CN114890903B - Preparation method of 1, 3-cyclohexanedimethylamine with high cis-form content - Google Patents
Preparation method of 1, 3-cyclohexanedimethylamine with high cis-form content Download PDFInfo
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- CN114890903B CN114890903B CN202210637275.0A CN202210637275A CN114890903B CN 114890903 B CN114890903 B CN 114890903B CN 202210637275 A CN202210637275 A CN 202210637275A CN 114890903 B CN114890903 B CN 114890903B
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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 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 82
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 48
- 239000001257 hydrogen Substances 0.000 claims abstract description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 26
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 20
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 17
- 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 claims abstract description 9
- 230000009471 action Effects 0.000 claims abstract description 4
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 20
- 239000010931 gold Substances 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 230000002378 acidificating effect Effects 0.000 claims description 15
- 239000002808 molecular sieve Substances 0.000 claims description 14
- 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 14
- 239000010955 niobium Substances 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 238000004898 kneading Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052680 mordenite Inorganic materials 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 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
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 1
- 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
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 32
- 230000004913 activation Effects 0.000 description 22
- 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
- 238000004817 gas chromatography Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 12
- 238000001179 sorption measurement Methods 0.000 description 11
- 208000012839 conversion disease Diseases 0.000 description 9
- 229910052737 gold Inorganic materials 0.000 description 9
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000001354 calcination Methods 0.000 description 7
- 241000282326 Felis catus Species 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects 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
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 239000012295 chemical reaction liquid Substances 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
- 229920002451 polyvinyl alcohol Polymers 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
- 239000002131 composite material Substances 0.000 description 4
- 239000004310 lactic acid Substances 0.000 description 4
- 235000014655 lactic acid Nutrition 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920002647 polyamide 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
- 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
- -1 alicyclic diamine compound Chemical class 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 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
- 150000002825 nitriles Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 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 description 2
- 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- XZAHJRZBUWYCBM-UHFFFAOYSA-N [1-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1(CN)CCCCC1 XZAHJRZBUWYCBM-UHFFFAOYSA-N 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 230000008859 change Effects 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
- 238000001125 extrusion Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 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
- 238000000746 purification Methods 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
- 239000002202 Polyethylene glycol Substances 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
- 235000003704 aspartic acid Nutrition 0.000 description 1
- 230000008901 benefit 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000015165 citric acid Nutrition 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
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 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
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007789 gas Substances 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
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000005913 hydroamination reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 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
- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical compound N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 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
- 125000002560 nitrile group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 1
- 229920006391 phthalonitrile polymer Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 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
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 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
- 239000000376 reactant Substances 0.000 description 1
- 230000002441 reversible 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
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-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-cyclohexanedimethylamine with high cis-form content. The method comprises the following steps: (a) The m-xylylenediamine is subjected to hydrogenation reaction under the condition of a hydroisomerization bifunctional catalyst and hydrogen to obtain 1, 3-cyclohexanedimethylamine with cis-form/trans-form of 70/30-75/25; (b) And (3) carrying out isomerization reaction on the 1, 3-cyclohexanedimethylamine obtained in the step (a) under the action of a hydroisomerization bifunctional catalyst and hydrogen to obtain the 1, 3-cyclohexanedimethylamine with high cis-form content of cis-form/trans-form of 85/15-90/10. By controlling the reaction temperature in the two-step reaction process, the hydrogenation reaction of the m-xylylenediamine and the isomerization reaction of the 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 the m-xylylenediamine is 100%, and the yield of the 1, 3-cyclohexanedimethylamine product with high cis-form content is more than 98%.
Description
Technical Field
The invention relates to a preparation method of 1, 3-cyclohexanedimethylamine, in particular to a preparation method of 1, 3-cyclohexanedimethylamine with high yield and high cis-form content.
Background
Cyclohexane dimethylamine is an industrially important compound used as a raw material for an epoxy curing agent, polyamide, polyurethane, and the like. Cyclohexane dimethylamine has both cis isomer and trans isomer derived from cyclohexane ring, and it is known that a polymer using cyclohexane dimethylamine has a large change in physical properties depending on the isomer ratio of cis isomer to trans isomer. If the polyamide synthesized from 1, 3-cyclohexanediamine having a high cis content is highly crystalline, the polyamide synthesized from 1, 3-cyclohexanediamine having a high trans content is amorphous. And for example, the polyamide synthesized by taking 1, 4-cyclohexanediamine with high trans content as a raw material has the characteristics of high melting point and high heat resistance. Thus, it is important to control the ratio of cis and trans isomers in cyclohexanediamine.
The preparation method of cyclohexanedimethylamine mainly comprises a phthalonitrile hydrogenation method, a cyclohexanedimethanol hydroamination method and a xylylenediamine hydrogenation method. Among them, the xylylenediamine hydrogenation method has the advantages of high raw material conversion rate and product selectivity, easy separation and purification of the product, etc., becomes an industrial production method of cyclohexanediamine, and is also a method with more reports of the prior patent.
Patent CN101959848B discloses a catalyst for preparing cyclohexanediamine by catalytic hydrogenation of xylylenediamine and a preparation method thereof, the patent prepares a catalyst which takes bimetallic oxide as a carrier and Ru as an active component and adds a first auxiliary agent component and a second auxiliary agent component, in a system which does not use liquid ammonia and alkali metal hydroxide as deamination inhibitors, the conversion rate of raw materials is more than 99% and the selectivity of products is 97%, but the patent does not mention the problem of cis-trans isomers.
Patent CN114082428A discloses a supported Ru-Re catalyst with high activity, high selectivity and long service life, and a method for synthesizing an alicyclic diamine compound by catalytic hydrogenation of an aromatic diamine compound by using the catalyst, wherein the content of a key stereoisomer can be controlled in a proper range while the performance of the catalyst is considered, and the cis-form content in a product reaches more than 80% by taking m-xylylenediamine hydrogenation for preparing 1, 3-cyclohexanediamine as an example.
Patent CN111116381a discloses a method for preparing 1, 3-cyclohexanediamine by hydrogenating m-xylylenediamine, which adopts a semi-batch process, and requires strict control of the dripping speed of m-xylylenediamine, and simultaneously, increases the cis-body content in the hydrogenated product 1, 3-cyclohexanediamine by adding a rigid cyclic compound containing nitrogen into the reaction system, thus obtaining a product with the cis-body/trans-body ratio of more than 80/20. Also, the method requires the additional introduction of nitrogen-containing rigid cyclic compounds such as pyridine, quinoline and the like to cause permanent poisoning and deactivation of the catalyst, and has the problems of easy catalyst deactivation, low production efficiency and high separation energy consumption.
Patent CN105555754a discloses a method for isomerising cyclohexanedimethylamine, which comprises carrying out isomerisation reaction of 1, 3-cyclohexanedimethylamine in the presence of 4-methylbenzaldehyde and sodium amide to obtain 1, 3-cyclohexanedimethylamine, wherein the cis/trans ratio of the 1, 3-cyclohexanedimethylamine is increased from 74/26 to 80/20, the isomerisation yield is 94%, the method can increase the cis content of the 1, 3-cyclohexanedimethylamine to a certain extent, but the effect is not obvious, and 6% of the 1, 3-cyclohexanedimethylamine is converted into other impurities, and separation and purification of the product are needed again.
Patent CN102030657a discloses a method for synthesizing 3, 3-dimethyl-4, 4-diamino dicyclohexyl methane, which adopts a batch process, and the raw material 3, 3-dimethyl-4, 4-diamino diphenylmethane is prepared into a 3, 3-dimethyl-4, 4-diamino dicyclohexyl methane product under the action of hydrogen, ru-based catalyst and trace alkaline earth metal auxiliary agent, but the patent does not mention the problem of cis-trans isomerism.
Aiming at the problems existing in the above disclosed method for producing the 1, 3-cyclohexanedimethylamine with high cis-form content, a proper catalyst and a production process are needed to be found, so that the problems of catalyst activity, selectivity and stability are fundamentally solved, and meanwhile, the purposes of improving the production efficiency and the product quality are achieved by continuously optimizing the process conditions.
Disclosure of Invention
The invention aims to provide a preparation method of 1, 3-cyclohexanedimethylamine with high cis-form content, which adopts a hydroisomerization bifunctional catalyst and a two-stage variable temperature reaction process to simultaneously realize hydrogenation reaction of m-xylylenediamine and isomerization reaction of 1, 3-cyclohexanedimethylamine, and finally obtains a 1, 3-cyclohexanedimethylamine product with high yield and high cis-form content.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a preparation method of 1, 3-cyclohexanedimethylamine with high yield and high cis-form content comprises the following steps:
(a) The m-xylylenediamine is subjected to hydrogenation reaction under the condition of a hydroisomerization bifunctional catalyst and hydrogen to obtain 1, 3-cyclohexanedimethylamine with the cis-form/trans-form ratio in the range of 70/30-75/25;
(b) And (3) carrying out isomerization reaction on the 1, 3-cyclohexanediamine obtained in the step (a) under the action of a hydroisomerization bifunctional catalyst and hydrogen to obtain the 1, 3-cyclohexanediamine with high cis-form content, wherein the cis-form/trans-form ratio of the 1, 3-cyclohexanediamine is in the range of 85/15-90/10.
The hydroisomerization bifunctional catalyst in 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 component comprises PdO and Au 2 O 3 And Nb (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 adopting a conventional preparation method, such as an isovolumetric impregnation method, and is prepared by immersing the metal oxide in an aqueous solution containing soluble tin salt according to a proportion, drying and roasting.
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, preferably nitrate.
In the preparation method of the bimetallic oxide, the drying temperature is 90-140 ℃, preferably 100-130 ℃, and the drying time is 4-10 hours, preferably 6-8 hours; the temperature of calcination is 200-400 ℃, preferably 250-350 ℃; the calcination time is 3 to 10 hours, preferably 5 to 8 hours.
In the hydroisomerization bifunctional catalyst, the specific surface area of the carrier is 200m 2 /g-500m 2 /g, preferably 300m 2 /g-400m 2 Per gram, pore volume of 0.1ml/g to 0.60ml/g, preferably 0.3ml/g to 0.5ml/g, average pore diameter of 100 to 300nm, preferably 150 to 250nm; the acidic molecular sieve content in the support is from 90 to 98wt%, preferably from 93 to 96wt%, and the bimetallic oxide content is from 2 to 10wt%, preferably from 4 to 7wt%, based on the weight of the support.
The active components of the hydroisomerization bifunctional catalyst comprise the following components: based on the weight of the carrier,
the PdO content is 1 to 10wt%, preferably 4 to 8wt%;
Au 2 O 3 the content is 0.1-2wt%, preferably 0.5-1.5wt%;
Nb 2 O 5 the content is 0.05 to 1wt%, preferably 0.3 to 0.7wt%.
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 dispersing agent and a binder, kneading, forming, 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 a catalyst precursor, preferably in an equal 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, gelatin, 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 the corresponding metal element, preferably acetate.
In step (1), the binder is used in the form of a solution having a concentration of 5 to 20wt%, preferably 10 to 15wt% and an amount of 0.5:1-1:1, preferably 0.6:1-0.8:1 based on the sum of the weight of the acidic molecular sieve and the weight of the bimetallic oxide.
The dosage of the dispersing agent is 0.01:1-0.1:1, preferably 0.04:1-0.06:1 based on the sum of the weight of the acidic molecular sieve and the weight of the bimetallic oxide.
In the step (1), the drying temperature is 100-150 ℃, preferably 120-140 ℃, and the drying time is 2-10 hours, preferably 4-8 hours; the temperature of calcination is 400-800 ℃, preferably 500-600 ℃; the calcination time is 3 to 12 hours, preferably 5 to 10 hours.
In the step (2), the drying temperature is 100-150 ℃, preferably 120-140 ℃, and the drying time is 2-10 hours, preferably 4-8 hours; the calcination temperature is 200-500 ℃, preferably 300-400 ℃, and the calcination time is 2-10h, preferably 4-8h.
The hydroisomerization bifunctional catalyst needs to be activated to be active. The activation method comprises the following steps: the hydrogen flow is 1-10L/min/L cat, preferably the hydrogen flow is 3-7L/min/L cat, the absolute pressure is 2-10MPa, preferably 4-8MPa, and the activation temperature is 200-500 ℃, preferably 300-400 ℃ for 2-12h, preferably 4-10h.
The absolute reaction pressure in the step (a) is 2-10MPa, preferably 4-8MPa; the reaction temperature is 180-200 ℃, preferably 185-195 ℃; the space velocity of the raw material m-xylylenediamine is 1-5L/h/L cat, preferably 2-4L/h/L cat; the molar ratio of the hydrogen to the m-xylylenediamine is 3-8:1, preferably 4-6:1.
the absolute reaction pressure in step (b) is 2-10MPa, preferably 4-8MPa; the reaction temperature is 100-160 ℃, preferably 120-140 ℃; the space velocity of the raw material 1, 3-cyclohexanediamine is 1-5L/h/L cat, preferably 2-4L/h/L cat; the molar ratio of the hydrogen to the 1, 3-cyclohexanediamine is 3-8:1, preferably 4-6:1.
the invention surprisingly discovers that by adopting a hydroisomerization bifunctional catalyst and a two-stage variable temperature reaction process and controlling the change of 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 finally the 1, 3-cyclohexanedimethylamine product with high yield and high cis-form content is obtained. The conversion rate of the raw material m-xylylenediamine reaches 100 percent, and the yield of the 1, 3-cyclohexanedimethylamine product with high cis-form content is more than 98 percent. The reaction conditions for preparing the 1, 3-cyclohexanedimethylamine by the hydrogenation reaction of the m-xylylenediamine are severe, the hydrogenation reaction needs to be completed under high temperature and high pressure conditions in order to ensure high conversion rate and high selectivity, and isomerization reaction occurs in the hydrogenation reaction process, so that the 1, 3-cyclohexanedimethylamine product obtained by the hydrogenation reaction is a mixture of cis-form and trans-form, and generally the cis-form is relatively stable compared with the trans-form, but the cis-form/trans-form ratio in the 1, 3-cyclohexanedimethylamine obtained by the hydrogenation reaction can only be kept within the range of 70/30-75/25. The isomerization reaction of the 1, 3-cyclohexanediamine is exothermic reversible reaction, the temperature is reduced, the isomerization reaction is facilitated, namely the content of cis-form in isomers is improved, and meanwhile, the occurrence of side reactions such as decomposition reaction, polymerization reaction and the like can be restrained at low temperature, so that the high-yield product is facilitated. 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 realization of the double functions of hydrogenation and isomerization of the catalyst is ensured.
The invention prepares the acidic molecular sieve and the bimetallic oxide composite carrier loaded PdO and Au 2 O 3 And Nb (Nb) 2 O 5 Three-component bifunctional catalystThe catalyst is applied to catalytic hydroisomerization reaction, and can meet the requirement of active centers for hydrogenation and acidic centers for isomerization reaction. On one hand, the acidic molecular sieve has micropore characteristics, is beneficial to improving the dispersity of active metal and improves the activity of the catalyst; on the other hand, the bimetallic oxide has controllable mesoporous characteristic and proper specific surface area and pore volume, can provide diffusion channels for reactant molecules and product molecules, is beneficial to mass transfer in carrier pores, effectively avoids the generation of byproducts, and improves the selectivity of the catalyst. Finally, the bimetallic 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 inhibit the deamination condensation side reaction of the m-xylylenediamine in the hydrogenation reaction process, and improve the effective utilization rate of the m-xylylenediamine; in the isomerization reaction process, the content and the yield of cis-form 1, 3-cyclohexanediamine are improved.
In the hydrogenation reaction process, the active component PdO and Au 2 O 3 And Nb (Nb) 2 O 5 Producing synergistic effects, and improving 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, while trace nitrile substances remained in raw material m-xylylenediamine are the main factors causing the deactivation of the hydrogenation catalyst, and the active component Au 2 O 3 Enhances the adsorption of trace nitrile impurities in the raw materials and simultaneously the active component Au 2 O 3 The micro nitrile impurities in the raw materials can be hydrogenated and converted into amino, so that the toxicity of the micro nitrile groups in the m-xylylenediamine raw materials to a hydrogenation catalyst is avoided, and the service life of the catalyst is prolonged. At the same time Nb 2 O 5 Is advantageous for the 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 invention is further illustrated below in connection with the examples, but the invention is not limited to the examples listed but also includes equivalent improvements and variants of the solution defined in the claims appended hereto.
Gas chromatograph: shimadzu GC-2014 (FID) detector, SE-30 capillary column
300 ℃ of sample inlet and 270 ℃ of detector; heating program: the temperature was kept at 100℃for 5min, and then raised to 260℃at a rate of 20℃per min, and maintained for 10min.
In the examples the reactor is a fixed bed reactor.
Index of m-xylylenediamine: the content of m-xylylenediamine was 99.8% by weight, the content of 3-cyanobenzylamine was 0.15% by weight, and the content of isophthalonitrile was 0.05% by weight.
Determination of the content of active components in the catalyst: the content of active metal in the catalyst was measured by a plasma emission spectrometer.
Example 1
(1)SnO 2 Preparation of MgO
100g of MgO is immersed in 100ml of aqueous solution containing 26.6g of tin acetate, after adsorption equilibrium, the mixture is dried at 100 ℃ for 7h and baked at 250 ℃ for 8h, and SnO with the molar ratio of Sn to Mg of 0.03:1 is obtained 2 -MgO bimetallic oxide.
(2) Preparation of the Carrier
186g SAPO-11, 14g SnO 2 MgO, 8g polyvinylpyrrolidone and 120g of 10wt% aqueous solution of citric acid are mixed, followed by kneading and extrusion molding, drying at 130℃for 6 hours and baking at 400℃for 5 hours to obtain a carrier.
(3) Catalyst 4wt% PdO-0.5wt% 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 the carrier into 100ml of aqueous solution containing 8.71g of palladium nitrate dihydrate, 0.87g of gold nitrate and 0.91g of niobium nitrate by adopting an isovolumetric impregnation method, drying for 6h at 130 ℃ after adsorption balance, and roasting for 4h at 400 ℃ to obtain 4-0.5 wt% of PdO (gold) serving as a catalyst 2 O 3 -0.3wt％Nb 2 O 5 A carrier.
(4) Evaluation of catalyst
Catalyst evaluation was carried out by a continuous fixed bed process, and 100ml of hydroisomerization bifunctional catalyst was added to each of the fixed bed reactor I and the fixed bed reactor II. The hydrogen is adopted for activation, the hydrogen flow is 3L/min/L of catalyst, the activation pressure is 6MPa, the activation temperature is 350 ℃, and the activation time is 10h.
The reaction temperature of the fixed bed reactor I is 195 ℃, the reaction pressure is maintained at 6MPa, after the system is stable, the space velocity of the m-xylylenediamine is 2L/h/L Cat, and the molar ratio of the hydrogen to the m-xylylenediamine is 4:1, and the reaction conversion rate is 100.0% by gas chromatography analysis, the cis-trans isomer ratio of 1, 3-cyclohexanediamine is 70/30, and the yield is 99.5% based on m-xylylenediamine. After the catalyst was continuously operated for 500 hours, the reaction conversion was 99.6% by gas chromatography, the cis-trans isomer ratio of 1, 3-cyclohexanediamine was 71/29, and the yield was 99.0% based on m-xylylenediamine.
The reaction liquid extracted from the fixed bed reactor I directly enters the fixed bed reactor II as a raw material for reaction. The reaction temperature of the fixed bed reactor II was 120 ℃, the reaction pressure was maintained at 6MPa, the space velocity of 1, 3-cyclohexanedimethanamine was 2L/h/L Cat, and the molar ratio of hydrogen to 1, 3-cyclohexanedimethanamine was 4: 1. The cis-trans isomer ratio of 1, 3-cyclohexanediamine was 85/15 by gas chromatography, and the yield was 98.5% based on m-xylylenediamine.
Comparative example 1
(1) Catalyst preparation
200g of SAPO-11 was used, without SnO 2 MgO, the remainder of the procedure being as in example 1.
(2) Evaluation of catalyst
Activated and evaluated by the process of example 1, the reaction conversion in the fixed bed reactor I was 95.0%, the cis-trans isomer ratio of 1, 3-cyclohexanediamine was 72/28, and the yield was 91.5% based on m-xylylenediamine; the cis-trans isomer ratio of 1, 3-cyclohexanediamine in 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, SAPO-11 was not used, and the rest of the procedure was as in example 1.
(2) Evaluation of catalyst
Activated and evaluated by the procedure of example 1, the reaction conversion in the fixed bed reactor I was 90.2%, the cis-trans isomer ratio of 1, 3-cyclohexanediamine was 70/30, and the yield was 87.6% based on m-xylylenediamine; the cis-trans isomer ratio of 1, 3-cyclohexanediamine in the fixed bed reactor II was 82/18, and the yield was 75.8% based on m-xylylenediamine.
Comparative example 3
No gold nitrate was added during the catalyst preparation and the remainder was referred to in example 1. After the catalyst was continuously operated for 500 hours, the reaction conversion was 92.5% by gas chromatography, the cis-trans isomer ratio of 1, 3-cyclohexanediamine was 71/29, and the yield was 86.5% based on m-xylylenediamine.
Comparative example 4
Niobium nitrate was not added in the catalyst preparation, and the rest was as described in example 1. In the hydrogenation reaction, the reaction conversion rate was 96.5% by gas chromatography analysis, the cis-trans isomer ratio of 1, 3-cyclohexanedimethanamine was 72/28, and the yield was 93.2% based on m-xylylenediamine.
Comparative example 5
The isomerization temperature was controlled at 195℃and the remainder was as described in example 1. The cis-trans isomer ratio of 1, 3-cyclohexanediamine was 71/29 by gas chromatography, and the yield was 98.4% based on m-xylylenediamine.
Comparative example 6
According to the same manner as in example 1, snO having a Sn to Mg molar ratio of 0.2:1 is obtained 2 -MgO bimetallic oxide.
Under the condition of not changing other conditions, the conversion rate of hydrogenation reaction is 100.0 percent, the cis-trans isomer ratio of 1, 3-cyclohexanediamine is 71/29, and the yield is 97.2 percent calculated by m-xylylenediamine through gas chromatography analysis; in the isomerization reaction, the cis-trans isomer ratio of 1, 3-cyclohexanedimethylamine was 85/15, and the yield was 95.3% based on m-xylylenediamine.
Example 2
(1)SnO 2 Preparation of MgO
100g of MgO is immersed in 100ml of aqueous solution containing 35.5g of tin acetate, dried for 8 hours at 120 ℃ and roasted for 6 hours at 300 ℃ after adsorption equilibrium, and SnO with the Sn to Mg molar ratio of 0.04:1 is obtained 2 -MgO bimetallic oxide.
(2) Preparation of the Carrier
190g of SAPO-11 and 10g of SnO 2 MgO, 12g of polyvinylpyrrolidone and 160g of 12wt% aqueous solution of citric acid are mixed, followed by kneading and extrusion molding, drying at 120℃for 4 hours and calcining at 800℃for 7 hours to obtain a carrier.
(3) Catalyst 8wt% PdO-1wt% 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 adopting an isovolumetric impregnation method, drying for 4h at 120 ℃ and roasting for 6h at 200 ℃ after adsorption balance to obtain 8wt% PdO-1wt% Au of a catalyst 2 O 3 -0.5wt％Nb 2 O 5 A carrier.
(4) Evaluation of catalyst
Catalyst evaluation was carried out by a continuous fixed bed process, and 100ml of hydroisomerization bifunctional catalyst was added to each of the fixed bed reactor I and the fixed bed reactor II. The hydrogen is adopted for activation, the hydrogen flow is 5L/min/L of catalyst, the activation pressure is 8MPa, the activation temperature is 300 ℃, and the activation time is 6h.
The reaction temperature of the fixed bed reactor I is 185 ℃, the reaction pressure is maintained at 4MPa, after the system is stable, the space velocity of the m-xylylenediamine is 4L/h/L Cat, and the molar ratio of the hydrogen to the m-xylylenediamine is 6:1, and the reaction conversion rate is 100.0% by gas chromatography analysis, the cis-trans isomer ratio of 1, 3-cyclohexanediamine is 72/28, and the yield is 99.6% based on m-xylylenediamine.
The reaction liquid extracted from the fixed bed reactor I directly enters the fixed bed reactor II as a raw material for reaction. The reaction temperature of the fixed bed reactor II was 130 ℃, the reaction pressure was maintained at 4MPa, the space velocity of 1, 3-cyclohexanedimethanamine was 4L/h/L Cat, and the molar ratio of hydrogen to 1, 3-cyclohexanedimethanamine was 6:1. The cis-trans isomer ratio of 1, 3-cyclohexanediamine was 88/12 by gas chromatography, and the yield was 98.4% based on m-xylylenediamine.
Example 3
(1)SnO 2 Preparation of MgO
100g of MgO is immersed in 100ml of aqueous solution containing 44.4g of tin acetate, dried for 10h at 90 ℃ after adsorption equilibrium, and baked for 5h at 350 ℃ to obtain SnO with the molar ratio of Sn to Mg of 0.05:1 2 -MgO bimetallic oxide.
(2) Preparation of the Carrier
192g of SAPO-11 and 8g of SnO 2 Mixing MgO, 10g polyvinyl alcohol and 140g citric acid aqueous solution with 15wt% concentration, kneading and extruding to form, drying at 140 deg.c for 8 hr, and roasting at 500 deg.c for 10 hr to obtain composite carrier.
(3) Catalyst 6wt% PdO-1.5wt% 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 the composite carrier into 100ml of aqueous solution containing 13.06g of palladium nitrate dihydrate, 2.60g of gold nitrate and 2.43g of niobium nitrate by adopting an isovolumetric impregnation method, drying at 140 ℃ for 8h after adsorption balance, and roasting at 350 ℃ for 8h to obtain 6wt% PdO-1.5wt% Au of a catalyst 2 O 3 -0.8wt％Nb 2 O 5 A carrier.
(4) Evaluation of catalyst
Catalyst evaluation was carried out by a continuous fixed bed process, and 100ml of hydroisomerization bifunctional catalyst was added to each of the fixed bed reactor I and the fixed bed reactor II. The hydrogen is adopted for activation, the hydrogen flow is 7L/min/L of catalyst, the activation pressure is 4MPa, the activation temperature is 400 ℃, and the activation time is 4h.
The reaction temperature of the fixed bed reactor I is 190 ℃, the reaction pressure is maintained at 8MPa, after the system is stable, the space velocity of the m-xylylenediamine is 3L/h/L Cat, and the molar ratio of the hydrogen to the m-xylylenediamine is 8:1, and the reaction conversion rate is 100.0% by gas chromatography analysis, the cis-trans isomer ratio of 1, 3-cyclohexanediamine is 75/25, and the yield is 99.4% based on m-xylylenediamine.
The reaction liquid extracted from the fixed bed reactor I directly enters the fixed bed reactor II as a raw material for reaction. The reaction temperature of the fixed bed reactor II was 140 ℃, the reaction pressure was maintained at 8MPa, the space velocity of 1, 3-cyclohexanedimethanamine was 3L/h/L Cat, and the molar ratio of hydrogen to 1, 3-cyclohexanedimethanamine was 8: 1. The cis-trans isomer ratio of 1, 3-cyclohexanediamine was 90/10 by gas chromatography, and the yield was 98.7% based on m-xylylenediamine.
Example 4
(1)SnO 2 Preparation of ZnO
100g ZnO is immersed in 100ml water solution containing 8.9g tin acetate, after adsorption equilibrium, the mixture is dried for 4 hours at 140 ℃, and baked for 3 hours at 400 ℃ to obtain SnO with the molar ratio of Sn to Zn of 0.01:1 2 -ZnO bimetallic oxide.
(2) Preparation of the Carrier
180g mordenite, 20g SnO 2 Mixing ZnO, 2g of polyvinyl alcohol and 100g of lactic acid aqueous solution with the concentration of 5wt%, then kneading and extruding to form, drying at 150 ℃ for 2h, and roasting at 700 ℃ for 3h to obtain the carrier.
(3) Catalyst 1wt% PdO-2wt% 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 the carrier into 100ml of aqueous solution containing 2.18g of palladium nitrate dihydrate, 3.47g of gold nitrate and 0.15g of niobium nitrate by adopting an isovolumetric impregnation method, drying at 150 ℃ for 2h after adsorption balance, and roasting at 300 ℃ for 10h to obtain 1-2wt% of PdO catalyst 2 O 3 -0.05wt％Nb 2 O 5 A carrier.
(4) Evaluation of catalyst
Catalyst evaluation was carried out by a continuous fixed bed process, and 100ml of hydroisomerization bifunctional catalyst was added to each of the fixed bed reactor I and the fixed bed reactor II. The hydrogen is adopted for activation, the hydrogen flow is 1L/min/L of catalyst, the activation pressure is 10MPa, the activation temperature is 200 ℃, and the activation time is 2h.
The reaction temperature of the fixed bed reactor I is 180 ℃, the reaction pressure is maintained at 10MPa, after the system is stable, the space velocity of the m-xylylenediamine is 1L/h/L Cat, and the molar ratio of the hydrogen to the m-xylylenediamine is 5:1, and the conversion rate of the reaction is 100.0% by gas chromatography analysis, the cis-trans isomer ratio of the 1, 3-cyclohexanediamine is 73/27, and the yield is 99.8% based on m-xylylenediamine.
The reaction liquid extracted from the fixed bed reactor I directly enters the fixed bed reactor II as a raw material for reaction. The reaction temperature of the fixed bed reactor II is 100 ℃, the reaction pressure is maintained at 10MPa, the space velocity of the 1, 3-cyclohexanediamine is 1L/h/L Cat, and the molar ratio of the hydrogen to the 1, 3-cyclohexanediamine is 5:1. The cis-trans isomer ratio of 1, 3-cyclohexanediamine was 87/13, and the yield was 98.6% based on m-xylylenediamine by gas chromatography.
Example 5
(1)SnO 2 Preparation of BaO
100g of BaO is immersed in 100ml of aqueous solution containing 88.7g of tin acetate, after adsorption equilibrium, the mixture is dried at 130 ℃ for 6 hours and baked at 200 ℃ for 10 hours, and SnO with the molar ratio of Sn to Ba of 0.1:1 is obtained 2 BaO bimetallic oxide.
(2) Preparation of the Carrier
196g mordenite, 4g SnO 2 BaO, 20g of polyvinyl alcohol and 200g of aqueous solution of lactic acid with concentration of 20wt percent are mixed, then mixed, kneaded, extruded and molded, dried at 100 ℃ for 10 hours and baked at 600 ℃ for 12 hours to obtain a carrier.
(3) Catalyst 10wt% PdO-0.1wt% Au 2 O 3 -1wt％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 21.77g of palladium nitrate dihydrate, 0.17g of gold nitrate and 3.03g of niobium nitrate by adopting an isovolumetric impregnation method, drying the carrier for 10h at 100 ℃ after adsorption balance, and roasting the carrier for 2h at 500 ℃ to obtain 10wt% PdO-0.1wt% Au of a catalyst 2 O 3 -1wt％Nb 2 O 5 A carrier.
(4) Evaluation of catalyst
Catalyst evaluation was carried out by a continuous fixed bed process, and 100ml of hydroisomerization bifunctional catalyst was added to each of the fixed bed reactor I and the fixed bed reactor II. The hydrogen is adopted for activation, the hydrogen flow is 10L/min/L of catalyst, the activation pressure is 2MPa, the activation temperature is 500 ℃, and the activation time is 12h.
The reaction temperature of the fixed bed reactor I is 200 ℃, the reaction pressure is maintained at 2MPa, after the system is stable, the space velocity of the m-xylylenediamine is 5L/h/L Cat, and the molar ratio of the hydrogen to the m-xylylenediamine is 5:1, and the reaction conversion rate is 100.0% by gas chromatography analysis, the cis-trans isomer ratio of 1, 3-cyclohexanediamine is 71/29, and the yield is 99.1% based on m-xylylenediamine.
The reaction liquid extracted from the fixed bed reactor I directly enters the fixed bed reactor II as a raw material for reaction. The reaction temperature of the fixed bed reactor II was 160 ℃, the reaction pressure was maintained at 2MPa, the space velocity of 1, 3-cyclohexanedimethanamine was 5L/h/L Cat, and the molar ratio of hydrogen to 1, 3-cyclohexanedimethanamine was 5:1. The cis-trans isomer ratio of 1, 3-cyclohexanediamine was 86/14 as analyzed by gas chromatography, and the yield was 99.2% based on m-xylylenediamine.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. Not all embodiments are exhaustive. All obvious variations or modifications which come within the spirit of the invention are desired to be protected.
Claims (12)
1. A method for preparing 1, 3-cyclohexanedimethylamine with high cis-form content, which comprises the following steps:
(a) The m-xylylenediamine is subjected to hydrogenation reaction under the condition of a hydroisomerization bifunctional catalyst and hydrogen to obtain 1, 3-cyclohexanedimethylamine with the cis-form/trans-form ratio in the range of 70/30-75/25;
(b) Carrying out isomerization reaction on the 1, 3-cyclohexanedimethylamine obtained in the step (a) under the action of a hydroisomerization bifunctional catalyst and hydrogen to obtain high cis-form content 1, 3-cyclohexanedimethylamine with cis-form/trans-form ratio 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 component comprises PdO and Au 2 O 3 And Nb (Nb) 2 O 5 ；
The acidic molecular sieve is selected from one or more of ZSM-22, ZSM-48, SAPO-11 and mordenite;
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.
2. The method according to claim 1, wherein the molar ratio of Sn to the other metal element in the bimetallic oxide is 0.01:1 to 0.1:1.
3. The method according to claim 2, wherein the molar ratio of Sn to the other metal element is 0.03:1 to 0.05:1.
4. A process according to any one of claims 1 to 3, characterized in that in the hydroisomerization bifunctional catalyst, the specific surface area of the support is 200m 2 /g-500m 2 Per gram, the pore volume is 0.1ml/g-0.60ml/g, and the average pore diameter is 100-300nm; the content of the acidic molecular sieve in the carrier is 90-98wt%, and the content of the bimetallic oxide is 2-10wt%, based on the weight of the carrier.
5. The process according to claim 4, wherein the specific surface area of the support in the hydroisomerization bifunctional catalyst is 300m 2 /g-400m 2 Per gram, the pore volume is 0.3ml/g-0.5ml/g, and the average pore diameter is 150-250nm; the content of the acidic molecular sieve in the carrier is 93-96wt%, and the content of the bimetallic oxide is 4-7wt%, based on the weight of the carrier.
6. A process according to any one of claims 1 to 3, characterized in that the active component of the hydroisomerization bifunctional catalyst comprises the following composition: based on the weight of the carrier,
the content of PdO is 1-10wt%;
Au 2 O 3 the content is 0.1-2wt%;
Nb 2 O 5 the content is 0.05-1wt%.
7. The process of claim 6, wherein the active component of the hydroisomerization bifunctional catalyst comprises the following composition: based on the weight of the carrier,
the content of PdO is 4-8wt%;
Au 2 O 3 the content is 0.5-1.5wt%;
Nb 2 O 5 the content is 0.3-0.7wt%.
8. A process according to any one of claims 1 to 3, wherein the preparation of the hydroisomerisation bifunctional catalyst of steps (a) and (b) comprises the steps of:
(1) Preparation of the carrier:
mixing an acidic molecular sieve, a bimetallic oxide, a dispersing agent and a binder, kneading, forming, 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 a catalyst precursor.
9. The method of claim 8, wherein in step (1), the firing temperature is 400-800 ℃; roasting for 3-12h; in the step (2), the roasting temperature is 200-500 ℃, and the roasting time is 2-10h.
10. The method according to claim 9, wherein in the step (1), the baking temperature is 500 to 600 ℃; roasting for 5-10h; in the step (2), the roasting temperature is 300-400 ℃, and the roasting time is 4-8h.
11. A process according to any one of claims 1 to 3, wherein the absolute reaction pressure of step (a) is from 2 to 10MPa; the reaction temperature is 180-200 ℃; the absolute reaction pressure in the step (b) is 2-10MPa; the reaction temperature is 100-160 ℃.
12. The process of claim 11, wherein the absolute reaction pressure of step (a) is 4-8MPa; the reaction temperature is 185-195 ℃; the absolute reaction pressure of the step (b) is 4-8MPa; the reaction temperature is 120-140 ℃.
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