of preparation method of hydrogenation catalyst, comprises the following steps:
Step one, aluminum nitrate and magnesium nitrate or cerous nitrate are dissolved in deionized water, obtain mixed solution A;
Step 2, weigh alkali compoundss and be dissolved in deionized water configuration alkali compoundss aqueous solution B;
Step 3,65 DEG C, do not stop stirring under conditions of, while Deca mixed solution A and alkali compoundss aqueous solution B are carried out altogether
Precipitation, mixture ageing, filtration, drying, finally roasting 3 hours at 200 DEG C, obtain hydrotalcite supports;
Step 4, the powder that hydrotalcite supports are ground to form 30-50 mesh, add and are stirred into the ruthenium saline solution containing 35-40wt%
2-2.5 hours, stand overnight, and filter, and filter cake is washed to neutrality, are dried at 120 DEG C, and hydrogen reducing at 200 DEG C obtains catalyst
Ru/LDH。
5. the preparation method of hydrogenation catalyst according to claim 4, it is characterised in that:The mixed solution A concentration is
15-30wt%.
6. the preparation method of hydrogenation catalyst according to claim 4, it is characterised in that:The alkali compoundss aqueous solution
B is LiOH, NaOH, KOH or NH3·H2One kind in O, concentration is 10-25wt%.
7. a kind of application of hydrogenation catalyst, it is characterised in that:For 3,3 '-dimethyl -4,4 '-MDA hydrogenation
Synthetic reaction, reaction temperature is 160 DEG C, and Hydrogen Vapor Pressure is 8Mpa, and tetrahydrofuran 60mL, 5g 3 are added in 500ml reactors,
3 '-dimethyl -4,4 '-MDA, 0.8g hydrogenation catalysts, the response time is 5h.
8. the application of hydrogenation catalyst according to claim 7, it is characterised in that:3,3 '-dimethyl -4,4 '-diaminourea
Dicyclohexyl methyl hydride yield >=97%, 3,3 '-dimethyl -4,4 '-MDA product assay >=30wt%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610970790.5A CN106622220B (en) | 2016-10-28 | 2016-10-28 | Hydrogenation catalyst, preparation method and application |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610970790.5A CN106622220B (en) | 2016-10-28 | 2016-10-28 | Hydrogenation catalyst, preparation method and application |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106622220A true CN106622220A (en) | 2017-05-10 |
CN106622220B CN106622220B (en) | 2019-11-08 |
Family
ID=58820871
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610970790.5A Expired - Fee Related CN106622220B (en) | 2016-10-28 | 2016-10-28 | Hydrogenation catalyst, preparation method and application |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106622220B (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112110926A (en) * | 2020-09-29 | 2020-12-22 | 北京阳光诺和药物研究股份有限公司 | Method for preparing tebipenem pivoxil |
CN113289637A (en) * | 2021-06-15 | 2021-08-24 | 南京工业大学 | Hydrotalcite-like catalyst, preparation method and application thereof |
CN113522004A (en) * | 2021-08-11 | 2021-10-22 | 中建材蚌埠玻璃工业设计研究院有限公司 | CIGS tail gas purifying agent and preparation method thereof |
CN117358235A (en) * | 2023-08-01 | 2024-01-09 | 江苏清泉化学股份有限公司 | Catalyst for preparing MACM by continuous hydrogenation and preparation method and application thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
-
2016
- 2016-10-28 CN CN201610970790.5A patent/CN106622220B/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112110926A (en) * | 2020-09-29 | 2020-12-22 | 北京阳光诺和药物研究股份有限公司 | Method for preparing tebipenem pivoxil |
CN112110926B (en) * | 2020-09-29 | 2022-05-17 | 北京阳光诺和药物研究股份有限公司 | Method for preparing tebipenem pivoxil |
CN113289637A (en) * | 2021-06-15 | 2021-08-24 | 南京工业大学 | Hydrotalcite-like catalyst, preparation method and application thereof |
CN113522004A (en) * | 2021-08-11 | 2021-10-22 | 中建材蚌埠玻璃工业设计研究院有限公司 | CIGS tail gas purifying agent and preparation method thereof |
CN117358235A (en) * | 2023-08-01 | 2024-01-09 | 江苏清泉化学股份有限公司 | Catalyst for preparing MACM by continuous hydrogenation and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN106622220B (en) | 2019-11-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106622220B (en) | Hydrogenation catalyst, preparation method and application | |
CN101602644B (en) | Method for synthesizing decalin | |
CN110368933B (en) | Ruthenium-based ammonia synthesis catalyst with Ce-Ti composite oxide as carrier and preparation method thereof | |
Sun et al. | Effect of Organic Additives on the Performance of Nano‐sized Ru‐Zn Catalyst | |
CN112473663A (en) | Catalyst for preparing alicyclic amine from aromatic amine and preparation method and application thereof | |
CN106423284A (en) | Vinyl acetate catalyst and preparing method thereof | |
CN113797952B (en) | Catalyst for synthesizing alicyclic amine through selective hydrogenation saturation of benzene ring containing benzene ring amine compounds and preparation method thereof | |
CN103626988B (en) | A kind of continuous processing prepares the production method of Amino Terminated polyether(ATPE) | |
CN108558679B (en) | Synthetic method of Parylene A precursor | |
CN110756198A (en) | Ruthenium-aluminum oxide catalyst for selective hydrogenation of 4, 4' -diaminodiphenylmethane and preparation method and application thereof | |
CN101337895B (en) | Method for preparing 2,2'-di(trifluoromethyl)-4,4'-benzidine | |
WO2021027953A1 (en) | Preparation method for diphenylmethane diisocyanate | |
CN112125792A (en) | Method for co-producing hydroxycitronellal and hydroxycitronellal | |
CN104003892A (en) | Catalytic hydrogenation preparation method of 3,5-diaminobenzoic acid | |
CN107486208B (en) | Preparation method and application of carbon nanotube-loaded quaternary amorphous nickel-based catalyst | |
CN112774670A (en) | Application of rhodium monatomic catalyst in reaction for preparing m-chloroaniline through selective hydrogenation of m-chloronitrobenzene | |
CN116082165A (en) | Preparation method of 1, 3-cyclohexanediamine | |
CN105541637A (en) | Preparation method of 2,2'-bis-trifluoromethyl-4,4'-diaminodiphenyl | |
CN104276959A (en) | Synthetic process of rubber anti-ageing agent 4020 | |
CN113880730B (en) | Industrial method for continuously preparing hexamethylene diisocyanate | |
CN108855126B (en) | Shell-core catalyst for synthesizing m-phenylenediamine and preparation method thereof | |
CN108516939A (en) | A kind of preparation method of high anti-body 4,4 '-diamino-dicyclohexyl methane of content | |
CN111644196B (en) | High-selectivity preparation method of methylpentamethylenediamine by adopting composite catalytic system | |
CN113929584A (en) | Method for synthesizing 4, 4-diaminodicyclohexyl methane | |
CN107537496A (en) | A kind of macromolecular amine terminated polyether loaded catalyst |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20191108 Termination date: 20211028 |