CN107362797A - Nano ruthenium carbon catalyst and preparation method thereof and its application in 4,4 ' diamino-dicyclohexyl methanes are synthesized - Google Patents
Nano ruthenium carbon catalyst and preparation method thereof and its application in 4,4 ' diamino-dicyclohexyl methanes are synthesized Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- KEIQPMUPONZJJH-UHFFFAOYSA-N dicyclohexylmethanediamine Chemical class C1CCCCC1C(N)(N)C1CCCCC1 KEIQPMUPONZJJH-UHFFFAOYSA-N 0.000 title abstract 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 89
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 85
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 82
- 239000000243 solution Substances 0.000 claims description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 29
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 28
- 239000002243 precursor Substances 0.000 claims description 20
- 239000003610 charcoal Substances 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 11
- 239000002250 absorbent Substances 0.000 claims description 11
- 230000002745 absorbent Effects 0.000 claims description 11
- 239000002105 nanoparticle Substances 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000004280 Sodium formate Substances 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 6
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 6
- 235000019254 sodium formate Nutrition 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 5
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 235000011181 potassium carbonates Nutrition 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 4
- 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 3
- 239000006185 dispersion Substances 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- YLPJWCDYYXQCIP-UHFFFAOYSA-N nitroso nitrate;ruthenium Chemical compound [Ru].[O-][N+](=O)ON=O YLPJWCDYYXQCIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000006193 liquid solution Substances 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 8
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 150000003304 ruthenium compounds Chemical class 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 21
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- -1 Polyoxyethylene Polymers 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000010903 husk Substances 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NGIISMJJMXRCCT-UHFFFAOYSA-N [Ru].[N+](=O)(O)[O-] Chemical compound [Ru].[N+](=O)(O)[O-] NGIISMJJMXRCCT-UHFFFAOYSA-N 0.000 description 2
- YPPQDPIIWDQYRY-UHFFFAOYSA-N [Ru].[Rh] Chemical compound [Ru].[Rh] YPPQDPIIWDQYRY-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 206010054949 Metaplasia Diseases 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical class [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 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
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000005662 electromechanics Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009941 weaving 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
-
- B01J35/618—
-
- B01J35/638—
-
- 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
- B01J37/0201—Impregnation
-
- 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
Abstract
The invention discloses nano ruthenium carbon catalyst and preparation method thereof and its application in 4,4 ' diamino-dicyclohexyl methanes are synthesized.The catalyst includes carrier and active component, carrier is activated carbon, active component is ruthenium, load capacity accounts for 1~10wt% of catalyst quality, and catalyst preparation does presoma step load using two kinds containing ruthenium compound, and the decentralization of ruthenium is 60~68%, the catalyst is used for MDA catalytic hydrogenations and prepares PACM, MDA conversion ratios are more than 99.9%, and instead, anti-PACM content of isomer is less than 20%.Catalyst of the present invention and method do not add auxiliary agent, keep higher active and selective at lower pressures, and realize relatively low anti-, the stereoselectivity of anti-PACM content of isomer, prepare easy, and cost is cheap, suitable for industrialized production.
Description
Technical field
The invention belongs to catalyst technical field, and in particular to nano ruthenium carbon catalyst and preparation method thereof is synthesizing with it
Application in 4,4 '-diaminourea-dicyclohexyl methyl hydride.
Background technology
4, the hydrogenation products 4 of 4 '-MDA (MDA), 4 '-diaminourea-dicyclohexyl methyl hydride (H12MDA or
PACM) be the high saturated polyurethane dicyclohexyl methyl hydride diisocyanate for preparing superior performance of new generation important source material.Industry
On often using MDA as raw material, by Hydrogenation first be made PACM, then obtain high saturated polyurethane through phosgenation again.It is high
Saturated polyurethane has the characteristics of stable performance, oxidation resistance are strong, application field is wide, is widely used in and prepares light polyurethane painting
Material, paint, foamed plastics, various elastomers, adhesive, fiber, synthetic leather and paving material etc., its end product is related to
To important departments such as space flight, aviation, electromechanics, ship, vehicle, civil construction, light industry and weavings.
PACM has trans- anti-, cis- anti-, the cis- suitable different stereoisomer of three kinds of macroscopic properties, the ratio of components of isomers
Rate determines the property and purposes of PACM and its subsequent product.Wherein, trans- trans isomer content is 20% or so and less than 20%
PACM products, also known as PACM-20, be mainly used in high-quality transparent polyurethane synthesis.Since the nineties in last century,
PACM-20 demand increases, and industrial prospect is more and more extensive.But the separation of PACM isomer mixtures is difficult, thus it is straight in synthesis
The PACM-20 products stablized are connect as the emphasis in current PACM product developments.It is directed to both at home and abroad and is applied to the three-dimensional choosings of MDA
The catalyst for selecting hydrogenation has done numerous studies, and more main flow catalyst is for ruthenium, rhodium, ruthenium-rhodium catalyst now.
The MDA hydrogenation catalysts that patent CN1740139A, CN1919828A is mentioned be ruthenium or rhodium single-metal reforming catalyst or
Ruthenium/rhodium catalyst of mixing, does not mention the preparation method of catalyst and the Nomenclature Composition and Structure of Complexes of catalyst；Patent CN101966456A
A kind of MDA hydrogenation catalysts mentioned are monometallic ruthenium/gold/mesoporous carbon catalyst that ruthenium content is 0.5%~10%, and preparing needs
High-temperature roasting；Patent CN1775353A refer to the preparation of skeleton ruthenium catalyst, it is necessary first to which high-temperature fusion prepares alloy
RuAlNiMC, then remove aluminium with the NaOH aqueous solution and skeleton ruthenium catalyst is made, the catalyst activity is high, but preparation process high energy consumption；
Patent CN101050184A reports one kind and is catalyzed MDA Hydrogenations using support type high dispersive Ru for H12MDA method, the catalysis
The preparation method of agent, as colloid protective agent, has been synthesized stable using two kinds of Determination of Polyoxyethylene Non-ionic Surfactants in water
Scattered ruthenium colloidal solution, adsorbed using activated carbon, aluminum oxide, silica etc. as carrier, be prepared into loaded nano
Ruthenium catalyst, the preparation method brings the possibility that surfactant has pollution catalyst article into, and preparation method is complicated, prepares
Journey is difficult to control；Patent CN102631918A discloses a nanometer preparation method for ruthenium rhodium catalyst, will contain 0.05~
0.15mol/L RuCl3With 0.01~0.03mol/L RhCl3The aqueous solution add in isopropanol, the aqueous solution and isopropanol two
The volume ratio of person is 1:4~6, it is stirring evenly and then adding into 180~220 grams of micropore coal mass active carbon, at a temperature of 40~60 DEG C,
Stirring 10~12 hours, then temperature rising reflux reaction 4~8 hours, cooled and filtered, need to use organic solvent, effect on environment
Greatly.
The content of the invention
First technical problem to be solved by this invention is to provide a kind of nano ruthenium carbon catalyst, and the nano ruthenium carbon is urged
Agent includes carrier-activated carbon and active component-ruthenium nano particle, the activated carbon account for total catalyst weight 90~
99wt%, the ruthenium nano particle account for 1~10wt% of total catalyst weight；The specific surface area of the activated carbon be 1500~
2000m2/ g, 1.3~1.5mg/L of total pore volume, middle macropore volume account for more than the 50% of total pore volume.
Wherein, in above-mentioned nano ruthenium carbon catalyst, the decentralization of ruthenium nano particle is between 60~68%, ruthenium nano particle
Particle diameter be 1~5nm.
Second technical problem to be solved by this invention is to provide the preparation method of above-mentioned nano ruthenium carbon catalyst, described
Preparation method comprises the following steps：
(1) activated carbon is handled with the mixed solution containing 10~20wt% nitric acid and 0.1~2wt% sodium chlorate, institute
The liquid-solid ratio for stating mixed solution and activated carbon is 2~8, and treatment temperature is 30~80 DEG C, and the time is 1~12h, afterwards will be treated
Activated carbon be washed till neutrality, dry, obtain absorbent charcoal carrier；
(2) above-mentioned absorbent charcoal carrier is scattered in deionized water according to liquid-solid ratio 8~20, obtains activated carbon suspension；
(3) by acetylacetone,2,4-pentanedione ruthenium add with its etc. quality ethanol fully dissolve after, add 4 times of quality of acetylacetone,2,4-pentanedione ruthenium
Deionized water, or ruthenium acetate is dissolved in be its 5 times of quality deionized water in, be configured to ruthenium precursor solution 1；By described in
Ruthenium precursor solution 1 is added drop-wise in above-mentioned activated carbon suspension, dipping absorption；
(4) ruthenium trichloride or nitrosyl nitrate ruthenium are formulated as to the ruthenium precursor solution 2 of 5~20g/L containing ruthenium, by institute
State ruthenium precursor solution 2 to be added drop-wise in product made from step (3), dipping absorption；
(5) into product made from step (4), alkali lye regulation slurries pH to 8~12 is added dropwise, 20~60 DEG C after being added dropwise
It is incubated 1~4h；
(6) into product made from step (5), reducing agent is added dropwise, filtration washing obtains high-dispersion nano ruthenium Pd/carbon catalyst.
Wherein, in the preparation method of above-mentioned nano ruthenium carbon catalyst, the ruthenium precursor solution 1 and ruthenium precursor solution
Ruthenium quality in No. 2 is 1 ︰ 1~9 than scope.
Preferably, in the preparation method of above-mentioned nano ruthenium carbon catalyst, the ruthenium precursor solution 1 is molten with ruthenium presoma
Ruthenium quality in liquid 2 is 1 ︰ 4 than scope.
Wherein, the preparation method of above-mentioned nano ruthenium carbon catalyst, alkali lye is sodium hydroxide solution, carbon described in step (5)
At least one of sour hydrogen sodium solution, sodium carbonate liquor, potassium hydroxide solution, potassium bicarbonate solution and solution of potassium carbonate.
Wherein, the preparation method of above-mentioned nano ruthenium carbon catalyst, reducing agent described in step (6) are sodium borohydride, hydration
At least one of hydrazine, sodium formate, sodium hypophosphite and formaldehyde.
3rd technical problem to be solved by this invention is to provide above-mentioned nano ruthenium carbon catalyst and synthesized in catalytic hydrogenation
4, the application in 4 '-diaminourea-dicyclohexyl methyl hydride, with 4,4 '-diaminourea-diphenyl-methane for raw material, using tetrahydrofuran to be molten
Agent, the mass concentration of raw material are 10%~25%, and nano ruthenium carbon catalyst amount is the 4~10% of material quality, 140~
170 DEG C, 2~4h of hydrogenation reaction under the conditions of 4~6Mpa, synthesis 4,4 '-diaminourea-dicyclohexyl methyl hydride.
Compared with prior art, the beneficial effects of the invention are as follows：Nano ruthenium carbon catalyst preparation process is simple, and cost is low,
It is free from environmental pollution；Alkali metal, alkaline earth metal alkali need not be added in nano ruthenium carbon catalyst or add a base to suppress into reaction
The side reactions such as ammonolysis, help to reduce or homogeneous metal particle diameter without using auxiliary agent or protective agent, reduce catalyst to product
PACM pollution, it keeps higher active and selective at lower pressures, and realizes relatively low anti-, and trans- PACM is different
(anti-, trans- PACM content of isomer is easy less than 20%), preparing, and cost is cheap, suitable for work for the stereoselectivity of structure body content
Industry metaplasia is produced.
Brief description of the drawings
Fig. 1 is the transmission electron microscope picture of the nano ruthenium carbon catalyst of embodiment 3；
Fig. 2 be embodiment 3 pretreatment after activated carbon nitrogen Adsorption and desorption isotherms figure.
Embodiment
The invention provides a kind of nano ruthenium carbon catalyst, the nano ruthenium carbon catalyst includes carrier-activated carbon and work
Property component-ruthenium nano particle, the activated carbon account for 90~99wt% of total catalyst weight, and the ruthenium nano particle accounts for catalyst
1~10wt% of gross weight；The specific surface area of the activated carbon is 1500~2000m2/ g, 1.3~1.5mg/L of total pore volume, in
Macropore volume accounts for more than the 50% of total pore volume；The decentralization of ruthenium nano particle is between 60~68%, the particle diameter of ruthenium nano particle
For 1~5nm.
Further, present invention also offers the preparation method of above-mentioned nano ruthenium carbon catalyst, the preparation method to include
Following steps：
(1) activated carbon is handled with the mixed solution containing 10~20wt% nitric acid and 0.1~2wt% sodium chlorate, institute
The liquid-solid ratio for stating mixed solution and activated carbon is 2~8, and treatment temperature is 30~80 DEG C, and the time is 1~12h, afterwards will be treated
Activated carbon be washed till neutrality, dry, obtain absorbent charcoal carrier；
(2) above-mentioned absorbent charcoal carrier is scattered in deionized water according to liquid-solid ratio 8~20, obtains activated carbon suspension；
(3) by acetylacetone,2,4-pentanedione ruthenium add with its etc. quality ethanol fully dissolve after, add 4 times of quality of acetylacetone,2,4-pentanedione ruthenium
Deionized water, or ruthenium acetate is dissolved in be its 5 times of quality deionized water in, be configured to ruthenium precursor solution 1；By described in
Ruthenium precursor solution 1 is added drop-wise in above-mentioned activated carbon suspension, dipping absorption；
(4) ruthenium trichloride or nitrosyl nitrate ruthenium are formulated as to the ruthenium precursor solution 2 of 5~20g/L containing ruthenium, by institute
State ruthenium precursor solution 2 to be added drop-wise in product made from step (3), dipping absorption；Before the ruthenium precursor solution 1 and ruthenium
It is 1 ︰ 1~9 that the ruthenium quality in liquid solution 2, which is driven, than scope
(5) into product made from step (4), alkali lye regulation slurries pH to 8~12 is added dropwise, 20~60 DEG C after being added dropwise
It is incubated 1~4h；The alkali lye is sodium hydroxide solution, sodium bicarbonate solution, sodium carbonate liquor, potassium hydroxide solution, bicarbonate
At least one of potassium solution and solution of potassium carbonate；
(6) into product made from step (5), reducing agent is added dropwise, filtration washing obtains high-dispersion nano ruthenium Pd/carbon catalyst；
The reducing agent is at least one of sodium borohydride, hydrazine hydrate, sodium formate, sodium hypophosphite and formaldehyde.
Preferably, in the preparation method of above-mentioned nano ruthenium carbon catalyst, the ruthenium precursor solution 1 is molten with ruthenium presoma
Ruthenium quality in liquid 2 is 1 ︰ 4 than scope.
Further, present invention provides above-mentioned nano ruthenium carbon catalyst catalytic hydrogenation synthesize 4,4 '-diaminourea-
Application in dicyclohexyl methyl hydride, with 4,4 '-diaminourea-diphenyl-methane for raw material, using tetrahydrofuran as solvent, the quality of raw material
Concentration is 10%~25%, and nano ruthenium carbon catalyst amount is the 4~10% of material quality, at 140~170 DEG C, 4~6Mpa bars
2~4h of hydrogenation reaction under part, synthesis 4,4 '-diaminourea-dicyclohexyl methyl hydride.
The present invention is made further explanation and description below in conjunction with specific embodiment, but is not so limited the present invention's
Protection domain.
Embodiment 1
Activated Carbon Pretreatment：Activated carbon is placed in into mass fraction to stir for the sodium chlorate mixed solution of 10% nitric acid+0.5%
1h, wherein liquid-solid ratio are 6, and temperature is 80 DEG C.Filtering, wash to neutrality, dry absorbent charcoal carrier.
The above-mentioned activated carbons of 47.5g are weighed, 380mL deionized waters is added, stirring, weighs 1.24g ruthenium acetate (ruthenium contents
40.4%), it is dissolved in 6.2g water, is added drop-wise in activated carbon suspension, continues to stir 1h after being added dropwise, weigh 5.4g tri-chlorinations
Ruthenium (ruthenium content 37%), the solution 400mL of 5g/L containing ruthenium are configured to, are added drop-wise to above-mentioned activated carbon suspension adsorption equilibrium 90min, dripped
NaOH solution is added to adjust slurries pH to 8, heat up 60 DEG C of insulation 1h, and sodium borohydride is added dropwise and is reduced, filters, wash to filtrate not
Chloride ion-containing, dry Ru/C samples.
Embodiment 2
With embodiment 1, unlike concentration of nitric acid be 20%, density of sodium chlorate 2%, activated carbon and nitric acid and sodium chlorate
The solid-to-liquid ratio of mixed liquor is 8.
Embodiment 3
Activated Carbon Pretreatment：Coconut husk charcoal is placed in into mass fraction to stir for the sodium chlorate mixed solution of 10% nitric acid+0.5%
1h, wherein liquid-solid ratio are 6, and temperature is 60 DEG C.Filtering, wash to neutrality, dry absorbent charcoal carrier.
The above-mentioned activated carbons of 47.5g are weighed, 500mL deionized waters is added, stirring, weighs 1.24g ruthenium acetate (ruthenium contents
40.4%), it is dissolved in 6.2g water, is added drop-wise in activated carbon suspension, continues to stir 1h after being added dropwise, weigh 5.99g nitric acid
Ruthenium (ruthenium content 33.4%), the solution 400mL of 5g/L containing ruthenium are configured to, are added drop-wise to above-mentioned activated carbon suspension adsorption equilibrium 90min,
The mixed ammonium/alkali solutions regulation slurries pH to 10 of sodium acid carbonate and potassium hydroxide is added dropwise, heat up 60 DEG C of insulation 1h, and sodium formate is added dropwise and enters
Row reduction, filter, wash to filtrate not chloride ion-containing, dry Ru/C samples.
Embodiment 4
With embodiment 3, the difference is that the mixed solution that hydrazine hydrate and sodium hypophosphite is added dropwise is reduced.
Embodiment 5
Activated Carbon Pretreatment：Coconut husk charcoal is placed in into mass fraction to stir for the sodium chlorate mixed solution of 10% nitric acid+0.1%
12h, wherein liquid-solid ratio are 2, and temperature is 30 DEG C.Filtering, wash to neutrality, dry absorbent charcoal carrier.
The above-mentioned activated carbons of 47.5g are weighed, add 950mL deionized waters, stirring.Weigh 4.94g acetylacetone,2,4-pentanedione ruthenium (ruthenium contents
25.3%), it is dissolved in 4.94g ethanol, adds 19.8g deionized waters, be added drop-wise to after stirring in activated carbon suspension, is added dropwise
After continue stir 2h, weigh 3.38g ruthenium trichlorides (ruthenium content 37%), be configured to the solution 125mL of 10g/L containing ruthenium, dropwise addition
To above-mentioned activated carbon suspension adsorption equilibrium 60min, solution of potassium carbonate regulation slurries pH to 12 is added dropwise, is incubated in 20 DEG C of water-baths
4h, 4 times of the formaldehyde that ruthenium stoichiometry is added dropwise are reduced, and are filtered, are washed to filtrate not chloride ion-containing, dry Ru/C samples
Product.
Embodiment 6
The catalyst of embodiment 3 is prepared in PACM reaction for MDA catalytic hydrogenations.20g is put into 500mL autoclaves
MDA reactants, 200mL tetrahydrofurans, 0.4g catalyst Ru/C, autoclave is closed, nitrogen displacement air 3 times, is rushed using hydrogen
4MPa is depressed into, after being warming up to 170 DEG C, regulation hydrogen is 6MPa, starts stirring and timing, and it is anti-not reduce end to system pressure
Should, kettle is unloaded in cooling, samples gas chromatographic analysis.Reaction time 240min, conversion ratio 99.9%, PACM yields 85.3%, wherein
Trans- anti-PACM contents 18.8%.
Embodiment 7
The catalyst of embodiment 3 is prepared in PACM reaction for MDA catalytic hydrogenations.20g is put into 500mL autoclaves
MDA reactants, 200mL tetrahydrofurans, 2g catalyst Ru/C, autoclave is closed, nitrogen displacement air 3 times, uses hydrogen punching press
To 4MPa, after being warming up to 160 DEG C, regulation hydrogen is 6MPa, starts stirring and timing, does not reduce end reaction to system pressure,
Kettle is unloaded in cooling, samples gas chromatographic analysis.Reaction time 1500min, conversion ratio 99.9%, PACM yields 98.4%, wherein trans-
Anti- PACM contents 16.7%.
Embodiment 8
The catalyst of embodiment 3 is prepared in PACM reaction for MDA catalytic hydrogenations.20g is put into 500mL autoclaves
MDA reactants, 200mL tetrahydrofurans, 1g catalyst Ru/C, autoclave is closed, nitrogen displacement air 3 times, uses hydrogen punching press
To 4MPa, after being warming up to 160 DEG C, regulation hydrogen is 6MPa, starts stirring and timing, does not reduce end reaction to system pressure,
Kettle is unloaded in cooling, samples gas chromatographic analysis.Reaction time 180min, conversion ratio 99.9%, PACM yields 92.1%, wherein trans-
Anti- PACM contents 19.6%.
Comparative example 1
Activated Carbon Pretreatment：Coconut husk charcoal is placed in into mass fraction to stir for the sodium chlorate mixed solution of 10% nitric acid+0.5%
1h, wherein liquid-solid ratio are 6, and temperature is 60 DEG C.Filtering, wash to neutrality, dry absorbent charcoal carrier.
47.5g absorbent charcoal carriers are weighed, 500mL deionized waters is added, stirring, weighs 6.76g ruthenium trichloride (ruthenium contents
37%) the solution 500mL of 10g/L containing ruthenium, are configured to, are added drop-wise to above-mentioned activated carbon suspension adsorption equilibrium 90min, bicarbonate is added dropwise
The mixed ammonium/alkali solutions of sodium and potassium hydroxide adjust slurries pH to 10, and heat up 60 DEG C of insulation 1h, and sodium formate is added dropwise and is reduced, takes out
Filter, wash to filtrate not chloride ion-containing, dry Ru/C samples.
Catalyst will be prepared to prepare in PACM reaction for MDA catalytic hydrogenations.20g is put into 500mL autoclaves
MDA reactants, 200mL tetrahydrofurans, 2g catalyst Ru/C, autoclave is closed, nitrogen displacement air 3 times, uses hydrogen punching press
To 4MPa, after being warming up to 160 DEG C, regulation hydrogen is 6MPa, starts stirring and timing, does not reduce end reaction to system pressure,
Kettle is unloaded in cooling, samples gas chromatographic analysis.Reaction time 300min, conversion ratio 95%, PACM yields 56.1%, wherein trans- anti-
PACM contents 35.4%.
Comparative example 2
47.5g activated carbons are weighed, 500mL deionized waters is added, stirring, weighs 1.24g ruthenium acetates (ruthenium content 40.4%),
It is dissolved in 6.2g water, is added drop-wise in activated carbon suspension, continues to stir 1h after being added dropwise, weigh 5.99g nitric acid ruthenium (ruthenium contents
33.4%) the solution 400mL of 5g/L containing ruthenium, are configured to, are added drop-wise to above-mentioned activated carbon suspension adsorption equilibrium 90min, carbonic acid is added dropwise
The mixed ammonium/alkali solutions of hydrogen sodium and potassium hydroxide adjust slurries pH to 10, and heat up 60 DEG C of insulation 1h, and sodium formate is added dropwise and is reduced, takes out
Filter, wash to filtrate not chloride ion-containing, dry Ru/C samples.
Catalyst will be prepared to prepare in PACM reaction for MDA catalytic hydrogenations.20g is put into 500mL autoclaves
MDA reactants, 200mL tetrahydrofurans, 2g catalyst Ru/C, autoclave is closed, nitrogen displacement air 3 times, uses hydrogen punching press
To 4MPa, after being warming up to 160 DEG C, regulation hydrogen is 6MPa, starts stirring and timing, does not reduce end reaction to system pressure,
Kettle is unloaded in cooling, samples gas chromatographic analysis.Reaction time 300min, conversion ratio 88%, PACM yields 48.1%, wherein trans- anti-
PACM contents 50.6%.
Described above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications are also considered as
Protection scope of the present invention.
Claims (8)
1. nano ruthenium carbon catalyst, it is characterised in that the nano ruthenium carbon catalyst include carrier-activated carbon and active component-
Ruthenium nano particle, the activated carbon account for 90~99wt% of total catalyst weight, and the ruthenium nano particle accounts for total catalyst weight
1~10wt%；The specific surface area of the activated carbon is 1500~2000m2/ g, 1.3~1.5mg/L of total pore volume, in big hole body
Product accounts for more than the 50% of total pore volume.
2. nano ruthenium carbon catalyst according to claim 1, it is characterised in that ruthenium nanometer in the nano ruthenium carbon catalyst
For the decentralization of particle between 60~68%, the particle diameter of ruthenium nano particle is 1~5nm.
3. the preparation method of the nano ruthenium carbon catalyst described in claim 1 or 2, it is characterised in that the preparation method includes
Following steps：
(1) activated carbon is handled with the mixed solution containing 10~20wt% nitric acid and 0.1~2wt% sodium chlorate, it is described mixed
The liquid-solid ratio for closing solution and activated carbon is 2~8, and treatment temperature is 30~80 DEG C, and the time is 1~12h, afterwards by treated work
Property charcoal be washed till neutrality, dry, obtain absorbent charcoal carrier；
(2) above-mentioned absorbent charcoal carrier is scattered in deionized water according to liquid-solid ratio 8~20, obtains activated carbon suspension；
(3) by acetylacetone,2,4-pentanedione ruthenium add with its etc. quality ethanol fully dissolve after, add going for 4 times of quality of acetylacetone,2,4-pentanedione ruthenium
Ionized water, or ruthenium acetate is dissolved in be its 5 times of quality deionized water in, be configured to ruthenium precursor solution 1；Before the ruthenium
Drive liquid solution 1 to be added drop-wise in above-mentioned activated carbon suspension, dipping absorption；
(4) ruthenium trichloride or nitrosyl nitrate ruthenium are formulated as to the ruthenium precursor solution 2 of 5~20g/L containing ruthenium, by the ruthenium
Precursor solution 2 is added drop-wise in product made from step (3), dipping absorption；
(5) into product made from step (4), alkali lye regulation slurries pH to 8~12,20~60 DEG C of insulations after being added dropwise is added dropwise
1~4h；
(6) into product made from step (5), reducing agent is added dropwise, filtration washing obtains high-dispersion nano ruthenium Pd/carbon catalyst.
4. the preparation method of nano ruthenium carbon catalyst according to claim 3, it is characterised in that the ruthenium precursor solution
No. 1 is 1 ︰ 1~9 with the ruthenium quality ratio scope in ruthenium precursor solution 2.
5. the preparation method of nano ruthenium carbon catalyst according to claim 4, it is characterised in that the ruthenium precursor solution
No. 1 is 1 ︰ 4 with the ruthenium quality ratio scope in ruthenium precursor solution 2.
6. the preparation method of nano ruthenium carbon catalyst according to claim 3, it is characterised in that alkali described in step (5)
Liquid is that sodium hydroxide solution, sodium bicarbonate solution, sodium carbonate liquor, potassium hydroxide solution, potassium bicarbonate solution and potassium carbonate are molten
At least one of liquid.
7. the preparation method of nano ruthenium carbon catalyst according to claim 3, it is characterised in that described in step (6) also
Former agent is at least one of sodium borohydride, hydrazine hydrate, sodium formate, sodium hypophosphite and formaldehyde.
8. application of the nano ruthenium carbon catalyst in synthesis 4,4 '-diaminourea-dicyclohexyl methyl hydride described in claim 1 or 2,
Characterized in that, with 4,4 '-diaminourea-diphenyl-methane for raw material, using tetrahydrofuran as solvent, the mass concentration of raw material is 10%
~25%, nano ruthenium carbon catalyst amount is the 4~10% of material quality, is hydrogenated with 140~170 DEG C, under the conditions of 4~6Mpa anti-
Answer 2~4h, synthesis 4,4 '-diaminourea-dicyclohexyl methyl hydride.
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Application publication date: 20171121 |