CN117599793A - Method for preparing cyclohexylamine by taking cyclohexanol as raw material - Google Patents
Method for preparing cyclohexylamine by taking cyclohexanol as raw material Download PDFInfo
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- CN117599793A CN117599793A CN202311554376.2A CN202311554376A CN117599793A CN 117599793 A CN117599793 A CN 117599793A CN 202311554376 A CN202311554376 A CN 202311554376A CN 117599793 A CN117599793 A CN 117599793A
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- catalyst
- cyclohexylamine
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- cyclohexanol
- hydrogen
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- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 title claims abstract description 141
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000002994 raw material Substances 0.000 title abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 128
- 239000000047 product Substances 0.000 claims abstract description 34
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 31
- 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 29
- 238000005576 amination reaction Methods 0.000 claims abstract description 17
- 239000010949 copper Substances 0.000 claims abstract description 15
- 239000011701 zinc Substances 0.000 claims abstract description 15
- 239000007791 liquid phase Substances 0.000 claims abstract description 14
- 229910052788 barium Inorganic materials 0.000 claims abstract description 13
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 13
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 12
- 239000010941 cobalt Substances 0.000 claims abstract description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012071 phase Substances 0.000 claims abstract description 10
- 239000004480 active ingredient Substances 0.000 claims abstract description 7
- 239000006200 vaporizer Substances 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 3
- 230000003213 activating effect Effects 0.000 claims abstract description 3
- 238000005086 pumping Methods 0.000 claims abstract description 3
- 230000008016 vaporization Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 241000219782 Sesbania Species 0.000 claims description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 238000002309 gasification Methods 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 abstract description 19
- 239000007789 gas Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 150000002431 hydrogen Chemical class 0.000 abstract description 2
- 229910001868 water Inorganic materials 0.000 description 16
- 239000012043 crude product Substances 0.000 description 11
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- UDIPTWFVPPPURJ-UHFFFAOYSA-M Cyclamate Chemical compound [Na+].[O-]S(=O)(=O)NC1CCCCC1 UDIPTWFVPPPURJ-UHFFFAOYSA-M 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 239000000625 cyclamic acid and its Na and Ca salt Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 229960001462 sodium cyclamate Drugs 0.000 description 4
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000005913 hydroamination reaction Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000006268 reductive amination reaction Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- FECNOIODIVNEKI-UHFFFAOYSA-N 2-[(2-aminobenzoyl)amino]benzoic acid Chemical class NC1=CC=CC=C1C(=O)NC1=CC=CC=C1C(O)=O FECNOIODIVNEKI-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000008122 artificial sweetener Substances 0.000 description 1
- 235000021311 artificial sweeteners Nutrition 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- -1 coatings Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229940109275 cyclamate Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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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
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
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- 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
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- 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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Abstract
The invention belongs to the field of chemical industry, and particularly relates to a production method for preparing cyclohexylamine from cyclohexanol and a related catalyst. The invention provides a catalyst for preparing cyclohexylamine, which consists of active ingredients and a catalyst carrier: the active component consists of cobalt accounting for 0.1 to 20 percent, copper accounting for 0.1 to 2 percent, zinc accounting for 0.1 to 2 percent and barium accounting for 0.1 to 2 percent of the weight of the catalyst; the catalyst carrier is the rest. The invention also provides a method for preparing cyclohexylamine by using cyclohexanol as a raw material by using the catalyst, which comprises the following steps: activating the catalyst with hydrogen, pumping cyclohexanol, liquid ammonia and hydrogen into a vaporizer, vaporizing and then carrying out a reactor, and carrying out amination reaction under the action of the activated catalyst; the amination reaction product is cooled to form a liquid phase product and a gas phase product, wherein the liquid phase product comprises cyclohexylamine. The invention improves the selectivity of dicyclohexylamine through improving the performance of the catalyst.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a production method for preparing cyclohexylamine from cyclohexanol and a related catalyst.
Background
Cyclohexylamine is also called hexahydroaniline, and is an important chemical organic intermediate. Cyclohexylamine is an organic compound, colorless liquid, has strong ammonia smell and has strong organic alkali property. The application fields of cyclohexylamine mainly comprise the following four aspects:
1. the most important use of cyclohexylamine is in the manufacture of rubber accelerator CBS. The rubber accelerator can obviously improve the processability of rubber, and improve the ageing resistance, the oxidation resistance and the vulcanization resistance of the rubber, so that the rubber product is more durable and environment-friendly.
2. Another important use of cyclohexylamine is as a raw material for the manufacture of sodium cyclamate. Because the sodium cyclamate has good heat stability and pure taste, the sodium cyclamate is widely applied to food and beverage enterprises.
3. Cyclohexylamine can be used as a pH regulator for boiler feed water. Cyclohexylamine belongs to volatile substances, and can be easily diffused into the whole system after being added into cyclohexylamine, and can be used as a boiler water treatment agent, a corrosion inhibitor, a rubber accelerator and an organic synthesis intermediate.
4. Cyclohexylamine is a good solvent, and can be applied to resins, coatings, fats and paraffin oils, and can also be used for preparing desulfurizing agents, plastic and textile chemical assistants, metal corrosion inhibitors, emulsifying agents, preservatives, antistatic agents, latex coagulants, petroleum additives, bactericides, pesticides and dye intermediates. The cyclohexylamine sulfonate can be used as artificial sweetener for food, beverage and medicine.
Among them, the main uses of cyclohexylamine are focused on both rubber accelerators and cyclamate. In recent years, the demand of the cyclohexylamine market in China steadily increases due to the rapid development of downstream product markets such as rubber accelerator CBS, sodium cyclamate and the like.
The existing cyclohexylamine preparation methods mainly comprise an aniline catalytic hydrogenation method, a cyclohexanol catalytic amination method, a cyclohexanone hydroamination method, a nitrobenzene catalytic hydrogenation method, a phenol reductive amination method and the like.
The method comprises the following steps:
1. the industrial production method in China adopts an aniline catalytic hydrogenation method to prepare cyclohexylamine, and adopts cobalt-based or nickel-based catalysts, so that the method has the advantages of easily available raw materials, high safety and high atom utilization rate.
2. The one-pot method for catalyzing and generating the cyclohexylamine by using the nitrobenzene is economical and simple, but the raw materials are not easy to obtain, and the industrial condition is not provided. The research is mainly focused on noble metal Ru and Ni-based catalysts.
3. The hydrogenation amination method of cyclohexanone is divided into two steps, firstly generates imine, and then reacts with hydrogen to generate cyclohexane. The cyclohexanone raw material is easy to obtain, but the homogeneous catalyst system in the process has the problems of difficult catalyst recovery, harsh reaction conditions (4.0-4.5 MPa) and the like; for heterogeneous catalysts, ru, co, cu, ni and other catalysts have been studied, and the stability of the catalysts is a problem, so that the production cost is relatively high, and the catalysts are rarely adopted in industrial devices.
4. The raw materials of the phenol reductive amination method are easy to obtain, the reaction time of the method is long, the catalytic effect is not ideal, and various byproducts are easy to generate.
5. The cyclohexene direct amination method has the advantages of rich raw material sources, short flow, easy refining and separation, but has the defects of low conversion rate, low equipment utilization rate, high reaction condition requirement and the like. The process has harsh reaction conditions and low yield, and does not have industrialized conditions at present.
6. The chlorocyclohexane catalytic ammonolysis method has long process route, and the product contains hydrogen chloride, has high requirement on equipment and does not have industrial conditions.
7. There have been reported a cyclohexanol catalytic amination method at abroad, in which Cu-Zn or Ni-Co is used as a catalyst, cyclohexanol and ammonia are introduced under a pressurized state, the reaction temperature is 160-180 ℃, and cyclohexylamine and dicyclohexylamine are generated, wherein the ratio of the cyclohexylamine to the dicyclohexylamine is 3:1. the reaction conversion rate is low and is only 70-80%.
In recent years, the following technical scheme is also disclosed:
1) ACS Catalysis,2013,3 (1): 112-117 uses Ni/Al 2 O 3 The catalyst reacts for 28 hours at 160 ℃ without an external hydrogenation source, the conversion rate of cyclohexanol reaches 96 percent, the selectivity of cyclohexylamine is close to 100 percent, but toxic and high-boiling-point (144 ℃) o-xylene is adopted as a solvent, and the catalyst is not friendly to the environment.
2) Literature Catalysts,2016,6 (5): three catalysts of Raney Ni, ni/Al2O3 and Ni/C are studied in 1-10 for the amination reaction of cyclohexanol in water and low boiling point solvent to obtain cyclohexanol conversion of over 85% and cyclohexylamine selectivity of over 90%.
3) Journal of Catalysis,2019, 378:392-401 to prepare 1% (w) Pt-1% (w) Co/CeO2 catalyst for hydroamination of alcohols. The reaction is carried out for 8 hours at 180 ℃, the conversion rate of the cyclohexanol is more than 99%, and the yield of the cyclohexylamine is 73.1%.
4) ACS Sustainable Chemistry & Engineering,2022, 10 (40): 13367-13379, and reacting in a fixed bed reactor at 170 deg.C with cyclohexanol conversion rate over 98% and cyclohexylamine selectivity over 95%.
5) In the CN114805088A patent, co, ni, mg, cu, zn metal supported catalyst is adopted, cyclohexanol and cyclohexanone are used as raw materials to react in a fixed bed reactor, the conversion rate of the raw materials is more than 96%, the product proportion of cyclohexylamine and dicyclohexylamine is regulated through the regulation proportion of ammonia and hydrogen, and the selectivity of cyclohexylamine and dicyclohexylamine is more than 96%. But the cost for preparing the catalyst is high and the economic benefit is low.
Adjusting the proportion of the cyclohexane and the dicyclohexylamine in the product by controlling the proportion of the ammonia and the hydrogen; the molar ratio of ammonia to hydrogen is 1:2.5 to 4.0, the product is mainly dicyclohexylamine; the molar ratio of ammonia to hydrogen is 1.5-4.5: in the case of 1, the product is mainly cyclohexylamine.
0 to 50wt% of Co, 0 to 55wt% of Ni, 0 to 35wt% of Mg, 0 to 60wt% of Cu, 0 to 45wt% of Zn and a carrier, wherein the carrier comprises alumina, silica or a combination thereof. Preferably, the catalyst comprises: 0 to 40 weight percent of Co, 5 to 50 weight percent of Ni, 3 to 21 weight percent of Mg, 5 to 30 weight percent of Cu and 5 to 40 weight percent of Zn.
The above-mentioned technological processes for preparing cyclohexylamine by using cyclohexanol method are only studied in laboratory, and are not industrialized.
Disclosure of Invention
The invention aims to provide a production method for preparing cyclohexylamine by taking cyclohexanol as a raw material.
In order to solve the technical problems, the invention provides a catalyst (supported metal catalyst) for preparing cyclohexylamine, which consists of active components and a catalyst carrier: the active component consists of cobalt accounting for 0.1 to 20 percent, copper accounting for 0.1 to 2 percent, zinc accounting for 0.1 to 2 percent and barium accounting for 0.1 to 2 percent of the weight of the catalyst; the catalyst carrier is the rest.
As an improvement of the catalyst for preparing cyclohexylamine of the present invention: the active component consists of 15 to 19.5 percent of cobalt, 0.5 to 1.5 percent of copper, 0.5 to 1.5 percent of zinc and 1 to 1.5 percent of barium which account for the weight of the catalyst.
Further improvements as catalysts for the preparation of cyclohexylamine according to the invention: the active ingredients consist of 19.5% cobalt, 1.5% copper, 0.5% zinc and 1.0% barium by weight of the catalyst.
The invention also provides a preparation method of the catalyst for preparing cyclohexylamine, which comprises the following steps:
(1) uniformly mixing pseudo-boehmite, sesbania powder, deionized water and nitric acid, extruding and forming, and then drying and roasting to obtain a catalyst carrier;
the pseudo-boehmite is as follows: sesbania powder: deionized water: nitric acid = 100: (5±0.5): (150±20): (3.+ -. 0.3) weight ratio;
(2) preparing a mixed solution composed of nitrates of active ingredients, pouring the mixed solution into the catalyst carrier obtained in the step (1), and carrying out impregnation-roasting to obtain a supported catalyst;
description: the water absorption of the catalyst carrier can be measured in a conventional manner, and the prepared mixed solution of nitrate must be completely absorbed by the catalyst carrier; in addition, since the catalyst is calcined, a metal oxide is attached to the supported catalyst;
(3) and (3) reducing the supported catalyst obtained in the step (2) by hydrogen at a high temperature to obtain the supported metal catalyst.
Description: the metal oxide is reduced with hydrogen at high temperature to form the corresponding metal.
As an improvement to the process for preparing a catalyst for preparing cyclohexylamine of the present invention, in the step (1):
the drying is as follows: drying at 100-120 deg.c for 3+/-0.5 hr;
the roasting is as follows: heating to 280+/-30 ℃, roasting for 2+/-0.5 hours, and then heating to 400+/-50 ℃ and roasting for 10+/-1 hour.
As a further improvement of the process for preparing a catalyst for cyclohexylamine of the present invention, in the step (2): the number of times of impregnation-roasting is 2 (secondary impregnation and secondary roasting are adopted);
each impregnation-calcination is: the impregnation time is 2+/-0.5 hours, then the impregnated catalyst carrier is dried (dried to be free from dripping water), and then is placed in a baking oven at 110+/-20 ℃ for drying for 3+/-0.5 hours, and then is baked at 425+/-50 ℃ for 5+/-0.5 hours.
As a further improvement of the process for producing a catalyst for producing cyclohexylamine of the present invention, in the step (3), hydrogen gas at a high temperature is reduced to: hydrogen pressure 0.05MPa, temperature 450-480 ℃ and airspeed 1000h -1 Reducing for 10-12 hours.
The invention also provides a method for preparing cyclohexylamine by using cyclohexanol as a raw material by using the catalyst, which comprises the following steps:
1) Filling the prepared supported metal catalyst into a reactor, and activating with hydrogen to obtain an activated catalyst;
2) Pumping cyclohexanol, liquid ammonia and hydrogen into a vaporizer, vaporizing and then carrying out a reactor, and carrying out amination reaction under the action of an activated catalyst;
ammonia: hydrogen: the mol ratio of cyclohexanol is 2-10: 5:1, a step of; the reaction temperature is 160-200 ℃ (preferably 160-180 ℃); the reaction pressure is 0.8-1.5 Mpa (preferably 1.0-1.3 Mpa), the reaction space velocity (liquid volume space velocity) is 0.2-0.6 h -1 (preferably 0.25 to 0.6 h) -1 )；
Description: the feeding proportion is controlled by a cyclohexanol metering pump, a liquid ammonia metering pump and a hydrogen flowmeter; the system pressure is regulated by a back pressure valve on the blow-down line.
Description: the space velocity of the reaction is the amount of cyclohexanol per unit time over the unit catalyst.
3) And cooling the amination reaction product to form a liquid-phase product and a gas-phase product, wherein the liquid-phase product comprises cyclohexylamine.
The method comprises the following steps:
the top of the crude product tank is provided with a vent pipeline which is connected with the water absorption system, the vent pipeline is divided into two paths, one path is a vent valve, the other path is provided with a back pressure valve, and the back pressure valve is used for adjusting the reaction pressure in the reactor; the uncondensed gas after the gas-liquid cooling is discharged through an emptying valve, and the uncondensed gas contains hydrogen and the like;
the amination reaction product is cooled to form a liquid-phase product and a gas-phase product, the liquid-phase product is stored in the crude product tank, and the gas-phase product is discharged to a water absorption system through a vent pipeline at the top of the crude product tank.
As an improvement of the method for preparing cyclohexylamine by using cyclohexanol as a raw material of the invention: the gasification temperature in the vaporizer is 160-180 ℃.
The crude product of the invention adopts gas chromatography and internal standard analysis, the conversion rate of cyclohexanol can reach more than 98 percent, and the total selectivity of cyclohexylamine and dicyclohexylamine can reach more than 99.5 percent.
Conversion of cyclohexanol = (total cyclohexanol concentration-residual cyclohexanol concentration)/total cyclohexanol concentration 100%;
total selectivity of cyclohexylamine and dicyclohexylamine = (cyclohexylamine concentration + dicyclohexylamine concentration)/total cyclohexanol concentration-remaining cyclohexanol concentration ×100%.
The reaction equation:
△H＝-14.62KJ/mol
△H＝-50.34KJ/mol
the beneficial effects of the invention are mainly as follows:
1. the experiment adopts Co/Cu/Zn/Ba metal supported catalyst to prepare the cyclohexylamine, the reaction condition of the cyclohexylamine is mild, the preparation process of the catalyst is simple, and the catalyst has better catalytic performance.
2. The catalyst prepared by the invention has the advantages of high conversion rate, high catalyst activity and long service life, and is suitable for preparing cyclohexylamine from cyclohexanol.
And the selectivity of dicyclohexylamine is improved and the cost for preparing the catalyst is reduced by improving the performance of the catalyst.
3. Cyclohexylamine and dicyclohexylamine are produced by catalyst preparation and cyclohexanol process.
4. The auxiliary agent (barium) can lead the catalyst to be uniformly dispersed, improve the activity stability of the catalyst, further improve the catalytic performance, lead the catalyst to have interaction with the oxide, change the structural state and the distribution form of the oxide, and lead the catalyst to exist in a high dispersion form. The research results show that the auxiliary agents such as barium metal and the like also have a certain effect on improving the performance of the catalyst.
5. The catalyst prepared by the invention has the advantages of high conversion rate, high catalyst activity and long service life, and is suitable for preparing cyclohexylamine from cyclohexanol. And the selectivity of dicyclohexylamine is improved and the cost for preparing the catalyst is reduced by improving the performance of the catalyst.
The conversion rate of cyclohexanol is higher than 98%, and the selectivity of cyclohexylamine and dicyclohexylamine is higher than 99%.
The amination process of cyclohexanol has the characteristics of green and environment-friendly process, good atom economy and water as a theoretical byproduct; in particular, the catalyst does not depend on an external hydrogenation source, so that the development of a process route with high conversion rate, high selectivity and high stability has extremely high value and can be applied to industrial mass production.
Detailed Description
The invention will be further described with reference to the following specific examples, but the scope of the invention is not limited thereto:
catalyst example 1:
1) Uniformly mixing 100g of pseudo-boehmite and 5g of sesbania powder, then weighing 150g of deionized water, adding 3g of nitric acid into water, uniformly mixing, extruding and molding by using a strip extruder, drying at 110 ℃ for 3 hours after airing, heating to 280 ℃ in a muffle furnace, roasting for 2 hours, and then heating to 400 ℃ for 10 hours to obtain a catalyst carrier;
2) Setting the components of the catalyst, namely 19.5 percent of Co, 1.5 percent of Cu, 0.5 percent of Zn, 1 percent of Ba and the balance of catalyst carrier; the mass percent is as follows;
according to the proportion relation of the active components and according to the water absorption rate of the catalyst carrier, preparing a nitrate mixed solution consisting of cobalt nitrate, copper nitrate, zinc nitrate, barium nitrate and water; the amount of water used must ensure that the nitrate mixed solution is fully absorbed by the catalyst support.
Pouring the nitrate mixed solution into the catalyst carrier obtained in the step 1) for impregnation, and adopting secondary impregnation and secondary roasting, wherein each impregnation-roasting is as follows: soaking for 2 hours, then airing the soaked catalyst (airing until no water drops), drying in a baking oven at 110 ℃ for 3 hours, roasting at 425 ℃ for 5 hours, and repeating the soaking-roasting to obtain the supported catalyst cat.1.
Due to the calcination, a metal oxide adheres to the supported catalyst.
3) Filling the supported catalyst obtained in the step 2) into a reactor with an inner diameter of 5.6cm and a height of 12cm,the amount of the supported metal catalyst was about 250ml, and hydrogen reduction was performed: the reduction condition is hydrogen pressure 0.05MPa, temperature 450 ℃ and airspeed 1000h -1 Reducing for 12 hours under the condition; to obtain the supported metal catalyst.
Description: the metal oxide is reduced with hydrogen at high temperature to form the corresponding metal.
Catalyst example 2-1: the active components of catalyst example 1 were "changed from" 19.5% cobalt, 1.5% copper, 0.5% zinc and 1% barium "to" 15% cobalt, 0.5% copper, 1.5% zinc and 1.5% barium ", the remainder being identical to catalyst example 1. The supported catalyst cat.2 was obtained.
Catalyst example 2-2: the active components of example 1 were "changed from" 19.5% cobalt, 1.5% copper, 0.5% zinc and 1% barium "to" 19.5% cobalt, 1% copper, 1% zinc and 1% barium ", the remainder being identical to catalyst example 1. The supported catalyst cat.3 was obtained.
The process for preparing cyclohexylamine by using cyclohexanol as a raw material comprises the following steps: the catalyst is filled in the reactor, the raw material cyclohexanol is metered and pressurized by a advection pump, then enters a vaporizer together with liquid ammonia from a metering pump of a double plunger pump and hydrogen from a steel cylinder, is heated to 160-180 ℃ and gasified, and then enters the reactor, and amination reaction is carried out on the catalyst bed. Therefore, the feeding proportion is controlled by a cyclohexanol metering pump, a liquid ammonia metering pump and a hydrogen flowmeter. The product obtained by the amination reaction is cooled to form a liquid-phase product and a gas-phase product, the liquid-phase product and the gas-phase product enter a crude product tank, an emptying pipeline is arranged at the top of the crude product tank and is connected with a water absorption system, an emptying valve and a back pressure valve are respectively arranged on the emptying pipeline, and the back pressure valve is used for adjusting the reaction pressure in the reactor. The uncondensed gas after the gas-liquid cooling is discharged through an emptying valve, and the uncondensed gas contains hydrogen and the like; another function of the blow-off valve is: and when the pressure is abnormal, the pressure is released by venting.
The crude product (liquid phase product) comprises cyclohexylamine, dicyclohexylamine, cyclohexanol, liquid ammonia, etc., and can be worked up as follows: distilling off a small amount of liquid ammonia through an ammonia tower, collecting a fraction at 130-134 ℃ through a rectifying tower to obtain a cyclohexylamine product, and collecting a fraction at 150-152 ℃ through a vacuum rectifying tower (-0.09 MPa) to obtain a dicyclohexylamine product, thereby obtaining the purified cyclohexylamine (with purity more than or equal to 99.5%) and dicyclohexylamine (with purity more than or equal to 99.5%).
The gas phase product is mainly composed of the following components: liquid ammonia, methane, hydrogen; thus, an alkaline solution is formed after entering the water absorption system, and the other water-insoluble materials are vented to the atmosphere.
See in particular the examples below.
Example 1:
the reactor was charged with 250ml of the supported metal catalyst cat.1 prepared in catalyst example 1, and the starting ammonia: hydrogen: cyclohexanol was used in a molar ratio of 8:5:1 are put into a vaporizer together, heated and gasified, and then put into a reactor for 0.25h at 160 ℃ under 1.3MPa -1 Amination occurs at space velocity.
And (3) enabling a liquid-phase product and a gas-phase product formed after the amination reaction product is condensed and cooled to enter a crude product tank, storing the liquid-phase product in the crude product tank, and discharging the gas-phase product to a water absorption system through a vent pipeline at the top of the crude product tank.
The liquid phase product is a crude product of cyclohexane, the cyclohexanol conversion rate is 98.3%, the cyclohexane selectivity is 99.59% and the dicyclohexylamine selectivity is 0.24% by gas chromatography and internal standard analysis.
Example 2-1: the "supported metal catalyst cat.1 prepared in the catalyst-filled example 1" of example 1 was changed to "supported metal catalyst cat.2 prepared in the catalyst-filled example 2-1", the amount was kept unchanged, still 250ml, and the rest was identical to example 1. The cyclohexanol conversion was 96.5% and the cyclohexylamine selectivity was 98.52%.
Example 2-2: the "supported metal catalyst cat.1 prepared in catalyst-loaded example 1" of example 1 was changed to "supported metal catalyst cat.3 prepared in catalyst-loaded example 2-2", the amount was kept unchanged, still 250ml, and the rest was identical to example 1. The cyclohexanol conversion was 97.6% and the cyclohexylamine selectivity was 94.81%.
Examples 3 to 6, "ammonia: hydrogen: the molar ratio of cyclohexanol, the reaction temperature, and the reaction pressure were changed as described in the following Table 1, and the remainder was the same as in example 1.
TABLE 1
Examples 7 to 8, the "reaction space velocity" was changed as described in Table 2 below, and the remainder was the same as in example 1.
TABLE 2
| Space velocity of reaction | Cyclohexanol conversion | Cyclohexylamine selectivity | |
| Example 1 | 0.25h -1 | 98.3％ | 99.59％ |
| Example 7 | 0.4h -1 | 98.1％ | 99.73％ |
| Example 8 | 0.6h -1 | 96.4％ | 99.67％ |
Comparative examples 1-1 to 1-4 the active ingredients in example 1 were modified as described in the following Table 3, and the remainder was identical to example 1.
The results obtained are compared with the present invention as shown in Table 3 below.
TABLE 3 Table 3
Example 9 continuous operation and use of catalyst
The reaction was continued as described in example 1 using the supported metal catalyst cat.1 after the reaction of example 1, the remainder being identical to example 1, the number of days of continuous operation and the corresponding results being given in Table 4 below.
TABLE 4 Table 4
Example 10:
the fixed bed reactor device is filled with catalyst cat.1.16 tons, liquid mass space velocity is 0.25h < -1 >, ammonia-hydrogen alcohol mole ratio is 5:5:1, reactor 170 ℃, synthesis pressure is 1.2MPa, cyclohexanol conversion is 98.15%, cyclohexylamine selectivity is 93.09%, dicyclohexylamine selectivity is 6.19%.
Finally, it should also be noted that the above list is merely a few specific embodiments of the present invention. Obviously, the invention is not limited to the above embodiments, but many variations are possible. All modifications directly derived or suggested to one skilled in the art from the present disclosure should be considered as being within the scope of the present invention.
Claims (9)
1. A catalyst for the preparation of cyclohexylamine, characterized by consisting of an active ingredient and a catalyst support:
the active component consists of cobalt accounting for 0.1 to 20 percent, copper accounting for 0.1 to 2 percent, zinc accounting for 0.1 to 2 percent and barium accounting for 0.1 to 2 percent of the weight of the catalyst; the catalyst carrier is the rest.
2. Catalyst for the preparation of cyclohexylamine according to claim 1, characterized in that: the active component consists of 15 to 19.5 percent of cobalt, 0.5 to 1.5 percent of copper, 0.5 to 1.5 percent of zinc and 1 to 1.5 percent of barium which account for the weight of the catalyst.
3. Catalyst for the preparation of cyclohexylamine according to claim 2, characterized in that: the active ingredients consist of 19.5% cobalt, 1.5% copper, 0.5% zinc and 1.0% barium by weight of the catalyst.
4. A process for preparing a catalyst for the preparation of cyclohexylamine as claimed in any one of claims 1 to 3, characterized by comprising the steps of:
(1) uniformly mixing pseudo-boehmite, sesbania powder, deionized water and nitric acid, extruding and forming, and then drying and roasting to obtain a catalyst carrier;
the pseudo-boehmite is as follows: sesbania powder: deionized water: nitric acid = 100: (5±0.5): (150±20): (3.+ -. 0.3) weight ratio;
(2) preparing a mixed solution composed of nitrates of active ingredients, pouring the mixed solution into the catalyst carrier obtained in the step (1), and carrying out impregnation-roasting to obtain a supported catalyst;
(3) and (3) reducing the supported catalyst obtained in the step (2) by hydrogen at a high temperature to obtain the supported metal catalyst.
5. Process for the preparation of a catalyst for the preparation of cyclohexylamine according to claim 4, characterized in that in step (1):
the drying is as follows: drying at 100-120 deg.c for 3+/-0.5 hr;
the roasting is as follows: heating to 280+/-30 ℃, roasting for 2+/-0.5 hours, and then heating to 400+/-50 ℃ and roasting for 10+/-1 hour.
6. The process for preparing a catalyst for cyclohexylamine according to claim 5, characterized in that in the step (2): the number of times of dipping-roasting is 2;
each impregnation-calcination is: the impregnation time is 2+/-0.5 hours, then the impregnated catalyst carrier is dried, and then is placed in a baking oven at 110+/-20 ℃ for drying for 3+/-0.5 hours, and is baked at 425+/-50 ℃ for 5+/-0.5 hours.
7. Process for the preparation of a catalyst for the preparation of cyclohexylamine according to claim 6, characterized in that in step (3):
hydrogen reduction at high temperature is: hydrogen pressure 0.05MPa, temperature 450-480 ℃ and airspeed 1000h -1 Reducing for 10-12 hours.
8. Process for the preparation of cyclohexylamine starting from cyclohexanol using a catalyst according to any of claims 1 to 7, characterized in that it comprises the following steps:
1) Filling the prepared supported metal catalyst into a reactor, and activating with hydrogen to obtain an activated catalyst;
2) Pumping cyclohexanol, liquid ammonia and hydrogen into a vaporizer, vaporizing and then carrying out a reactor, and carrying out amination reaction under the action of an activated catalyst;
ammonia: hydrogen: the mol ratio of cyclohexanol is 2-10: 5:1, a step of; the reaction temperature is 160-200 ℃; the reaction pressure is 0.8-1.5 Mpa, and the reaction space velocity is 0.2-0.6 h -1 ；
3) And cooling the amination reaction product to form a liquid-phase product and a gas-phase product, wherein the liquid-phase product comprises cyclohexylamine.
9. The process for preparing cyclohexylamine from cyclohexanol as claimed in claim 8, wherein: the gasification temperature in the vaporizer is 160-180 ℃.
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