CN117945922A - Method for co-producing hexamethylenediamine and cyclohexylimine - Google Patents
Method for co-producing hexamethylenediamine and cyclohexylimine Download PDFInfo
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- CN117945922A CN117945922A CN202211351246.4A CN202211351246A CN117945922A CN 117945922 A CN117945922 A CN 117945922A CN 202211351246 A CN202211351246 A CN 202211351246A CN 117945922 A CN117945922 A CN 117945922A
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- Prior art keywords
- cyclohexylimine
- tower
- reaction
- material containing
- ammonification
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- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 title claims abstract description 128
- NNGAQKAUYDTUQR-UHFFFAOYSA-N cyclohexanimine Chemical compound N=C1CCCCC1 NNGAQKAUYDTUQR-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000004176 ammonification Methods 0.000 claims abstract description 107
- 239000000463 material Substances 0.000 claims abstract description 104
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 87
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 43
- 239000000047 product Substances 0.000 claims abstract description 41
- 238000005915 ammonolysis reaction Methods 0.000 claims abstract description 40
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims abstract description 35
- NPEIGRBGMUJNFE-UHFFFAOYSA-N 1-aminohexan-1-ol Chemical compound CCCCCC(N)O NPEIGRBGMUJNFE-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 26
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000007098 aminolysis reaction Methods 0.000 claims abstract description 4
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000010992 reflux Methods 0.000 claims description 15
- 208000005156 Dehydration Diseases 0.000 claims description 13
- 230000018044 dehydration Effects 0.000 claims description 13
- 238000006297 dehydration reaction Methods 0.000 claims description 13
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 7
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 4
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000012847 fine chemical Substances 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 description 31
- 239000011148 porous material Substances 0.000 description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- -1 hexamethylenediamine imine Chemical class 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- OWIUPIRUAQMTTK-UHFFFAOYSA-M n-aminocarbamate Chemical compound NNC([O-])=O OWIUPIRUAQMTTK-UHFFFAOYSA-M 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 5
- 239000007809 chemical reaction catalyst Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229940053662 nickel sulfate Drugs 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- 241000219793 Trifolium Species 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 150000005837 radical ions Chemical class 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LUKZNWIVRBCLON-GXOBDPJESA-N Ciclesonide Chemical compound C1([C@H]2O[C@@]3([C@H](O2)C[C@@H]2[C@@]3(C[C@H](O)[C@@H]3[C@@]4(C)C=CC(=O)C=C4CC[C@H]32)C)C(=O)COC(=O)C(C)C)CCCCC1 LUKZNWIVRBCLON-GXOBDPJESA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229940063013 borate ion Drugs 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229960003728 ciclesonide Drugs 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- FTLHORLYDROOSU-UHFFFAOYSA-N indium(3+);trinitrate;pentahydrate Chemical compound O.O.O.O.O.[In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FTLHORLYDROOSU-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- YRKCZRMEPGLHRN-UHFFFAOYSA-K lanthanum(3+);triacetate;hydrate Chemical compound O.[La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O YRKCZRMEPGLHRN-UHFFFAOYSA-K 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229940006163 selenate ion Drugs 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001502 supplementing effect Effects 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
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of fine chemical industry, and discloses a method for co-producing hexamethylenediamine into cyclohexylimine, which comprises the following steps: (1) Under the condition of ammonification reaction, enabling hexanediol and ammonia to perform ammonification reaction to obtain an ammonification reaction product, and separating the ammonification reaction product to obtain a material containing cyclohexylimine, hexamethylenediamine, a material containing amino hexanol and a material containing carbon dodecyl diamine; returning at least part of the material containing amino hexanol to the ammonification reaction, returning part of the material containing cyclohexylimine to the ammonification reaction, extracting the rest material containing cyclohexylimine as a product, and controlling the weight ratio of the material containing cyclohexylimine extracted as the product to the material containing cyclohexylimine returned to the ammonification reaction to be 0.01-0.8; (2) Under the ammonolysis reaction condition, the aminolysis reaction of the laurylamine in the material containing the dodecylamine is carried out to obtain an ammonolysis product. The yield of hexamethylenediamine and cyclohexylimine can be flexibly adjusted under the condition of ensuring higher total yield of hexamethylenediamine and cyclohexylimine.
Description
Technical Field
The invention relates to the field of fine chemical industry, in particular to a method for co-producing hexamethylenediamine and cyclohexylimine.
Background
Hexamethylenediamine is an important chemical raw material, and the main application of hexamethylenediamine is to react with adipic acid to produce polyamide nylon 66, and can be produced by adiponitrile, caprolactam and the like, but almost all methods for producing hexamethylenediamine on a large scale are carried out by hydrogenation of adiponitrile. Global adiponitrile has long been limited by its technical barriers in a highly monopoly pattern. Prior to 2019, domestic adiponitrile requirements were only dependent on importation. In recent years, domestic hexamethylenediamine is produced by hydrogenation of imported adiponitrile raw materials. In order to break through the key technology of hexamethylenediamine production, the research and development of adiponitrile domestic technology is broken through, and a plurality of adiponitrile domestic production devices are arranged. However, the diaminocyclohexane impurity generated in the adiponitrile hydrogenation process is difficult to separate, and seriously affects the quality of nylon 66. At present, the demand of hexamethylenediamine in China is 60 ten thousand tons, and the market price is 2.0-3.5 ten thousand yuan/ton.
The cyclohexylimine is an important organic fine chemical, is widely used as an intermediate of medicines and pesticides, and can also be used in the fields of textile, rubber, fiber, resin, water treatment, metal corrosion prevention and the like. Because of the difficulty in selecting the catalyst for synthesis, only a few countries in the world can produce the catalyst. The production process of the cyclohexylimine mainly adopts a caprolactam hydrogenation process. The demand of the full-sphere cyclohexylimine in 2021 is 1.87 ten thousand tons, and the same proportion is increased by 5.1 percent. For a long time, the cyclohexylimine in China is always imported. At present, the annual capacity of the domestic ciclesonide is about 4000 tons/year, the market price is 4.0-4.5 ten thousand yuan/ton, the price is high, and the large-scale application of the cyclohexylimine in more fields is limited.
In order to explore a novel green synthesis process of organic amine, a process for preparing hexamethylenediamine by adopting hexanediol ammonification is proposed, but the method has the common problem that the conversion rate of the hexanediol and the selectivity of the hexamethylenediamine are not high. CN114433086a developed a catalyst for catalyzing hydro-ammonification of alcohols to synthesize organic amine, which, although used for hydro-ammonification of alcohols, has improved catalytic activity and selectivity, but still cannot meet the requirement of industrial production on hexamethylenediamine yield. In addition, the high-carbon organic amine is easily polymerized in the process of preparing the hexamethylenediamine by ammoniation of the hexanediol, and if the product is not recycled, the product can only be discharged as waste liquid, so that the overall yield of the target hexamethylenediamine is low.
Disclosure of Invention
The invention aims to solve the problems of low yield of hexamethylenediamine prepared by ammonification reaction and low import and yield dependence of hexamethylenediamine in the prior art, and provides a method for co-producing hexamethylenediamine and hexamethylenediamine.
In order to achieve the above object, the present invention provides a method for co-producing hexamethylenediamine with cyclohexylimine, comprising:
(1) Under the condition of ammonification reaction, enabling hexanediol and ammonia to perform ammonification reaction to obtain an ammonification reaction product, and separating the ammonification reaction product to obtain a material containing cyclohexylimine, hexamethylenediamine, a material containing amino hexanol and a material containing carbon dodecyl diamine; returning at least part of the material containing amino hexanol to the ammonification reaction, returning part of the material containing cyclohexylimine to the ammonification reaction, extracting the rest material containing cyclohexylimine as a product, and controlling the weight ratio of the material containing cyclohexylimine extracted as the product to the material containing cyclohexylimine returned to the ammonification reaction to be 0.01-0.8;
(2) Under the ammonolysis reaction condition, the aminolysis reaction of the laurylamine in the material containing the dodecylamine is carried out to obtain an ammonolysis product.
The method for co-producing the hexamethylenediamine and the cyclohexylimine has the following characteristics:
(1) The ammonia process disclosed by the invention can break through the current situation that adiponitrile raw materials and technology are monopoly abroad, so that the key raw materials of nylon 66 are homemade. The process flow has high intrinsic safety, does not relate to highly toxic nitrile chemicals, has simple technical route and is environment-friendly.
(2) The invention can fully utilize the enterprises of the prior hexanediol resources, provides a method for preparing hexamethylenediamine and co-producing hexamethylenediamine imine by the hydro-ammoniation of hexanediol, simultaneously obtains two products with high added value and optimistic market prospect, improves the flexibility of the hexanediol ammoniation device, and can carry out the production of the device according to the market demands and the price of hexamethylenediamine and hexamethylenediamine imine by the enterprises. Under the preferred condition, the obtained hexamethylenediamine product has stable yield, high purity, high yield and less impurities; the purity of the cyclohexylimine product obtained by co-production is high and the impurity is less.
(3) According to the invention, the weight ratio of the material containing the cyclohexylimine extracted as the product to the material containing the cyclohexylimine returned to the ammonification reaction is controlled, so that the yield of the hexamethylenediamine and the cyclohexylimine can be flexibly regulated under the condition of ensuring higher total yield of the hexamethylenediamine and the cyclohexylimine, the adaptability of enterprises to markets is improved, and the production direction can be timely regulated according to market demands. The method is simple, easy to adjust and high in adaptability. The method of the invention also reduces the discharge of waste liquid and improves the utilization rate of raw materials.
Drawings
FIG. 1 is a process flow diagram of example 1 of the present invention;
fig. 2 is a process flow diagram of embodiment 2 of the present invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present invention, the carbazamide means an amine compound having 12 carbon atoms.
The invention provides a method for co-producing hexamethylenediamine into cyclohexylimine, which comprises the following steps:
(1) Under the condition of ammonification reaction, enabling hexanediol and ammonia to perform ammonification reaction to obtain an ammonification reaction product, and separating the ammonification reaction product to obtain a material containing cyclohexylimine, hexamethylenediamine, a material containing amino hexanol and a material containing carbon dodecyl diamine; returning at least part of the material containing amino hexanol to the ammonification reaction, returning part of the material containing cyclohexylimine to the ammonification reaction, extracting the rest material containing cyclohexylimine as a product, and controlling the weight ratio of the material containing cyclohexylimine extracted as the product to the material containing cyclohexylimine returned to the ammonification reaction to be 0.01-0.8;
(2) Under the ammonolysis reaction condition, the aminolysis reaction of the laurylamine in the material containing the dodecylamine is carried out to obtain an ammonolysis product.
According to the invention, preferably, the weight ratio of the material comprising cyclohexylimine withdrawn as product to the material comprising cyclohexylimine returned to the ammoniation reaction is controlled to be in the range of 0.05 to 0.7.
According to the invention, the weight ratio of the material containing amino hexanol to fresh hexanediol in the return ammonification reaction is preferably controlled to be 0.03-13, preferably 0.05-10.
Since the amounts of cyclohexylimine and amino-hexanol produced in the ammonification reaction are small at the beginning of the reaction, the whole of the cyclohexylimine-containing stream and the amino-hexanol-containing stream is returned to the ammonification reaction in the initial stage of the reaction. In the stable operation stage of the reaction, the amounts of the cyclohexylimine and the amino-hexanol generated in the ammonification reaction are large, all the amino-hexanol generated at the moment returns to the ammonification reaction, part of the cyclohexylimine returns to the ammonification reaction, and the rest of the cyclohexylimine is extracted as a product. The mass ratios of the amino-hexanol-containing stream to fresh hexanediol, and of the material comprising cyclohexylimine withdrawn as product to the material comprising cyclohexylimine returned to the ammoniation reaction given in the examples are all mass ratios during the steady operation of the reaction.
In a preferred embodiment of the invention, the mass ratio of the material comprising amino hexanol to fresh hexanediol is controlled and the weight ratio of the material comprising cyclohexane imine withdrawn as product to the material comprising cyclohexane imine returned to the ammonification reaction is controlled such that the total yield of cyclohexane imine and hexamethylenediamine is higher, compared to the material comprising amino hexanol alone or the material comprising cyclohexane imine alone being returned to the ammonification reaction.
According to the present invention, preferably, the ammonification reaction is carried out in the presence of hydrogen: ammonia: the mole ratio of the hexanediol is 0.1-10:17-60:1, preferably 0.2-5:21-50:1, the temperature of the ammonification reaction is 120-230 ℃, preferably 135-215 ℃; the pressure of the ammonification reaction is 6.5-16MPaG, preferably 8-16MPaG, and the liquid phase volume space velocity of the fresh hexanediol is 0.07-7h -1, preferably 0.1-3.9h -1.
In the present invention, the catalyst used for the ammonification reaction may be a catalyst for the ammonification reaction commonly used in the art, for example, CN114433086a. Preferably, the catalyst comprises a support and an active component and optionally an auxiliary agent supported on the support, the support comprising a doping element, alumina and optionally other supports, wherein the other supports are selected from at least one of silica, molecular sieves and diatomaceous earth; pore volume of the carrier with the pore diameter smaller than 7.5nm accounts for less than 20 percent of the pore volume of the carrier, pore volume of the carrier with the pore diameter smaller than 9nm accounts for less than 40 percent of the pore volume of the carrier, and pore volume of the carrier with the pore diameter larger than 27nm accounts for less than 5 percent of the pore volume of the carrier; the ammonia adsorption amount of the carrier is 0.3-0.6mmol/g; the L acid of the carrier accounts for more than 90% of the sum of the L acid and the B acid; the active component is cobalt and/or nickel.
According to the ammonification catalyst of the present invention, preferably, the support is selected from alumina doped with at least one of silica, molecular sieve and diatomaceous earth, and alumina undoped. The content of the alumina carrier in the carrier is 65% by weight or more, preferably 75% by weight or more of the total amount of the alumina carrier and other carriers.
According to the ammonification reaction catalyst of the present invention, preferably, the carrier may further include a doping element in an amount of 0.05 to 3 wt%, more preferably 0.08 to 2wt%, and still more preferably 0.1 to 1.5 wt% based on the total weight of the components other than the doping element in the carrier. The components other than the doping elements mainly refer to the alumina in the support and optionally other supports.
According to the ammonification reaction catalyst of the present invention, preferably, the doping element in the carrier is derived from acid radical ions excluding chloride ions. Since the incorporated hetero elements are introduced during the preparation of the carrier, the incorporated hetero elements are mainly present in the bulk phase of the carrier.
According to the ammonification reaction catalyst of the present invention, preferably, the acid radical ion may be at least one selected from nonmetallic acid radical ions, and further preferably at least one selected from borate ion, fluoride ion, phosphate ion, sulfate ion and selenate ion. The doping element is preferably at least one selected from the group consisting of boron, fluorine, phosphorus, sulfur and selenium.
According to the ammonification reaction catalyst of the present invention, preferably, the pore volume of the carrier having a pore diameter of less than 7.5nm is 5to 17%, more preferably 5to 10%, the pore volume of the carrier having a pore diameter of 7.5nm or more and less than 9nm is 5to 17%, the pore volume of the carrier having a pore diameter of 9nm or more and less than 27nm is 61 to 89.5%, and the pore volume of the carrier having a pore diameter of more than 27nm is 0.5 to 5%, more preferably 0.5 to 3%. The inventors of the present invention found that the catalyst of which the pore structure satisfies this preferred embodiment has more excellent catalytic performance.
According to the ammonification reaction catalyst of the present invention, preferably, the ammonia adsorption amount of the carrier is preferably 0.3 to 0.5mmol/g.
According to the ammonification catalyst of the present invention, preferably, the L acid of the carrier accounts for 92-100%, preferably 96-100%, of the sum of the L acid and the B acid. The L-acid ratio was measured by pyridine probe adsorption spectroscopy.
According to the ammonification catalyst of the present invention, preferably, the specific surface area of the carrier is 105-220m 2/g, and the pore volume of the carrier is 0.4-1.1ml/g.
The ammonification catalyst according to the present invention may preferably contain the active component in an amount of 5 to 42g, preferably 10 to 35g, per 100g of the carrier based on the components other than the doping element. According to the invention, the catalyst may further comprise an auxiliary agent in order to better exert the performance of the catalyst of the invention, to adjust the reaction product ratio, and to reduce unwanted side reactions. The auxiliary agent may be selected from at least one of group VIB, group VIIB, group IB, group IIB and the lanthanide series, preferably at least one of Cr, mo, W, mn, re, cu, ag, au, zn, la and Ce.
The ammonification catalyst according to the present invention preferably contains the auxiliary in an amount of 0 to 10g, preferably 0.5 to 6g, per 100 g of the carrier based on the components other than the doping element.
In the invention, the form of the ammonification reactor adopted in the ammonification reaction and the ammonification reaction is not limited, and all reactors which can ensure the stable operation of the reaction, such as a fixed bed reactor, a high-pressure reaction kettle, a fluidized bed reactor, a trickle bed reactor and the like, can be used.
According to the invention, the ammonolysis reaction is preferably carried out in the presence of hydrogen and ammonia, hydrogen: ammonia: the molar ratio of the materials containing the carbon dodecyl amine calculated by the bis (hexamethylenetetramine) is 0.1-17:17-100:1, preferably 0.12-15:20-90: the ammonolysis reaction temperature is 140-280 ℃, preferably 155-275 ℃, the ammonolysis reaction pressure is 10-22MPaG, preferably 11-20MPaG, and the liquid phase volume space velocity of the carbonaceous dodecyl amine material is 0.04-6h -1, preferably 0.05-2h -1.
In the invention, the ammonolysis catalyst can be prepared by the following method:
(1) Preparing a carrier: the method comprises the steps of (1) contacting a mixture of pseudo-boehmite, silica sol and calcium nitrate with an aqueous solution containing nitric acid and phosphoric acid, and then kneading, drying and roasting sequentially;
(2) Immersing the carrier in the aqueous solution containing nickel sulfate, lanthanum acetate and indium nitrate, drying at 100-140 deg.C for 2-6h, and calcining at 350-450 deg.C for 2-6h.
According to the method for preparing an ammonolysis catalyst of the present invention, preferably, in the step (1), the silica sol is used in an amount of 0.6 to 0.8g, and the calcium nitrate is used in an amount of 0.1 to 0.4g, and the aqueous solution containing nitric acid and phosphoric acid is used in an amount of 0.2 to 0.5g, per gram of pseudo-boehmite.
According to the method for producing an ammonolysis catalyst of the present invention, preferably, in the step (1), the content of nitric acid in the aqueous solution containing nitric acid and phosphoric acid is 10 to 25% by weight, and the content of phosphoric acid is 5 to 15% by weight.
According to the preparation method of the ammonolysis catalyst of the invention, preferably, in the step (1), the drying temperature is 100-140 ℃ and the drying time is 1-6h.
According to the preparation method of the ammonolysis catalyst of the present invention, preferably, in the step (2), the nickel sulfate is used in an amount of 0.6 to 0.85g, the lanthanum acetate is used in an amount of 0.06 to 0.08g, and the indium nitrate is used in an amount of 0.055 to 0.065g per gram of the carrier.
According to the method for producing an ammonolysis catalyst of the present invention, preferably, in the step (2), the concentration of nickel sulfate in the aqueous solution containing nickel sulfate, lanthanum acetate and indium nitrate is 20 to 25% by weight, the concentration of lanthanum acetate is 1.5 to 2.5% by weight, and the concentration of indium nitrate is 1.5 to 2.5% by weight. The impregnation method is preferably an isovolumetric impregnation method, and the impregnation may be performed in multiple times.
According to the present invention, preferably, the ammoniation reaction product is isolated in such a way that: sending the ammoniation reaction product into a light component removal tower to separate the cyclohexylimine and the water, and obtaining a material containing the cyclohexylimine and the water at the top of the light component removal tower; feeding tower kettle materials of the light component removal tower into a rectifying tower to separate hexamethylenediamine, and obtaining hexamethylenediamine products at the top of the rectifying tower; and (3) feeding the tower kettle material of the rectifying tower into a heavy-removal tower to separate the amino-hexanol, obtaining the material containing the amino-hexanol at the tower top of the heavy-removal tower, and obtaining the material containing the carbon-dodecamine at the tower kettle. Wherein, the material containing amino hexanol also comprises hexanediol.
According to the present invention, preferably, the operating conditions of the light ends column include: the tower bottom temperature is 110-350 ℃, preferably 150-300 ℃, the tower top temperature is 30-70 ℃, preferably 40-60 ℃, the reflux ratio is 0.1-10, preferably 1-8, the tower top operation pressure is-0.1 MPaG to 1MPaG, preferably-0.09 MPaG to 0.6MPaG, and the tower plate number is 10-60, preferably 15-45.
According to the present invention, preferably, the operating conditions of the rectification column include: the tower bottom temperature is 110-350 ℃, preferably 120-300 ℃, the tower top temperature is 100-160 ℃, preferably 110-150 ℃, the reflux ratio is 0.5-15, preferably 1-12, the tower top operation pressure is-0.1 MPaG to 1MPaG, preferably-0.09 MPaG to 0.6MPaG, and the tower plate number is 20-60 blocks, preferably 25-50 blocks.
According to the present invention, preferably, the operating conditions of the de-weight column include: the tower bottom temperature is 120-350 ℃, preferably 130-300 ℃, the tower top temperature is 130-200 ℃, preferably 140-180 ℃, the reflux ratio is 0.5-15, preferably 1-12, the tower top operation pressure is-0.1 MPaG to 0.5MPaG, preferably-0.09 MPaG to 0.4MPaG, and the tower plate number is 20-100 blocks, preferably 30-80 blocks.
According to the invention, the process preferably further comprises subjecting the material comprising cyclohexylimine and water to a dehydration treatment to obtain a material comprising cyclohexylimine, the dehydration treatment being under conditions such that the cyclohexylimine content of the material comprising cyclohexylimine is higher than 95% by weight.
According to the invention, the means of dehydration may be conventional in the art, but in order to further reduce the water content of the cyclohexylimine-containing stream, it is preferred that the dehydration is performed using a dehydration column, the operating conditions of which include: the weight ratio of entrainer to cyclohexylimine-containing stream is from 9 to 105:1, the temperature of a tower kettle is 60-230 ℃, the temperature of a tower top is 30-60 ℃, the reflux ratio is 0.5-16, the operating pressure of the tower top is-0.08 MPaG to 2.5MPaG, and the number of tower plates is 20-70; the entrainer may be at least one of cyclohexane, n-hexane, trimethylpentane, p-methyl cumene, dioxane, phenol, cresol, butyl ether, amyl ether and isoamyl ether.
According to the invention, preferably, the method further comprises recovering hydrogen and ammonia in the ammonification reaction product, and then sequentially feeding the hydrogen and ammonia to a light component removal tower, a rectifying tower and a heavy component removal tower for separation to obtain a material containing the cyclohexylimine, the hexamethylenediamine, the material containing the amino hexanol and the material containing the carbon dodecamine. More preferably, the way to recover hydrogen and ammonia in the ammonification reaction product comprises removing hydrogen and ammonia by flash evaporation and recondensing, returning hydrogen to the ammonification reactor in a gas phase form through a compressor, and pumping liquid ammonia back to the ammonification reactor.
In the present invention, it is understood that since part of ammonia and hydrogen are consumed in the ammonification reaction or part of ammonia and hydrogen are released as purge gas at the time of recovery, it is necessary to supplement fresh hexanediol in the course of the ammonification reaction while supplementing a proper amount of fresh ammonia and hydrogen.
The present invention will be described in detail by examples. In the following examples of the present invention,
The composition of the product was analyzed by gas chromatography.
Yield of hexamethylenediamine = molar amount of hexamethylenediamine product/(molar amount of fresh hexanediol x 100%).
Yield of cyclohexylimine = molar amount of cyclohexylimine product/(molar amount of fresh hexanediol x 100%).
Preparation example 1
Preparation of ammonolysis catalysts by a multi-step impregnation process:
(1) Pseudo-boehmite (specific surface area 310m 2/g, pore volume 1.19ml/g, produced by the aluminum sulfate method), 94.2g, silica sol (JN-40) 72.5g and calcium nitrate tetrahydrate 25.26g were weighed. Placing pseudoboehmite into a kneader, adding weighed silica sol and calcium nitrate tetrahydrate into 24.77g of water to prepare a solution, adding the solution into the kneader and fully stirring the solution with the pseudoboehmite, adding an aqueous solution prepared from 16.51g of water, 4.71g of nitric acid and 2.83g of phosphoric acid, fully stirring the solution, kneading and extruding the solution into clover, drying the clover at 120 ℃ for 4 hours, roasting the clover at 900 ℃ in a muffle furnace for 6 hours, and cooling the mixture to prepare the carrier.
(2) 100.77G of nickel sulfate hexahydrate (technical grade, purity 98%), 5.69g of lanthanum acetate monohydrate and 5.96g of indium nitrate pentahydrate were added to 134.78mL of water to prepare an aqueous solution, and the solution was loaded on 73.25g of the carrier obtained in the step (1) by an isovolumetric impregnation method in two times, and after each impregnation, it was dried at 120 ℃ for 4 hours, and after the two times of impregnation, it was baked at 390 ℃ for 4 hours.
Example 1
In this example, hexamethylenediamine and cyclohexylimine were produced by the process shown in FIG. 1
(1) Ammonification is carried out under the action of an ammonification catalyst and under the hydrogen condition
The ammonification catalyst was prepared according to the method of example 3 in CN114433086a, and was activated with hydrogen at 220 ℃ for 2 hours before use. The raw materials of hexanediol, ammonia and hydrogen are sent into an ammonification reactor filled with an ammonification catalyst to carry out ammonification reaction on the hexanediol and the ammonia, wherein the ammonification reaction temperature is 160 ℃, the ammonification reaction pressure is 12.2MPa, and the liquid volume space velocity of fresh hexanediol is 0.5h -1. The molar ratio of hydrogen, ammonia and hexanediol in the material at the feed inlet of the ammonification reactor is controlled to be 2:30:1.
(2) Recovery of hydrogen and ammonia from ammoniated reaction products
Sending an ammonification reaction product discharged from an ammonification reactor into a hydrogen-ammonia recovery system, removing hydrogen and ammonia by adopting a flash evaporation and recondensing mode, returning the hydrogen to the ammonification reactor through a compressor, pumping liquid ammonia back to the ammonification reactor, and recycling hydrogen mainly comprises: 39.36mol% of ammonia and 60.64mol% of hydrogen; the circulating ammonia mainly comprises the following components: 97.22mol% of ammonia, 1.41mol% of water, 1.28mol% of cyclohexylimine and 0.05mol% of hexamethylenediamine.
(3) Separation of remaining ammoniated reaction products
The reaction product after ammonia and hydrogen are removed enters a rectification separation unit, the rectification separation unit comprises a light component removal tower, a rectification tower and a heavy component removal tower which are sequentially connected, the light component removal tower removes the cyclohexylimine and water, the rectification tower removes the hexamethylenediamine, and the heavy component removal tower removes the carbon dodecamine to obtain the amino hexanol and the hexanediol. The operating conditions of the light ends column include: the column bottom temperature was 265 ℃, the column top temperature was 40 ℃, the reflux ratio was 6, the column top operating pressure was 0.2MPaG, and the number of trays was 50. And (3) extracting a material containing cyclohexylimine and water from the top of the light component removing tower. The operating conditions of the rectification column include: the column bottom temperature was 285 ℃, the column top temperature was 120 ℃, the reflux ratio was 5, the column top operating pressure was 0.2MPaG, and the number of trays was 50. The main content of hexamethylenediamine product extracted from the top of the rectifying tower is 99.8wt%. The operating conditions of the heavy ends removal column include: the temperature of the tower bottom is 300 ℃, the temperature of the tower top is 150 ℃, the reflux ratio is 4, the operating pressure of the tower top is 0.1MPaG, and the number of tower plates is 60. And (3) extracting a material containing the carbon dodecyl amine from the tower bottom of the de-weight tower, and conveying the tower bottom material of the de-weight tower to an ammonolysis unit. The material containing amino hexanol extracted from the top of the de-weight tower is returned to the ammonification reactor, and the weight ratio of the material containing amino hexanol returned to the ammonification reactor to fresh hexanediol is controlled to be 0.9.
(4) Dewatering of materials containing cyclohexylimine and water
The material containing the cyclohexylimine and water, and the entrainer isopropyl ether were sent to a dehydration column for dehydration treatment to obtain a material containing the cyclohexylimine (the cyclohexylimine content is 97.49 wt%). Wherein the weight ratio of entrainer to cyclohexylimine-containing stream is 70: the operation conditions of the dehydration tower comprise: the temperature of the tower bottom is 160 ℃, the temperature of the tower top is 40 ℃, the reflux ratio is 5, the operating pressure of the tower top is 0.1MPaG, and the number of tower plates is 60. Part of the material containing the cyclohexylimine is returned to the ammonification reactor, the rest of the material containing the cyclohexylimine is taken out as a product, and the weight ratio of the material containing the cyclohexylimine which is taken out as the product to the material containing the cyclohexylimine which is returned to the ammonification reaction is controlled to be 0.06.
(5) Heavy component ammonolysis reaction
And (3) conveying the tower bottom stream of the heavy removal tower in the step (3) to an ammonolysis reactor filled with an ammonolysis catalyst, adding hydrogen and liquid ammonia, and decomposing the carbazate in the tower bottom stream under the condition of hydrogen to generate hexamethylenediamine and cyclohexylimine, wherein part of carbazate can generate heavier carbazate heavy components. Wherein, hydrogen: ammonia: the molar ratio of the carbonaceous dodecyl amine based on the bis (hexamethylenetetramine) material was 2:42:1, the ammonolysis reaction temperature is 170 ℃, the ammonolysis reaction pressure is 18MPaG, and the liquid phase volume space velocity of the carbonaceous dodecyl amine is 0.5h -1. Separating the ammonolysis reaction product to obtain an ammonolysis recovery product and a heavy component (carbon octadecylamine), returning the ammonolysis recovery product to the step (2), and discharging the heavy component as waste liquid.
The purity of hexamethylenediamine in this example was 99.8% by weight, and the purity of the co-produced cyclohexylimine was 97.49% by weight. The total molar yield of hexamethylenediamine and cyclohexylimine was 97.52%, with the co-production of 2.4kg of cyclohexylimine per 100kg of hexamethylenediamine.
Example 2
In this example, hexamethylenediamine and cyclohexylimine were produced by the process shown in FIG. 2
The procedure of example 1 was followed, except that the ammonification catalyst was a catalyst prepared in accordance with the procedure of example 5 in CN114433086 a; and controlling the weight ratio of the material containing the amino hexanol to the fresh hexanediol which is returned to the ammonification reactor to be 0.9; controlling the weight ratio of the material containing the cyclohexylimine extracted as the product to the material containing the cyclohexylimine which is returned to the ammonification reaction to be 0.06; in the step (5), ammonia and hydrogen obtained by gas-liquid separation of an ammonolysis reaction product are sent to the step (2), a liquid phase remained by gas-liquid separation is rectified to obtain a mixed product containing hexamethylenediamine and cyclohexylimine, the mixed product is sent to the step (3), and the remaining heavy component (carbon octadecylamine) is discharged as waste liquid.
The hexamethylenediamine purity of this example was 99.8% by weight, and the purity of the co-produced cyclohexylimine was 97.37% by weight. The total yield of hexamethylenediamine and cyclohexylimine was 98.43%. 3kg of cyclohexylimine are co-produced per 100kg of hexamethylenediamine.
Example 3
In this example, hexamethylenediamine and cyclohexylimine were produced by the process shown in FIG. 1
(1) Ammonification is carried out under the action of an ammonification catalyst and under the hydrogen condition
The ammonification catalyst was prepared according to the method of example 3 in CN114433086a, and was activated with hydrogen at 200 ℃ for 2 hours before use. The raw materials of hexanediol, ammonia and hydrogen are sent into an ammonification reactor filled with an ammonification catalyst to carry out ammonification reaction on the hexanediol and the ammonia, wherein the ammonification reaction temperature is 165 ℃, the ammonification reaction pressure is 13MPa, and the liquid volume space velocity of the fresh hexanediol is 1.5h -1. The molar ratio of hydrogen, ammonia and hexanediol in the material at the feed inlet of the ammonification reactor is controlled to be 3:30:1.
(2) Recovery of hydrogen and ammonia from ammoniated reaction products
The ammonification reaction product discharged from the ammonification reactor enters a hydrogen-ammonia recovery system, hydrogen and ammonia are removed by adopting a flash evaporation and recondensing mode, the hydrogen is returned to the ammonification reactor in a gas phase form through a compressor, liquid ammonia is pumped back to the ammonification reactor, and the circulating hydrogen mainly comprises: 39.28mol% of ammonia and 60.72mol% of hydrogen; the circulating ammonia mainly comprises the following components: 97.64mol% of ammonia, 1.14mol% of water, 1.15mol% of cyclohexylimine and 0.04mol% of hexamethylenediamine.
(3) Separation of remaining ammoniated reaction products
The reaction product after ammonia and hydrogen are removed enters a rectification separation unit, the rectification separation unit comprises a light component removal tower, a rectification tower and a heavy component removal tower which are sequentially connected, the light component removal tower removes the cyclohexylimine and water, the rectification tower removes the hexamethylenediamine, and the heavy component removal tower removes the carbon dodecamine to obtain the amino hexanol and the hexanediol. The operating conditions of the light ends column include: the column bottom temperature was 160 ℃, the column top temperature was 40 ℃, the reflux ratio was 6, the column top operating pressure was-0.09 MPaG, and the number of trays was 50. And (3) extracting a material containing cyclohexylimine and water from the top of the light component removing tower. The operating conditions of the rectification column include: the temperature of the tower bottom is 180 ℃, the temperature of the tower top is 120 ℃, the reflux ratio is 5, the operating pressure of the tower top is-0.09 MPaG, and the number of tower plates is 50. The main content of hexamethylenediamine product extracted from the top of the rectifying tower is 99.8wt%. The operating conditions of the heavy ends removal column include: the temperature of the tower bottom is 200 ℃, the temperature of the tower top is 150 ℃, the reflux ratio is 4, the operating pressure of the tower top is-0.09 MPaG, and the number of tower plates is 60. And (3) extracting a material containing the carbon dodecyl amine from the tower bottom of the de-weight tower, and conveying the tower bottom material of the de-weight tower to an ammonolysis unit. The top material of the de-weight tower is returned to the ammonification reactor, and the weight ratio of the material containing amino hexanol returned to the ammonification reactor to fresh hexanediol is controlled to be 0.8.
(4) Dewatering of materials containing cyclohexylimine and water
The material containing the cyclohexylimine and water, and the entrainer isopropyl ether are sent into a dehydration tower for dehydration treatment to obtain the material containing the cyclohexylimine (the cyclohexylimine content is 98.05 wt%). Wherein the weight ratio of entrainer to cyclohexylimine-containing stream is 80: the operation conditions of the dehydration tower comprise: the temperature of the tower bottom is 100 ℃, the temperature of the tower top is 50 ℃, the reflux ratio is 6, the operating pressure of the tower top is-0.08 MPaG, and the number of tower plates is 60. Part of the cyclohexylimine is returned to the ammonification reactor, the rest of the cyclohexylimine is extracted as a product, and the weight ratio of the material containing the cyclohexylimine extracted as the product to the material containing the cyclohexylimine which is returned to the ammonification reaction is controlled to be 0.67.
(5) Heavy component ammonolysis reaction
And (3) conveying the tower bottom stream of the heavy removal tower in the step (3) to an ammonolysis reactor filled with an ammonolysis catalyst, adding hydrogen and liquid ammonia, and decomposing the carbazate in the tower bottom stream under the condition of hydrogen to generate hexamethylenediamine and cyclohexylimine, wherein part of carbazate can generate heavier carbazate heavy components. Wherein, hydrogen: ammonia: the molar ratio of the carbonaceous dodecyl amine based on the bis (hexamethylenetetramine) material was 3:42:1, the ammonolysis reaction temperature is 175 ℃, the ammonolysis reaction pressure is 17MPaG, and the liquid phase volume space velocity of the carbonaceous dodecyl amine is 2.5h -1. . Separating the ammonolysis reaction product to obtain an ammonolysis recovery product and a heavy component (carbon octadecylamine), returning the ammonolysis recovery product to the step (2), and discharging the heavy component as waste liquid.
The hexamethylenediamine purity of this example was 99.8% by weight, and the purity of the co-produced cyclohexylimine was 98.05% by weight. The total yield of hexamethylenediamine and cyclohexylimine was 98.9%. 16.82kg of cyclohexylimine are co-produced per 100kg of hexamethylenediamine.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A method for co-producing hexamethylenediamine with cyclohexylimine, comprising the steps of:
(1) Under the condition of ammonification reaction, enabling hexanediol and ammonia to perform ammonification reaction to obtain an ammonification reaction product, and separating the ammonification reaction product to obtain a material containing cyclohexylimine, hexamethylenediamine, a material containing amino hexanol and a material containing carbon dodecyl diamine; returning at least part of the material containing amino hexanol to the ammonification reaction, returning part of the material containing cyclohexylimine to the ammonification reaction, extracting the rest material containing cyclohexylimine as a product, and controlling the weight ratio of the material containing cyclohexylimine extracted as the product to the material containing cyclohexylimine returned to the ammonification reaction to be 0.01-0.8;
(2) Under the ammonolysis reaction condition, the aminolysis reaction of the laurylamine in the material containing the dodecylamine is carried out to obtain an ammonolysis product.
2. Process according to claim 1, wherein the weight ratio of the cyclohexylimine-containing material withdrawn as product to the cyclohexylimine-containing material returned to the ammoniation reaction is controlled to be in the range of 0.05-0.7.
3. The process according to claim 1, wherein the weight ratio of the amino hexanol containing material to fresh hexanediol in the return ammonification reaction is controlled to be 0.03-13, preferably 0.05-10.
4. The process of claim 1, wherein the ammonification reaction is performed in the presence of hydrogen, hydrogen: ammonia: the mole ratio of the hexanediol is 0.1-10:17-60:1, preferably 0.2-5:21-50:1, a step of; the temperature of the ammonification reaction is 120-230 ℃, preferably 135-215 ℃; the pressure of the ammonification reaction is 6.5-16MPaG, preferably 8-16MPaG; the liquid phase volume space velocity of the fresh hexanediol is from 0.07 to 7h -1, preferably from 0.1 to 3.9h -1.
5. The method of claim 1, wherein the ammonolysis reaction is performed in the presence of hydrogen and ammonia, hydrogen: ammonia: the molar ratio of the materials containing the carbon dodecyl amine calculated by the bis (hexamethylenetetramine) is 0.1-17:17-100:1, preferably 0.12-15:20-90:1, a step of; the ammonolysis reaction temperature is 140-280 ℃, preferably 155-275 ℃; the pressure of the ammonolysis reaction is 10-22MPaG, preferably 11-20MPaG; the liquid phase volume space velocity of the carbonaceous dodecyl amine material is 0.04-6h -1, preferably 0.05-2h -1.
6. The method of any one of claims 1-5, wherein the ammonification reaction product is isolated by: sending the ammoniation reaction product into a light component removal tower to separate the cyclohexylimine and the water, and obtaining a material containing the cyclohexylimine and the water at the top of the light component removal tower; feeding tower kettle materials of the light component removal tower into a rectifying tower to separate hexamethylenediamine, and obtaining hexamethylenediamine products at the top of the rectifying tower; and (3) feeding the tower kettle material of the rectifying tower into a heavy-removal tower to separate the amino-hexanol, obtaining the material containing the amino-hexanol at the tower top of the heavy-removal tower, and obtaining the material containing the carbon-dodecamine at the tower kettle.
7. The method of claim 6, wherein the operating conditions of the light ends column comprise: the temperature of the tower bottom is 110-350 ℃, the temperature of the tower top is 30-70 ℃, the reflux ratio is 0.1-10, the operating pressure of the tower top is-0.1 MPaG to 1MPaG, and the number of tower plates is 10-60.
8. The method of claim 6, wherein the operating conditions of the rectification column comprise: the temperature of the tower bottom is 110-350 ℃, the temperature of the tower top is 100-160 ℃, the reflux ratio is 0.5-15, the operating pressure of the tower top is-0.1 MPaG to 1MPaG, and the number of tower plates is 20-60.
9. The method of claim 6, wherein the operating conditions of the de-duplication column comprise: the temperature of the tower bottom is 120-350 ℃, the temperature of the tower top is 130-200 ℃, the reflux ratio is 0.5-15, the operating pressure of the tower top is-0.1 MPaG to 0.5MPaG, and the number of tower plates is 20-100.
10. Process according to claim 6, wherein the process further comprises subjecting the material comprising cyclohexylimine and water to a dehydration treatment to obtain a material comprising cyclohexylimine, the dehydration treatment being under conditions such that the cyclohexylimine content of the material comprising cyclohexylimine is higher than 95wt%.
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