CN114890903A - Preparation method of 1, 3-cyclohexanedimethanamine with high cis-isomer content - Google Patents
Preparation method of 1, 3-cyclohexanedimethanamine with high cis-isomer content Download PDFInfo
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- CN114890903A CN114890903A CN202210637275.0A CN202210637275A CN114890903A CN 114890903 A CN114890903 A CN 114890903A CN 202210637275 A CN202210637275 A CN 202210637275A CN 114890903 A CN114890903 A CN 114890903A
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- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 44
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 19
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 18
- 230000009471 action Effects 0.000 claims abstract description 4
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 22
- 239000010931 gold Substances 0.000 claims description 19
- 230000002378 acidificating effect Effects 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000002808 molecular sieve Substances 0.000 claims description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 13
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 229910052680 mordenite Inorganic materials 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 150000002821 niobium Chemical class 0.000 claims description 3
- 150000002940 palladium Chemical class 0.000 claims description 3
- 239000012018 catalyst precursor Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 claims 1
- 238000007039 two-step reaction Methods 0.000 abstract description 2
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 17
- 239000002994 raw material Substances 0.000 description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 15
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 14
- 238000004817 gas chromatography Methods 0.000 description 14
- 238000001179 sorption measurement Methods 0.000 description 12
- 229910052737 gold Inorganic materials 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000003213 activating effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 241000282326 Felis catus Species 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- ZVUZTTDXWACDHD-UHFFFAOYSA-N gold(3+);trinitrate Chemical compound [Au+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O ZVUZTTDXWACDHD-UHFFFAOYSA-N 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- KUJRRRAEVBRSIW-UHFFFAOYSA-N niobium(5+) pentanitrate Chemical compound [Nb+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUJRRRAEVBRSIW-UHFFFAOYSA-N 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- -1 alicyclic diamine compound Chemical class 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 208000012839 conversion disease Diseases 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- JUBNUQXDQDMSKL-UHFFFAOYSA-N palladium(2+);dinitrate;dihydrate Chemical compound O.O.[Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O JUBNUQXDQDMSKL-UHFFFAOYSA-N 0.000 description 5
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 239000004310 lactic acid Substances 0.000 description 4
- 235000014655 lactic acid Nutrition 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 3
- 238000010923 batch production Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- ABIJRNDFOJAXMV-UHFFFAOYSA-N cyclohexane;n-methylmethanamine Chemical compound CNC.C1CCCCC1 ABIJRNDFOJAXMV-UHFFFAOYSA-N 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000002779 inactivation Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- SBUXRMKDJWEXRL-ROUUACIJSA-N cis-body Chemical compound O=C([C@H]1N(C2=O)[C@H](C3=C(C4=CC=CC=C4N3)C1)CC)N2C1=CC=C(F)C=C1 SBUXRMKDJWEXRL-ROUUACIJSA-N 0.000 description 2
- 150000001923 cyclic compounds Chemical class 0.000 description 2
- 230000009615 deamination Effects 0.000 description 2
- 238000006481 deamination reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000002560 nitrile group Chemical group 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 2
- 229920006391 phthalonitrile polymer Polymers 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- 239000001431 2-methylbenzaldehyde Substances 0.000 description 1
- XFKPORAVEUOIRF-UHFFFAOYSA-N 3-(aminomethyl)benzonitrile Chemical compound NCC1=CC=CC(C#N)=C1 XFKPORAVEUOIRF-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910020994 Sn-Zn Inorganic materials 0.000 description 1
- 229910009069 Sn—Zn Inorganic materials 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000008044 alkali metal hydroxides 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
- 125000003368 amide group Chemical group 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000007697 cis-trans-isomerization reaction Methods 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 238000005913 hydroamination reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- SBUXRMKDJWEXRL-ZWKOTPCHSA-N trans-body Chemical compound O=C([C@@H]1N(C2=O)[C@H](C3=C(C4=CC=CC=C4N3)C1)CC)N2C1=CC=C(F)C=C1 SBUXRMKDJWEXRL-ZWKOTPCHSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/70—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines
- C07C209/72—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines by reduction of six-membered aromatic rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/26—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of 1, 3-cyclohexanedimethanamine with high cis-form content. The method comprises the following steps: (a) m-xylylenediamine is subjected to hydrogenation reaction under a hydroisomerization bifunctional catalyst and hydrogen to obtain 1, 3-cyclohexanedimethylamine with cis/trans bodies of 70/30-75/25; (b) and (b) carrying out isomerization reaction on the 1, 3-cyclohexanedimethanamine obtained in the step (a) under the action of a hydroisomerization bifunctional catalyst and hydrogen to obtain the 1, 3-cyclohexanedimethanamine with high cis-form content of the cis-form body/trans-form body at 85/15-90/10. By controlling the reaction temperature in the two-step reaction process, the hydrogenation reaction of m-xylylenediamine and the isomerization reaction of 1, 3-cyclohexanedimethylamine are simultaneously realized, and the 1, 3-cyclohexanedimethylamine product with high yield and high cis-form content is obtained. The conversion rate of m-xylylenediamine is 100 percent, and the yield of the 1, 3-cyclohexanedimethylamine product with high cis-isomer content is more than 98 percent.
Description
Technical Field
The invention relates to a preparation method of 1, 3-cyclohexanedimethanamine, in particular to a preparation method of 1, 3-cyclohexanedimethanamine with high yield and high cis-isomer content.
Background
Cyclohexanedimethanamine is an industrially important compound used as a raw material for epoxy curing agents, polyamides, polyurethanes, and the like. Cyclohexanedimethanamine has both cis-isomer and trans-isomer derived from a cyclohexane ring, and a polymer using cyclohexanedimethanamine is known to have greatly changed physical properties depending on the isomer ratio of cis-isomer to trans-isomer. For example, a polyamide synthesized from a 1, 3-cyclohexyldimethylamine having a high cis-isomer content has high crystallinity, and a polyamide synthesized from a 1, 3-cyclohexyldimethylamine having a high trans-isomer content is amorphous. In addition, for example, the polyamide synthesized by using the 1, 4-cyclohexyldimethylamine with high trans content as the raw material has the characteristics of high melting point and high heat resistance. Thus, it is extremely important to control the ratio of cis-trans isomers in cyclohexyldimethylamine.
The cyclohexane dimethylamine is prepared mainly by phthalonitrile hydrogenation, cyclohexanedimethanol hydroamination and xylylenediamine hydrogenation. Among them, the xylylenediamine hydrogenation method has the advantages of high conversion rate of raw materials, high product selectivity, easy separation and purification of products, etc., and is an industrial production method of cyclohexyldimethylamine, which is also a method reported in many existing patents.
Patent CN101959848B discloses a catalyst for preparing cyclohexane dimethylamine by catalytic hydrogenation of xylylenediamine and its preparation method, wherein the catalyst is prepared by using bimetallic oxide as carrier and Ru as active component, and adding first and second auxiliary components, and in the system without using liquid ammonia and alkali metal hydroxide as deamination inhibitor, the conversion rate of raw material is above 99%, and the product selectivity is 97%, but the patent does not mention the problem of cis-trans isomer.
The patent CN114082428A discloses a supported Ru-Re catalyst with high activity, high selectivity and long service life and a method for synthesizing alicyclic diamine compound by using the catalyst to carry out catalytic hydrogenation on aromatic diamine compound, the patent can control the content of key stereoisomer in a proper range while considering the performance of the catalyst, taking the example of preparing 1, 3-cyclohexyldimethylamine by hydrogenation on m-xylylenediamine, the cis-isomer content in the product reaches more than 80 percent, the method adopts a semi-batch process, the dripping speed of m-xylylenediamine needs to be strictly controlled, the catalyst inactivation caused by overhigh concentration of m-xylylenediamine in a reaction system is avoided, meanwhile, competitive adsorption of nitrile compound needs to be additionally introduced to desorb the product from the surface of the catalyst, but the nitrile compound causes permanent poisoning and inactivation of the catalyst, and the method has the defects of easy catalyst inactivation, long service life, and the like, Low production efficiency and high separation energy consumption.
Patent CN111116381A discloses a method for preparing 1, 3-cyclohexyldimethylamine by hydrogenation of m-xylylenediamine, which adopts a semi-batch process, requires strict control of the dropping speed of m-xylylenediamine, and simultaneously, increases the cis-body content in the hydrogenated product 1, 3-cyclohexyldimethylamine by adding a nitrogen-containing rigid cyclic compound into the reaction system, so as to obtain a product with the cis-body/trans-body ratio above 80/20. Also, the method requires additional introduction of nitrogen-containing rigid cyclic compounds such as pyridine, quinoline, etc. to cause permanent poisoning deactivation of the catalyst, and also has the problems of easy catalyst deactivation, low production efficiency and high separation energy consumption.
Patent CN105555754A discloses a method for isomerizing cyclohexane dimethylamine, in which the isomerization reaction of 1, 3-cyclohexane dimethylamine is carried out in the presence of 4-methylbenzaldehyde and sodium amide, the cis/trans ratio in 1, 3-cyclohexane dimethylamine is increased from 74/26 to 80/20, the isomerization yield is 94%, although the method can improve the cis content in 1, 3-cyclohexane dimethylamine to some extent, the effect is not significant, and 6% of 1, 3-cyclohexane dimethylamine is converted into other impurities, and separation and purification of the product are required again.
Patent CN102030657A discloses a method for synthesizing 3, 3-dimethyl-4, 4-diaminodicyclohexyl methane, which adopts a batch process, and the 3, 3-dimethyl-4, 4-diaminodiphenyl methane as raw material is prepared into a 3, 3-dimethyl-4, 4-diaminodicyclohexyl methane product under the action of hydrogen, a Ru-based catalyst and a trace amount of alkaline earth metal auxiliary agent, but the patent does not mention the problem of cis-trans isomerization.
In view of the problems in the disclosed method for producing 1, 3-cyclohexanedimethanamine with high cis-isomer content, a suitable catalyst and production process are urgently needed to be found, the problems of activity, selectivity and stability of the catalyst are fundamentally solved, and meanwhile, the purposes of improving the production efficiency and the product quality are achieved by continuously optimizing process conditions.
Disclosure of Invention
The invention aims to provide a preparation method of 1, 3-cyclohexanedimethanamine with high cis-form content, which adopts a hydrogenation isomerization bifunctional catalyst and a two-stage temperature-changing reaction process to simultaneously realize the hydrogenation reaction of m-xylylenediamine and the isomerization reaction of 1, 3-cyclohexanedimethanamine, and finally obtains a high-yield 1, 3-cyclohexanedimethanamine product with high cis-form content.
In order to realize the purpose, the invention adopts the following technical scheme:
a preparation method of 1, 3-cyclohexanedimethanamine with high yield and high cis-isomer content comprises the following steps:
(a) m-xylylenediamine is subjected to hydrogenation reaction under a hydroisomerization bifunctional catalyst and hydrogen to obtain 1, 3-cyclohexanedimethylamine with a cis-isomer/trans-isomer ratio in the range of 70/30-75/25;
(b) and (b) carrying out isomerization reaction on the 1, 3-cyclohexanedimethanamine obtained in the step (a) under the action of a hydroisomerization bifunctional catalyst and hydrogen to obtain the 1, 3-cyclohexanedimethanamine with high cis-isomer content, wherein the cis-isomer/trans-isomer ratio is in the range of 85/15-90/10.
The hydroisomerization bifunctional catalyst in the steps (a) and (b) comprises an active component and a carrier, wherein the carrier comprises an acidic molecular sieve and a bimetallic oxide.
The active components comprise PdO and Au 2 O 3 And Nb 2 O 5 。
The acidic molecular sieve is selected from one or more of ZSM-22, ZSM-48, SAPO-11 and mordenite, preferably SAPO-11 and/or mordenite, more preferably SAPO-11.
The bimetallic oxide is selected from SnO 2 -BaO、SnO 2 -MgO、SnO 2 -MnO 2 、SnO 2 -Fe 2 O 3 、SnO 2 -ZnO and SnO 2 One or more of CaO, preferably SnO 2 -BaO、SnO 2 MgO and SnO 2 -one or more of ZnO, more preferably SnO 2 -MgO。
Preferably, the molar ratio of Sn to the other metal element in the bimetallic oxide is from 0.01:1 to 0.1:1, preferably from 0.03:1 to 0.05: 1.
The bimetal oxide is prepared by a conventional preparation method, such as an isometric impregnation method, by soaking the metal oxide in an aqueous solution containing soluble tin salt according to a proportion, drying and roasting to obtain the bimetal oxide.
In the preparation method of the bimetallic oxide, the soluble tin salt is selected from one or more of sulfate, nitrate and organic acid salt of tin, and nitrate is preferred.
In the preparation method of the bimetallic oxide, the drying temperature is 90-140 ℃, preferably 100-130 ℃, and the drying time is 4-10h, preferably 6-8 h; the roasting temperature is 200-400 ℃, preferably 250-350 ℃; the roasting time is 3-10h, preferably 5-8 h.
In the hydroisomerization bifunctional catalyst, the specific surface area of a carrier is 200m 2 /g-500m 2 Per g, preferably 300m 2 /g-400m 2 The pore volume is 0.1ml/g to 0.60ml/g, preferably 0.3ml/g to 0.5ml/g, and the average pore diameter is 100-300nm, preferably 150-250 nm; the acidic molecular sieve is present in the support in an amount of from 90 to 98 wt%, preferably from 93 to 96 wt%, and the bimetallic oxide is present in an amount of from 2 to 10 wt%, preferably from 4 to 7 wt%, based on the weight of the support.
The active component of the hydroisomerization bifunctional catalyst comprises the following components: based on the weight of the carrier,
the PdO content is from 1 to 10% by weight, preferably from 4 to 8% by weight;
Au 2 O 3 the content is 0.1-2 wt%, preferably 0.5-1.5 wt%;
Nb 2 O 5 the content is 0.05-1 wt%, preferably 0.3-0.7 wt%.
The preparation method of the hydroisomerization bifunctional catalyst in the steps (1) and (2) comprises the following steps:
(1) preparation of the carrier:
mixing an acidic molecular sieve, a bimetallic oxide, a dispersant and a binder, kneading, molding, drying and roasting to obtain a carrier;
(2) preparation of the catalyst:
immersing the carrier obtained in the step (1) in an aqueous solution containing soluble palladium salt, gold salt and niobium salt, drying and roasting to obtain the catalyst precursor, and preferably immersing in the same volume.
In step (1), the binder is selected from one or more of citric acid, glutamic acid, aspartic acid, lactic acid, pyruvic acid, preferably citric acid and/or lactic acid.
The dispersing agent is selected from one or more of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol and gelatin, and is preferably polyvinylpyrrolidone and/or polyvinyl alcohol.
The soluble palladium salt, gold salt and niobium salt in the step (2) are selected from one or more of sulfate, nitrate and acetate of corresponding metal elements, and acetate is preferred.
In step (1), the binder is used in the form of a solution having a concentration of 5 to 20% by weight, preferably 10 to 15% by weight, in an amount of 0.5: 1-1: 1, preferably 0.6: 1-0.8: based on the weight sum of the acidic molecular sieve and the bimetallic oxide.
The dosage of the dispersant is 0.01:1-0.1:1, preferably 0.04: 1-0.06: based on the weight sum of the acidic molecular sieve and the bimetallic oxide.
In the step (1), the drying temperature is 100-150 ℃, preferably 120-140 ℃, and the drying time is 2-10h, preferably 4-8 h; the roasting temperature is 400-800 ℃, preferably 500-600 ℃; the roasting time is 3-12h, preferably 5-10 h.
In the step (2), the drying temperature is 100-150 ℃, preferably 120-140 ℃, and the drying time is 2-10h, preferably 4-8 h; the roasting temperature is 200-500 ℃, preferably 300-400 ℃, and the roasting time is 2-10h, preferably 4-8 h.
The hydroisomerization bifunctional catalyst needs to be activated to have activity. The activation method comprises the following steps: the hydrogen flow is 1-10L/min/L cat, preferably 3-7L/min/L cat, the absolute pressure is 2-10MPa, preferably 4-8MPa, the activation temperature is 200-500 ℃, preferably 300-400 ℃ for 2-12h, preferably 4-10 h.
The absolute reaction pressure in the step (a) is 2-10MPa, preferably 4-8 MPa; the reaction temperature is 180-200 ℃, preferably 185-195 ℃; the space velocity of the raw material of m-xylylenediamine is 1-5L/h/L cat, preferably 2-4L/h/L cat; the molar weight ratio of the hydrogen to the m-xylylenediamine is 3-8: 1, preferably 4 to 6: 1.
the absolute reaction pressure in the step (b) is 2-10MPa, preferably 4-8 MPa; the reaction temperature is 100-160 ℃, preferably 120-140 ℃; the space velocity of the raw material 1, 3-cyclohexane dimethylamine is 1-5L/h/L cat, preferably 2-4L/h/L cat; the molar weight ratio of hydrogen to 1, 3-cyclohexanedimethanamine is 3-8: 1, preferably 4 to 6: 1.
the invention surprisingly discovers that a 1, 3-cyclohexanedimethanamine product with high yield and high cis-isomer content is finally obtained by adopting a hydroisomerization bifunctional catalyst and a two-stage temperature-changing reaction process and controlling the change of reaction temperature in the two-step reaction process and simultaneously realizing the hydrogenation reaction of m-xylylenediamine and the isomerization reaction of 1, 3-cyclohexanedimethanamine. The conversion rate of the raw material of m-xylylenediamine reaches 100 percent, and the yield of the 1, 3-cyclohexane dimethylamine product with high cis-form content is more than 98 percent. The reaction conditions for preparing 1, 3-cyclohexanedimethanamine by m-xylylenediamine hydrogenation are harsh, the hydrogenation needs to be completed under high temperature and high pressure conditions in order to ensure high conversion rate and high selectivity, and isomerization reaction is accompanied in the hydrogenation process, so that the 1, 3-cyclohexanedimethanamine product obtained by the hydrogenation reaction is a mixture of cis-isomer and trans-isomer, usually the cis-isomer is relatively stable compared with the trans-isomer, but the cis-isomer/trans-isomer ratio in the 1, 3-cyclohexanedimethanamine obtained by the hydrogenation reaction can only be maintained in the range of 70/30-75/25. The isomerization reaction of the 1, 3-cyclohexanedimethylamine is an exothermic reversible reaction, the temperature is reduced, the isomerization reaction is facilitated, namely, the content of cis-isomer in the isomer is facilitated to be increased, and meanwhile, the occurrence of side reactions such as decomposition reaction, polymerization reaction and the like can be inhibited at low temperature, so that the high-yield product is facilitated to be obtained. Therefore, the hydrogenation reaction needs to be controlled at a higher reaction temperature, and the isomerization reaction needs to be controlled at a lower reaction temperature, so that the dual functions of hydrogenation and isomerization of the catalyst are realized.
The invention prepares the acidic molecular sieve and the bimetallic oxide composite carrier loaded with PdO and Au 2 O 3 And Nb 2 O 5 The three-component bifunctional catalyst is applied to catalytic hydroisomerization reaction, and not only has an active center capable of meeting hydrogenation requirements, but also can meet the acid center of isomerization reaction. On one hand, the acidic molecular sieve has the micropore characteristic, so that the dispersity of active metals is improved, and the activity of the catalyst is improved; on the other hand, the bimetallic oxide has controllable mesoporous characteristic and appropriate specific surface area and pore volume, can provide diffusion channels for reactant molecules and product molecules, is beneficial to mass transfer of the reactant molecules and the product molecules in carrier pores, and effectively avoids generation of byproducts, thereby improving selectivity of the catalyst. Finally, the bimetal oxide has certain alkalinity, can reduce the acidity of the surface of the acidic molecular sieve and regulate and control the active site of the catalyst, effectively inhibits the deamination condensation side reaction of m-xylylenediamine in the hydrogenation reaction process, and improves the effective utilization rate of the m-xylylenediamine; in the isomerization reaction process, the content and the yield of the cis-form 1, 3-cyclohexanedimethylamine are improved.
In the hydrogenation reaction process, active components PdO and Au 2 O 3 And Nb 2 O 5 Produces synergistic effect and improves the activity and selectivity of the hydrogenation catalyst. In the invention, PdO is the main active component in the catalyst and plays a decisive role in the hydrogenation of m-phenylenediamine, and the residual trace nitrile substances in the raw material of m-xylylenediamine are used as catalystThe main factor causing the deactivation of the hydrogenation catalyst, and the active component Au 2 O 3 The introduction of the active component enhances the adsorption of trace nitrile-based impurities in the raw materials, and simultaneously, the active component Au 2 O 3 Can hydrogenate and convert trace nitrile group impurities in the raw materials into amido, avoids the poison of the trace nitrile group in the m-xylylenediamine raw materials to the hydrogenation catalyst, and improves the service life of the catalyst. At the same time, Nb 2 O 5 Advantageous introduction of PdO and Au 2 O 3 Dispersing, inhibiting the agglomeration of active metal, and further improving the activity and selectivity of the catalyst.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the examples listed, and it should also include equivalent modifications and variations to the technical solutions defined in the claims appended to the present application.
Gas chromatograph: shimadzu GC-2014(FID) detector, SE-30 capillary column
The sample inlet is 300 ℃, and the detector is 270 ℃; temperature rising procedure: keeping the temperature at 100 deg.C for 5min, and raising the temperature to 260 deg.C at 20 deg.C/min for 10 min.
The reactor in the examples is a fixed bed reactor.
Meta-xylylenediamine index: 99.8 wt% of m-xylylenediamine, 0.15 wt% of 3-cyanobenzylamine, 0.05 wt% of m-phthalonitrile, Shanghai Tahe chemical Co., Ltd.
And (3) measuring the content of active components in the catalyst: and measuring the content of the active metal in the catalyst by using a plasma emission spectrometer.
Example 1
(1)SnO 2 Preparation of-MgO
Soaking 100g MgO in 100ml water solution containing 26.6g tin acetate, drying at 100 deg.C for 7 hr after adsorption equilibrium, and calcining at 250 deg.C for 8 hr to obtain SnO with Sn to Mg molar ratio of 0.03:1 2 -a MgO bimetallic oxide.
(2) Preparation of the support
186g of SAPO-11 and 14g of SnO 2 MgO, 8g of polyvinylpyrrolidone and 120g of a 10 wt% aqueous solution of citric acid were mixed, kneaded, extruded and molded, dried at 130 ℃ for 6 hours, and calcined at 400 ℃ for 5 hours to obtain a carrier.
(3) Catalyst 4 wt% PdO-0.5 wt% Au 2 O 3 -0.3wt％Nb 2 O 5 Preparation of the support
Weighing 100g of the carrier obtained in the step (2), adding 100ml of aqueous solution containing 8.71g of palladium nitrate dihydrate, 0.87g of gold nitrate and 0.91g of niobium nitrate by an isovolumetric impregnation method, drying at 130 ℃ for 6h after adsorption equilibrium, and roasting at 400 ℃ for 4h to obtain the catalyst 4 wt% PdO-0.5 wt% Au 2 O 3 -0.3wt％Nb 2 O 5 A carrier.
(4) Evaluation of catalyst
And (3) evaluating the catalyst by adopting a continuous fixed bed process, and respectively adding 100ml of hydroisomerization bifunctional catalyst into the first fixed bed reactor and the second fixed bed reactor. Activating with hydrogen at 3L/min/L catalyst, 6MPa for 10h, and 350 deg.C.
And (2) keeping the reaction temperature of the fixed bed reactor at 195 ℃, the reaction pressure at 6MPa, and after the system is stable, keeping the space velocity of m-xylylenediamine at 2L/h/L Cat, wherein the molar ratio of hydrogen to m-xylylenediamine is 4: the reaction was carried out at 1, and the conversion of the reaction was 100.0% by gas chromatography, the cis-trans isomer ratio of 1, 3-cyclohexanedimethylamine was 70/30, and the yield was 99.5% based on m-xylylenediamine. After the catalyst is continuously operated for 500 hours, the reaction conversion rate is 99.6 percent, the cis-trans isomer proportion of 1, 3-cyclohexane dimethylamine is 71/29 through gas chromatographic analysis, and the yield is 99.0 percent based on m-xylylenediamine.
And directly taking the reaction liquid extracted from the first fixed bed reactor as a raw material to enter a second fixed bed reactor for reaction. And (2) maintaining the reaction temperature of the fixed bed reactor II at 120 ℃, the reaction pressure at 6MPa, the space velocity of the 1, 3-cyclohexanedimethanamine at 2L/h/L Cat, and the molar ratio of hydrogen to the 1, 3-cyclohexanedimethanamine at 4:1, reacting. By gas chromatography analysis, the cis-trans isomer ratio of 1, 3-cyclohexanedimethanamine was 85/15, and the yield was 98.5% based on m-xylylenediamine.
Comparative example 1
(1) Catalyst preparation
200g of SAPO-11 was used, SnO was not used 2 MgO, the rest of the procedure is the same as in example 1.
(2) Evaluation of catalyst
By activating and evaluating the process of example 1, the reaction conversion of the fixed bed reactor one was 95.0%, the cis-trans isomer ratio of 1, 3-cyclohexanedimethanamine was 72/28, and the yield was 91.5%, based on m-xylylenediamine; the cis-trans isomer ratio of 1, 3-cyclohexanedimethanamine of the second fixed bed reactor was 86/14, and the yield was 89.3% based on m-xylylenediamine.
Comparative example 2
(1) Catalyst preparation
200g SnO was used 2 MgO, without SAPO-11, the rest of the procedure is the same as in example 1.
(2) Evaluation of catalyst
By activating and evaluating the process of example 1, the reaction conversion of the fixed bed reactor one was 90.2%, the cis-trans isomer ratio of 1, 3-cyclohexanedimethanamine was 70/30, and the yield was 87.6%, based on m-xylylenediamine; the cis-trans isomer ratio of 1, 3-cyclohexanedimethanamine of the second fixed bed reactor was 82/18, and the yield was 75.8% based on m-xylylenediamine.
Comparative example 3
The catalyst was prepared without addition of gold nitrate, except as in example 1. After the catalyst is continuously operated for 500 hours, the reaction conversion rate is 92.5 percent, the cis-trans isomer proportion of 1, 3-cyclohexanedimethanamine is 71/29 and the yield is 86.5 percent by the weight of m-xylylenediamine through gas chromatography analysis.
Comparative example 4
Niobium nitrate was not added in the preparation of the catalyst, and the rest was referred to example 1. In the hydrogenation reaction, gas chromatography analysis showed that the reaction conversion was 96.5%, the cis-trans isomer ratio of 1, 3-cyclohexanedimethylamine was 72/28, and the yield was 93.2% based on m-xylylenediamine.
Comparative example 5
The isomerization temperature was controlled at 195 ℃ and otherwise referred to in example 1. By gas chromatography analysis, the cis-trans isomer ratio of 1, 3-cyclohexanedimethanamine was 71/29, and the yield was 98.4% based on m-xylylenediamine.
Comparative example 6
SnO having a Sn to Mg molar ratio of 0.2:1 was prepared according to the same preparation method as in example 1 2 -a MgO bimetallic oxide.
Under the condition that other conditions are not changed, the conversion rate of hydrogenation reaction is 100.0 percent, the proportion of cis-trans isomers of 1, 3-cyclohexanedimethanamine is 71/29, and the yield is 97.2 percent based on m-xylylenediamine through gas chromatography analysis; in the isomerization reaction, the cis-trans isomer ratio of 1, 3-cyclohexanedimethanamine was 85/15, and the yield was 95.3% based on m-xylylenediamine.
Example 2
(1)SnO 2 Preparation of-MgO
Soaking 100g MgO in 100ml water solution containing 35.5g tin acetate, after adsorption equilibrium, drying at 120 deg.C for 8 hr, and calcining at 300 deg.C for 6 hr to obtain SnO with Sn to Mg molar ratio of 0.04:1 2 -a MgO bimetallic oxide.
(2) Preparation of the support
190g of SAPO-11 and 10g of SnO 2 MgO, 12g of polyvinylpyrrolidone and 160g of a 12% strength by weight aqueous citric acid solution, followed by kneading, extruding, molding, drying at 120 ℃ for 4 hours and baking at 800 ℃ for 7 hours to obtain a carrier.
(3) Catalyst 8 wt% PdO-1 wt% Au 2 O 3 -0.5wt％Nb 2 O 5 Preparation of the support
Weighing 100g of the carrier obtained in the step (2), adding the carrier into 100ml of aqueous solution containing 17.42g of palladium nitrate dihydrate, 1.37g of gold nitrate and 1.52g of niobium nitrate by an isovolumetric impregnation method, drying the carrier at 120 ℃ for 4h after adsorption equilibrium, and roasting the carrier at 200 ℃ for 6h to obtain the catalyst 8 wt% PdO-1 wt% Au 2 O 3 -0.5wt％Nb 2 O 5 A carrier.
(4) Evaluation of catalyst
And (3) evaluating the catalyst by adopting a continuous fixed bed process, and respectively adding 100ml of hydroisomerization bifunctional catalyst into the first fixed bed reactor and the second fixed bed reactor. Activating with hydrogen at 5L/min/L under 8MPa at 300 deg.C for 6 h.
And (2) keeping the reaction temperature of the fixed bed reactor at 185 ℃, the reaction pressure at 4MPa, and after the system is stable, keeping the space velocity of m-xylylenediamine at 4L/h/L Cat, wherein the molar ratio of hydrogen to m-xylylenediamine is 6: the reaction was carried out at 1, and the conversion of the reaction was 100.0% by gas chromatography, the cis-trans isomer ratio of 1, 3-cyclohexanedimethylamine was 72/28, and the yield was 99.6% based on m-xylylenediamine.
And directly taking the reaction liquid extracted from the first fixed bed reactor as a raw material to enter a second fixed bed reactor for reaction. And (2) maintaining the reaction temperature of the fixed bed reactor II at 130 ℃, the reaction pressure at 4MPa, the space velocity of the 1, 3-cyclohexanedimethanamine at 4L/h/L Cat, and the molar ratio of hydrogen to the 1, 3-cyclohexanedimethanamine at 6: 1, reacting. By gas chromatography analysis, the cis-trans isomer ratio of 1, 3-cyclohexanedimethanamine was 88/12, and the yield was 98.4% based on m-xylylenediamine.
Example 3
(1)SnO 2 Preparation of-MgO
Soaking 100g MgO in 100ml aqueous solution containing 44.4g tin acetate, drying at 90 deg.C for 10 hr after adsorption equilibrium, and calcining at 350 deg.C for 5 hr to obtain SnO with Sn to Mg molar ratio of 0.05:1 2 -a MgO bimetallic oxide.
(2) Preparation of the support
192g of SAPO-11 and 8g of SnO 2 MgO, 10g of polyvinyl alcohol and 140g of a 15 wt% citric acid aqueous solution were mixed, kneaded, extruded, molded, dried at 140 ℃ for 8 hours, and calcined at 500 ℃ for 10 hours to obtain a composite carrier.
(3) Catalyst 6 wt% PdO-1.5 wt% Au 2 O 3 -0.8wt％Nb 2 O 5 Preparation of Complex Carrier
Weighing 100g of the composite carrier obtained in the step (2), adding 100ml of aqueous solution containing 13.06g of palladium nitrate dihydrate, 2.60g of gold nitrate and 2.43g of niobium nitrate by an isovolumetric impregnation method, drying at 140 ℃ for 8h after adsorption equilibrium, and roasting at 350 ℃ for 8h to obtain the catalyst 6 wt% PdO-1.5 wt%Au 2 O 3 -0.8wt％Nb 2 O 5 A carrier.
(4) Evaluation of catalyst
And (3) evaluating the catalyst by adopting a continuous fixed bed process, and respectively adding 100ml of hydroisomerization bifunctional catalyst into the first fixed bed reactor and the second fixed bed reactor. Activating with hydrogen at a flow rate of 7L/min/L under 4MPa at 400 deg.C for 4 h.
And (2) keeping the reaction temperature of the fixed bed reactor I at 190 ℃, the reaction pressure at 8MPa, and after the system is stable, keeping the space velocity of m-xylylenediamine at 3L/h/L Cat, wherein the molar ratio of hydrogen to m-xylylenediamine is 8: the reaction was carried out at 1, and the conversion of the reaction was 100.0% by gas chromatography, the cis-trans isomer ratio of 1, 3-cyclohexanedimethylamine was 75/25, and the yield was 99.4% based on m-xylylenediamine.
And directly taking the reaction liquid extracted from the first fixed bed reactor as a raw material to enter a second fixed bed reactor for reaction. And (2) maintaining the reaction temperature of the fixed bed reactor II at 140 ℃, the reaction pressure at 8MPa, and under the conditions that the space velocity of the 1, 3-cyclohexanedimethanamine is 3L/h/L Cat, the molar ratio of hydrogen to the 1, 3-cyclohexanedimethanamine is 8: 1, reacting. By gas chromatography analysis, the cis-trans isomer ratio of 1, 3-cyclohexanedimethanamine was 90/10, and the yield was 98.7% based on m-xylylenediamine.
Example 4
(1)SnO 2 Preparation of-ZnO
Soaking 100g ZnO in 100ml water solution containing 8.9g tin acetate, drying at 140 deg.C for 4 hr after adsorption equilibrium, and calcining at 400 deg.C for 3 hr to obtain SnO with Sn-Zn molar ratio of 0.01:1 2 -ZnO bimetallic oxide.
(2) Preparation of the support
180g of mordenite and 20g of SnO 2 -ZnO, 2g polyvinyl alcohol and 100g lactic acid aqueous solution with the concentration of 5 wt% are mixed, then mixed, kneaded, extruded and molded, dried at 150 ℃ for 2h, and calcined at 700 ℃ for 3h to obtain the carrier.
(3) Catalyst 1 wt% PdO-2 wt% Au 2 O 3 -0.05wt％Nb 2 O 5 Preparation of the support
Weighing 100g of the carrier obtained in the step (2), adding 100ml of aqueous solution containing 2.18g of palladium nitrate dihydrate, 3.47g of gold nitrate and 0.15g of niobium nitrate by an isovolumetric impregnation method, drying at 150 ℃ for 2h after adsorption equilibrium, and roasting at 300 ℃ for 10h to obtain the catalyst 1 wt% PdO-2 wt% Au 2 O 3 -0.05wt％Nb 2 O 5 A carrier.
(4) Evaluation of catalyst
And (3) evaluating the catalyst by adopting a continuous fixed bed process, and respectively adding 100ml of hydroisomerization bifunctional catalyst into the first fixed bed reactor and the second fixed bed reactor. Activating with hydrogen at a flow rate of 1L/min/L, an activation pressure of 10MPa, an activation temperature of 200 ℃ and an activation time of 2 h.
And (2) keeping the reaction temperature of the fixed bed reactor I at 180 ℃, the reaction pressure at 10MPa, and after the system is stable, keeping the space velocity of m-xylylenediamine at 1L/h/L Cat, wherein the molar ratio of hydrogen to m-xylylenediamine is 5: the reaction was carried out at 1, and the conversion of the reaction was 100.0% by gas chromatography, the cis-trans isomer ratio of 1, 3-cyclohexanedimethylamine was 73/27, and the yield was 99.8% based on m-xylylenediamine.
And directly taking the reaction liquid extracted from the first fixed bed reactor as a raw material to enter a second fixed bed reactor for reaction. And (2) maintaining the reaction temperature of the fixed bed reactor II at 100 ℃, the reaction pressure at 10MPa, the space velocity of the 1, 3-cyclohexanedimethanamine at 1L/h/L Cat, and the molar ratio of hydrogen to the 1, 3-cyclohexanedimethanamine at 5:1, reacting. By gas chromatography analysis, the cis-trans isomer ratio of 1, 3-cyclohexanedimethanamine was 87/13, and the yield was 98.6% based on m-xylylenediamine.
Example 5
(1)SnO 2 Preparation of-BaO
Soaking 100g BaO in 100ml water solution containing 88.7g tin acetate, drying at 130 deg.C for 6 hr after adsorption equilibrium, and calcining at 200 deg.C for 10 hr to obtain SnO with Sn to Ba molar ratio of 0.1:1 2 -a BaO bimetallic oxide.
(2) Preparation of the support
196g of mordenite, 4g of SnO 2 BaO, 20g polyethyleneAlcohol and 200g of a 20 wt% aqueous solution of lactic acid were mixed, kneaded, extruded, molded, dried at 100 ℃ for 10 hours, and calcined at 600 ℃ for 12 hours to obtain a carrier.
(3) Catalyst 10 wt% PdO-0.1 wt% Au 2 O 3 -1wt％Nb 2 O 5 Preparation of the support
Weighing 100g of the carrier obtained in the step (2), adding 100ml of aqueous solution containing 21.77g of palladium nitrate dihydrate, 0.17g of gold nitrate and 3.03g of niobium nitrate by an isovolumetric impregnation method, drying at 100 ℃ for 10h after adsorption equilibrium, and roasting at 500 ℃ for 2h to obtain the catalyst 10 wt% PdO-0.1 wt% Au 2 O 3 -1wt％Nb 2 O 5 A carrier.
(4) Evaluation of catalyst
And (3) evaluating the catalyst by adopting a continuous fixed bed process, and respectively adding 100ml of hydroisomerization bifunctional catalyst into the first fixed bed reactor and the second fixed bed reactor. Activating with hydrogen at a flow rate of 10L/min/L under 2MPa at 500 deg.C for 12 h.
And (2) keeping the reaction temperature of the fixed bed reactor at 200 ℃, the reaction pressure at 2MPa, and after the system is stable, keeping the space velocity of m-xylylenediamine at 5L/h/L Cat, wherein the molar ratio of hydrogen to m-xylylenediamine is 5: the reaction was carried out at 1, and the conversion of the reaction was 100.0% by gas chromatography, the cis-trans isomer ratio of 1, 3-cyclohexanedimethylamine was 71/29, and the yield was 99.1% based on m-xylylenediamine.
And directly taking the reaction liquid extracted from the first fixed bed reactor as a raw material to enter a second fixed bed reactor for reaction. And (2) maintaining the reaction temperature of the fixed bed reactor II at 160 ℃, the reaction pressure at 2MPa, and under the conditions that the space velocity of the 1, 3-cyclohexanedimethanamine is 5L/h/L Cat, the molar ratio of hydrogen to the 1, 3-cyclohexanedimethanamine is 5:1, reacting. By gas chromatography analysis, the cis-trans isomer ratio of 1, 3-cyclohexanedimethanamine was 86/14, and the yield was 99.2% based on m-xylylenediamine.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. Not all embodiments are exhaustive. All obvious changes or modifications of the technical solution of the present invention are within the spirit of the present invention.
Claims (10)
1. A preparation method of 1, 3-cyclohexanedimethanamine with high cis-isomer content comprises the following steps:
(a) m-xylylenediamine is subjected to hydrogenation reaction under a hydroisomerization bifunctional catalyst and hydrogen to obtain 1, 3-cyclohexanedimethylamine with a cis-isomer/trans-isomer ratio in the range of 70/30-75/25;
(b) and (b) carrying out isomerization reaction on the 1, 3-cyclohexanedimethanamine obtained in the step (a) under the action of a hydroisomerization bifunctional catalyst and hydrogen to obtain the 1, 3-cyclohexanedimethanamine with high cis-isomer content, wherein the cis-isomer/trans-isomer ratio is in the range of 85/15-90/10.
2. The process of claim 1 wherein the hydroisomerization bifunctional catalyst in steps (a) and (b) comprises an active component and a support, said support comprising an acidic molecular sieve and a bimetallic oxide; the active components comprise PdO and Au 2 O 3 And Nb 2 O 5 。
3. The process according to claim 2, characterized in that the acidic molecular sieve is selected from one or more of ZSM-22, ZSM-48, SAPO-11 and mordenite, preferably SAPO-11 and/or mordenite, more preferably SAPO-11.
4. The method of claim 2, wherein said bimetallic oxide is selected from SnO 2 -BaO、SnO 2 -MgO、SnO 2 -MnO 2 、SnO 2 -Fe 2 O 3 、SnO 2 -ZnO and SnO 2 One or more of CaO, preferably SnO 2 -BaO、SnO 2 MgO and SnO 2 -one or more of ZnO, more preferably SnO 2 -MgO。
5. The method according to claim 4, wherein the molar ratio of Sn to the other metal element in the bimetallic oxide is 0.01:1 to 0.1:1, preferably 0.03:1 to 0.05: 1.
6. Process according to any one of claims 1 to 5, characterized in that in the hydroisomerization bifunctional catalyst, the specific surface area of the support is 200m 2 /g-500m 2 Per g, preferably 300m 2 /g-400m 2 The pore volume is 0.1ml/g to 0.60ml/g, preferably 0.3ml/g to 0.5ml/g, and the average pore diameter is 100-300nm, preferably 150-250 nm; the acidic molecular sieve is present in the support in an amount of from 90 to 98 wt%, preferably from 93 to 96 wt%, and the bimetallic oxide is present in an amount of from 2 to 10 wt%, preferably from 4 to 7 wt%, based on the weight of the support.
7. Process according to any one of claims 1 to 6, characterized in that the active component of the hydroisomerization bifunctional catalyst comprises the following composition: based on the weight of the carrier,
the PdO content is from 1 to 10% by weight, preferably from 4 to 8% by weight;
Au 2 O 3 the content is 0.1-2 wt%, preferably 0.5-1.5 wt%;
Nb 2 O 5 the content is 0.05-1 wt%, preferably 0.3-0.7 wt%.
8. The process according to any one of claims 1 to 7, wherein the preparation process of the hydroisomerization bifunctional catalyst in steps (1) and (2) comprises the following steps:
(1) preparation of the carrier:
mixing an acidic molecular sieve, a bimetallic oxide, a dispersant and a binder, kneading, molding, drying and roasting to obtain a carrier;
(2) preparation of the catalyst:
immersing the carrier obtained in the step (1) in an aqueous solution containing soluble palladium salt, gold salt and niobium salt, drying and roasting to obtain the catalyst precursor, and preferably immersing in the same volume.
9. The method as claimed in claim 8, wherein in the step (1), the roasting temperature is 400-800 ℃, preferably 500-600 ℃; the roasting time is 3-12h, preferably 5-10 h; in the step (2), the roasting temperature is 200-500 ℃, preferably 300-400 ℃, and the roasting time is 2-10h, preferably 4-8 h.
10. The process according to any one of claims 1 to 9, wherein the absolute reaction pressure in step (a) is from 2 to 10MPa, preferably from 4 to 8 MPa; the reaction temperature is 180-200 ℃, preferably 185-195 ℃; the absolute reaction pressure in the step (b) is 2-10MPa, preferably 4-8 MPa; the reaction temperature is between 100 ℃ and 160 ℃, and preferably between 120 ℃ and 140 ℃.
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