CN110511149A - A method of dimethylamine is directly produced by synthesis gas - Google Patents
A method of dimethylamine is directly produced by synthesis gas Download PDFInfo
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- CN110511149A CN110511149A CN201910536137.1A CN201910536137A CN110511149A CN 110511149 A CN110511149 A CN 110511149A CN 201910536137 A CN201910536137 A CN 201910536137A CN 110511149 A CN110511149 A CN 110511149A
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- Prior art keywords
- catalyst
- methanol
- dimethylamine
- molecular sieve
- synthesis gas
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- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 40
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 201
- 239000003054 catalyst Substances 0.000 claims abstract description 107
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims abstract description 71
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000002808 molecular sieve Substances 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000011258 core-shell material Substances 0.000 claims abstract description 9
- 238000010523 cascade reaction Methods 0.000 claims abstract description 4
- 210000004209 hair Anatomy 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 39
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 27
- 229910052710 silicon Inorganic materials 0.000 claims description 27
- 239000010703 silicon Substances 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 229910001868 water Inorganic materials 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000004570 mortar (masonry) Substances 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 239000006229 carbon black Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 229910001593 boehmite Inorganic materials 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 5
- 229910017119 AlPO Inorganic materials 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 159000000013 aluminium salts Chemical class 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 3
- 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 claims description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 238000002288 cocrystallisation Methods 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000012452 mother liquor Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 150000003751 zinc Chemical class 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000008878 coupling Effects 0.000 abstract description 4
- 238000010168 coupling process Methods 0.000 abstract description 4
- 238000005859 coupling reaction Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 17
- 238000002441 X-ray diffraction Methods 0.000 description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 15
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 12
- 238000006555 catalytic reaction Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000004176 ammonification Methods 0.000 description 8
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 6
- 239000005457 ice water Substances 0.000 description 6
- 239000008246 gaseous mixture Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 210000002268 wool Anatomy 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 150000003956 methylamines Chemical class 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910016523 CuKa Inorganic materials 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000010959 commercial synthesis reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
-
- 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
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J29/00—Catalysts comprising molecular sieves
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
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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
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- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a kind of methods that dimethylamine is directly produced by synthesis gas, it is characterized by: this method includes synthesising gas systeming carbinol reaction and two tandem reactions of methanol aminating reaction, wherein catalysts are made of catalyst for methanol and methylamine catalyst, this method carries out in continuous fixed bed hair reactor, reaction temperature is 200-400 DEG C, pressure is 0.1-5MPa, and feed gas volume ratio is H2/CO/NH3=1-3:1:1-3, catalyst for methanol and methylamine catalyst mass ratio are 1:0.5-5, and the present invention realizes that one-step method from syngas directly produces dimethylamine reaction by coupling catalyst for methanol and methylamine catalyst.Series-connected catalyst is formed by CuZnAl and core-shell structure compound molecular sieve by designing, has the advantages that synthesis is simple, catalyst is at low cost, equipment investment is low etc., realization significantly improves dimethylamine selectivity in product.
Description
Technical field
The invention belongs to the field of chemical synthesis, are related to sequential catalyst synthetic reaction technology, especially multi-functional composite catalyzing
Agent, specifically for a kind of method for directly producing dimethylamine by synthesis gas.
Background technique
Methylamine is important Organic Chemicals, is widely used in the industries such as medicine, pesticide, solvent, template, and purposes is wide
It is general.Industrially mostly use methanol in ammonia gas-phase catalysis synthesis of methylamines at present, but due to being controlled by thermodynamical equilibrium, a first
Amine/dimethylamine/trimethylamine equilibrium composition is 23/27/50 (mass ratio), and wherein the market demand of dimethylamine is maximum, is accounted for about
80% or more, it is the important source material for generating solvent dimethylformamide.
China's coal resource is abundant, and producing methanol as the synthesis gas in source using coal is an important energy development approach.It is early
Phase United States Patent (USP) US2821537, which reports mixed synthesis gas and ammonia, can directly produce methylamine (CO+H2+NH3→ CH3NH2+CH3-
NH-CH3+(CH3)3N), this route uses the direct synthesis of methylamines of one-stage process, and economic benefit and environment protection significance are very great.This road
Line includes following two steps: (1) synthesis gas synthesizing methanol, CO+H2→CH3OH, commercial synthesis catalyst for methanol CuZnAl are non-
It is often mature；(2) methanol vapor phase ammonification synthesis of methylamines, CH3OH+NH3→(CH3)1-3NH0-2+H2O, this step are dehydration, mesh
Preceding mainly molecular sieve catalyst.
Baiker etc. uses Cu/Al2O3Catalyst is in 0.6MPa, and 200-300 DEG C, CO/H2/NH3=1/1/3 reaction condition
Under, can direct synthesis of methylamines, wherein Cu be synthesis gas preparing methanol by hydrogenation catalyst, acid Al2O3It is catalyzed as catalysis methanol ammonification
Agent (Journal of the Chemical Society, Chemical Communications, 1995,1,73-74), but
Due to Al2O3The unordered property in duct causes trimethylamine proportion in product obviously higher to product without Studies On The Shape-selective Catalysis,
Dimethylamine is selectively lower.Mobil company utilizes the duct Studies On The Shape-selective Catalysis of molecular sieve within 1978, develops ZSM series point
Son sieve, increases substantially the selectivity of dimethylamine.
Dong chemical company, Japan in 1984 has been produced with being modified the work of MOR molecular sieve catalyst high selectivity dimethylamine
Industry, wherein dimethylamine is selectively up to 60%.But MOR is 12 member rings and 8 membered ring channel structures, the kinetic diameter of trimethylamine
For 0.39nm, in 12 member ring molecular sieve pore passages can free diffusing can inhibit trimethylamine therefore so reduce molecular sieve bore diameter
The disengaging in molecular sieve pore passage, and then realize shape selective catalysis.When the aperture of molecular sieve is straight less than or equal to front three amine molecule
When diameter, trimethylamine is not easily generated.Document (Chinese Journal of Catalysis, 2017,38,574-582；
Chemical Reviews, 2018,118,5265-5329) report the life that 8 member ring molecular sieve of aperture effectively inhibits trimethylamine
At wherein RHO molecular sieve has highest dimethylamine selectivity and minimum trimethylamine selectivity.
In conclusion either synthesising gas systeming carbinol reaction or methanol ammonification prepare methylamine reaction, the two reactions are equal
Industrialization.But it is sayed as above-mentioned, such as use synthesis gas and ammonia for raw material, coupling methanol-fueled CLC and methanol aminating reaction, directly
It delivers a child and produces dimethylamine, energy consumption can be effectively reduced, simplify reaction process, in industrial economy be and its advantageous technique.Therefore, to the greatest extent
Pipe is used for there are many catalyst of the reaction, but still needs to find a kind of effective catalyst, is met simultaneously:
(1) matching of two reaction process conditions of methanol-fueled CLC and methanol ammonification, such as temperature, pressure condition；
(2) the compounding mode of catalyst, such as physical mixed, two-phase method or catalyst with core-casing structure；
(3) the shape selective catalysis effect of molecular sieve controls molecular sieve pore passage structure, maximizes and realizes dimethylamine selectivity.
Summary of the invention
It is an object of the invention in place of overcome the deficiencies in the prior art, provide one kind directly to produce dimethylamine by synthesis gas
Method, this method realizes that synthesis gas is concatenated reaction selectivity synthesizing dimethylamine product in one section of reacting furnace, simplifies technique
Process, reduces equipment investment, and energy saving reduces cost.In addition, the present invention, which provides one kind, directly produces diformazan by synthesis gas
The method of the catalyst of amine, the composite molecular screen which is synthesized by solid-phase synthesis, to be urged with core-shell structure molecular sieve
Agent, high catalytic efficiency, while the catalyst preparation is simple to operation, low energy consumption, further reduced catalyst cost.
The present invention solves its technical problem and adopts the following technical solutions to achieve:
A method of dimethylamine directly being produced by synthesis gas, this method includes synthesising gas systeming carbinol reaction and methanol ammonification
Two tandem reactions are reacted, wherein catalysts are made of catalyst for methanol and methylamine catalyst, and this method is continuously being fixed
It is carried out in bed hair reactor, reaction temperature is 200-400 DEG C, pressure 0.1-5MPa, and feed gas volume ratio is H2/CO/NH3=
1-3:1:1-3, catalyst for methanol and methylamine catalyst mass ratio are 1:0.5-5, wherein synthesising gas systeming carbinol reaction is CO+2H2
→CH3OH, methanol aminating reaction are CH3OH+NH3→(CH3)1-3NH0-2+H2O。
Moreover, the catalyst for methanol be CuZnAl catalyst, weight percent composition CuO:30-60%,
ZnO:30-60%, Al2O3: 5-10%, the catalyst are prepared using coprecipitation.
Moreover, being shaped to beat piece, being sized to granularity for the catalyst is 20-80 mesh.
Moreover, the preparation method of the catalyst for methanol, comprising the following steps:
(1) by mantoquita, zinc salt and aluminium salt according to CuO:30-60%, ZnO:30-60%, Al2O3: 5-10% metal molar ratio
It is configured to mixing salt solution, copper salt solution and zinc solution are one in HCI solution, nitrate solution and acetate solution
Kind is several；
(2) mixing salt solution and precipitating reagent are reacted, and for the pH value of solution in 8-10, precipitation temperature is 40-80 DEG C, described
Precipitating reagent is Na2CO3、NaHCO3, NaOH, one or more of urea；
(3) after sediment is separated with mother liquor, sediment is cleaned using deionized water repeatedly, deionized water temperature is 40-60
DEG C, then in dry in air and roasting, drying temperature is 90-120 DEG C, drying time 12-24h, maturing temperature 300-
500 DEG C, calcining time 5-10h obtains catalyst for methanol.
Moreover, the methylamine catalyst is the composite molecular screen material with core-shell structure, center ZSM-5, ZSM-
One of 35 or two kind, shell SAPO-34, AlPO4One of -25 or two kind, shape existing for the composite molecular screen material
Formula includes at least one of physical mixed, cocrystallization structure.
Moreover, the methylamine catalyst is molecular sieve catalyst, prepared using solid-phase synthesis, structure is molecular sieve
The core-shell structure of molecular sieve is coated, wherein shell is that can choose SAPO-34, AlPO with 8 member ring topological structure molecular sieves4In -25
One kind or two kinds, core be with 10 member ring topological structure molecular sieves, one of ZSM-5, ZSM-35 or two kinds can be chosen.
Moreover, the preparation method of the methylamine catalyst, comprising the following steps:
(1) solid silicon source, silicon source, phosphorus source, template are added in agate mortar and grind 5-60min, be packed into water heating kettle,
In 100-250 DEG C of crystallization 16-240h, product is washed, dry, obtains molecular sieve core；
(2) molecular sieve core is nucleus in step (1), using second-crystallized method, molecule screen shell is grown on nucleus, in agate
Mixed molecular sieve core in mortar, template, grinds 5-60min at silicon source at room temperature, then the hydrothermal crystallizing at 100-250 DEG C
24-72h, product is washed, dry, and 300-600 DEG C of roasting 5-10h obtains methylamine catalyst.
Moreover, temperature dry in step (2) is 80-120 DEG C, drying time 6-24h.
Moreover, selected silicon source is white carbon black, SiO2One of gel, silicic acid, sodium metasilicate are a variety of, and selected silicon source is quasi-
One of boehmite, aluminum nitrate, sodium aluminate, aluminum sulfate and kaolin are a variety of, and selected phosphorus source is phosphoric acid, ammonium dihydrogen phosphate
One of or two kinds, the silicon source, silicon source, phosphorus source, the molar ratio of template be 1-50:0.1-1:0-1:0.1-1.
Moreover, the silicon source, the molar ratio of template are 1-50:0.1-1, the molecule screen shell is with silicon source mass ratio
10-100:1。
The advantages and positive effects of the present invention are:
1, the present invention is reacted by the reaction of coupling CO preparing methanol by hydrogenation and methanol ammonification methylamine, in a fixed bed reaction
Filling catalyst for methanol and methylamine catalyst in device, realize two reaction process conditions of methanol-fueled CLC and methanol ammonification matching and
Synthesis gas directly produces dimethylamine reaction.
2, the present invention has the composite molecular sieve catalyst of core-shell structure using solid-phase synthesis preparation, by controlling molecule
Cellular structure is sieved, using the shape selective catalysis effect of molecular sieve, realizes methanol ammonification synthesizing dimethylamine with high selectivity.
3, the present invention realizes that one-step method from syngas directly produces dimethylamine by coupling catalyst for methanol and methylamine catalyst
Reaction.Series-connected catalyst form by CuZnAl and core-shell structure compound molecular sieve by designing, have synthesis simply, catalyst at
The advantages such as this is low, equipment investment is low, realization significantly improve dimethylamine selectivity in product.
Detailed description of the invention
Fig. 1 one-step method from syngas produces dimethylamine artwork；
Fig. 2 is the XRD spectra of CuZnAl catalyst for methanol；
Fig. 3 is the XRD spectra of ZSM-5 molecular sieve；
Fig. 4 is the XRD spectra of ZSM-35 molecular sieve；
Fig. 5 is the XRD spectra of AlPO4-25 molecular sieve；
Fig. 6 is the XRD spectra of SAPO-34 molecular sieve；
Fig. 7 is the XRD spectra of HZSM-35@SAPO-34 molecular sieve；
Fig. 8 is the XRD spectra of HZSM-5@SAPO-34 molecular sieve；
Fig. 9 is the XRD spectra of HZSM-5@AlPO4-25 molecular sieve.
Specific embodiment
The invention will be further described with reference to the accompanying drawing and by specific embodiment, and following embodiment is descriptive
, it is not restrictive, this does not limit the scope of protection of the present invention.
A method of dimethylamine directly being produced by synthesis gas, as shown in Figure 1, this method includes synthesising gas systeming carbinol reaction
With two tandem reactions of methanol aminating reaction, wherein catalysts are made of catalyst for methanol and methylamine catalyst, this method
It is carried out in continuous fixed bed hair reactor, reaction temperature is 200-400 DEG C, pressure 0.1-5MPa, and feed gas volume ratio is
H2/CO/NH3=1-3:1:1-3, catalyst for methanol and methylamine catalyst mass ratio are 1:0.5-5, wherein synthesising gas systeming carbinol is anti-
It should be CO+2H2→CH3OH, methanol aminating reaction are CH3OH+NH3→(CH3)1-3NH0-2+H2O。
Moreover, the catalyst for methanol be CuZnAl catalyst, weight percent composition CuO:30-60%,
ZnO:30-60%, Al2O3: 5-10%, the catalyst are prepared using coprecipitation.
Moreover, being shaped to beat piece, being sized to granularity for the catalyst is 20-80 mesh.
Moreover, the preparation method of the catalyst for methanol, comprising the following steps:
(1) by mantoquita, zinc salt and aluminium salt according to CuO:30-60%, ZnO:30-60%, Al2O3: 5-10% metal molar ratio
It is configured to mixing salt solution, copper salt solution and zinc solution are one in HCI solution, nitrate solution and acetate solution
Kind is several；
(2) mixing salt solution and precipitating reagent are reacted, and for the pH value of solution in 8-10, precipitation temperature is 40-80 DEG C, described
Precipitating reagent is Na2CO3、NaHCO3, NaOH, one or more of urea；
(3) after sediment is separated with mother liquor, sediment is cleaned using deionized water repeatedly, deionized water temperature is 40-60
DEG C, then in dry in air and roasting, drying temperature is 90-120 DEG C, drying time 12-24h, maturing temperature 300-
500 DEG C, calcining time 5-10h obtains catalyst for methanol.
Moreover, the methylamine catalyst is the composite molecular screen material with core-shell structure, center ZSM-5, ZSM-
One of 35 or two kind, shell SAPO-34, AlPO4One of -25 or two kind, shape existing for the composite molecular screen material
Formula includes at least one of physical mixed, cocrystallization structure.
Moreover, the methylamine catalyst is molecular sieve catalyst, prepared using solid-phase synthesis, structure is molecular sieve
The core-shell structure of molecular sieve is coated, wherein shell is that can choose SAPO-34, AlPO with 8 member ring topological structure molecular sieves4In -25
One kind or two kinds, core be with 10 member ring topological structure molecular sieves, one of ZSM-5, ZSM-35 or two kinds can be chosen.
Moreover, the preparation method of the methylamine catalyst, comprising the following steps:
(1) solid silicon source, silicon source, phosphorus source, template are added in agate mortar and grind 5-60min, be packed into water heating kettle,
In 100-250 DEG C of crystallization 16-240h, product is washed, dry, obtains molecular sieve core；
(2) molecular sieve core is nucleus in step (1), using second-crystallized method, molecule screen shell is grown on nucleus, in agate
Mixed molecular sieve core in mortar, template, grinds 5-60min at silicon source at room temperature, then the hydrothermal crystallizing at 100-250 DEG C
24-72h, product is washed, dry, and 300-600 DEG C of roasting 5-10h obtains methylamine catalyst.
Moreover, temperature dry in step (2) is 80-120 DEG C, drying time 6-24h.
Moreover, selected silicon source is white carbon black, SiO2One of gel, silicic acid, sodium metasilicate are a variety of, and selected silicon source is quasi-
One of boehmite, aluminum nitrate, sodium aluminate, aluminum sulfate and kaolin are a variety of, and selected phosphorus source is phosphoric acid, ammonium dihydrogen phosphate
One of or two kinds, the silicon source, silicon source, phosphorus source, the molar ratio of template be 1-50:0.1-1:0-1:0.1-1.
Moreover, the silicon source, the molar ratio of template are 1-50:0.1-1, the molecule screen shell is with silicon source mass ratio
10-100:1。
The molecular sieve crystal form of preparation of the embodiment of the present invention is surveyed using Rigaku Ultima IV type X-ray diffractometer (XRD)
It is fixed, experiment condition are as follows: CuKa radiation, pipe press 40kV, tube current 40mA.
Embodiment 1
Catalyst for methanol CuZnAl synthesis: nine water of 10.87g nitrate trihydrate copper, 13.38g zinc nitrate hexahydrate and 3.75g is weighed
Aluminum nitrate is added in the beaker for filling 200mL, is kept for 60 DEG C, using the solution as solution A.It is dissolved in 100mL deionized water
9.54g sodium carbonate liquor, using the solution as B solution.B solution is slowly added dropwise into solution A, is vigorously stirred simultaneously, temperature maintains
60 DEG C, by pH in sodium carbonate liquor drop rate control system 8.6 or so.After the completion of to be precipitated, aged at room temperature is overnight, mistake
Filter, with 60 DEG C of deionized waters repeatedly wash precipitating 5 times to filtrate be neutrality, finally 350 DEG C in 120 DEG C of dry 6h, Muffle furnace
5h is roasted, CuZnAl catalyst for methanol is obtained, CuZnAl molar ratio is 45:45:10, CuZnAl sample XRD spectra such as Fig. 2 institute
Show.
Embodiment 2
The synthesis of HZSM-5 catalyst: white carbon black 4.87g, boehmite 0.48g, sodium hydroxide 0.28g, tetrapropyl bromination are weighed
Ammonium 0.25g is added in agate mortar, grinds 5-10min, is then added into water heating kettle, in 200 DEG C of crystallization 16h, crystallization
After, ice-water bath is chilled to room temperature, is washed with deionized repeatedly to neutrality, and 120 DEG C are dried overnight, and obtains NaZSM-5 points
Son sieve.By NaZSM-5 powder be added 1M aqueous ammonium nitrate solution in, solid-liquid mass ratio 1:10 is vigorously stirred, at 80 DEG C into
Row ion exchange, this process are repeated 3 times, and powder is finally roasted 5h in 500 DEG C of air, obtained in 120 DEG C of dry 6h after filtering
XRD spectra to HZSM-5 molecular sieve, ZSM-5 sample is as shown in Figure 3.
Embodiment 3
HZSM-35 Zeolite synthesis: weighing white carbon black 4.4g, aluminum nitrate 2.08g, sodium hydroxide 1.6g, ethylenediamine 2.8g,
It is added in agate mortar, grinds 5-10min, be then added into water heating kettle, crystallized at 200 DEG C for 24 hours, after crystallization, ice
Water-bath is chilled to room temperature, is washed with deionized repeatedly to neutrality, and 120 DEG C are dried overnight, and obtains NaZSM-35 molecular sieve.It will
NaZSM-35 powder is added in the aqueous ammonium nitrate solution of 1M, and solid-liquid mass ratio 1:10 is vigorously stirred, and ion is carried out at 80 DEG C
Exchange, this process are repeated 3 times, powder are finally roasted 5h in 500 DEG C of air, obtained in 120 DEG C of dry 6h after filtering
HZSM-35 molecular sieve, shown in the XRD spectra local, colloquial expressions 4 of ZSM-35 sample.
Embodiment 4
AlPO4- 25 Zeolite synthesis: white carbon black 0.40g, aluminium isopropoxide 4.18g, phosphoric acid 2.36g, dimethylamine are weighed
(40wt%) 1.35g is added in agate mortar, grinds 15-25min, is then added into water heating kettle, crystallizes at 200 DEG C
For 24 hours, after crystallization, ice-water bath is chilled to room temperature, is washed with deionized repeatedly to neutrality, and 120 DEG C are dried overnight, and finally exists
5h is roasted in 500 DEG C of air, obtains AlPO4- 25 molecular sieves, AlPO4The XRD spectra of -25 samples is as shown in Figure 5.
Embodiment 5
SAPO-34 Zeolite synthesis: white carbon black 0.15g, boehmite 0.58g, ammonium dihydrogen phosphate 0.52g, morpholine are weighed
1.30g is added in agate mortar, grinds 5-10min, is then added into water heating kettle, crystallizes for 24 hours at 200 DEG C, crystallization terminates
Afterwards, ice-water bath is chilled to room temperature, is washed with deionized repeatedly to neutrality, and 120 DEG C are dried overnight, finally in 500 DEG C of air
5h is roasted, obtains SAPO-34 molecular sieve, the XRD spectra of SAPO-34 sample is as shown in Figure 6.
Embodiment 6
The synthesis of HZSM-35@SAPO-34 composite molecular screen: HZSM-35 molecular sieve 1.0g prepared in embodiment 3 is weighed
It is fitted into agate, then weighs white carbon black 0.15g, boehmite 0.58g, ammonium dihydrogen phosphate 0.52g, morpholine 1.30g, addition is equipped with
In HZSM-35 molecular sieve agate mortar, 5-10min is ground, is then added into water heating kettle, crystallized at 200 DEG C for 24 hours, crystallization
After, ice-water bath is chilled to room temperature, is washed with deionized repeatedly to neutrality, and 120 DEG C are dried overnight, finally in 500 DEG C of skies
5h is roasted in gas, obtains HZSM-35@SAPO-34 methylamine catalyst, XRD spectra such as Fig. 7 of HZSM-35@SAPO-34 molecular sieve
It is shown.
Embodiment 7
The synthesis of HZSM-5@SAPO-34 composite molecular screen: HZSM-5 molecular sieve 1.0g dress prepared in embodiment 2 is weighed
Enter in agate, then weigh white carbon black 0.15g, boehmite 0.58g, ammonium dihydrogen phosphate 0.52g, morpholine 1.30g, addition is equipped with
In HZSM-5 molecular sieve agate mortar, 5-10min is ground, is then added into water heating kettle, crystallized at 200 DEG C for 24 hours, crystallization
After, ice-water bath is chilled to room temperature, is washed with deionized repeatedly to neutrality, and 120 DEG C are dried overnight, finally in 500 DEG C of skies
5h is roasted in gas, obtains HZSM-5@SAPO-34 methylamine catalyst, XRD spectra such as Fig. 8 institute of HZSM-5@SAPO-34 molecular sieve
Show.
Embodiment 8
HZSM-5@AlPO4The synthesis of -25 composite molecular screens: HZSM-5 molecular sieve 2.0g dress prepared in embodiment 2 is weighed
Enter in agate, weigh white carbon black 0.40g, aluminium isopropoxide 4.18g, phosphoric acid 2.36g, agate is added in dimethylamine (40wt%) 1.35g
In mortar, 15-25min is ground, is then added into water heating kettle, crystallized at 200 DEG C for 24 hours, after crystallization, ice-water bath chilling
It to room temperature, is washed with deionized repeatedly to neutrality, 120 DEG C are dried overnight, and finally roast 5h in 500 DEG C of air, obtain
HZSM-5@AlPO4- 25 molecular sieves, HZSM-5@AlPO4The XRD spectra of -25 molecular sieves is as shown in Figure 9.
Embodiment 9
It is packed into the CuZnAl catalyst for methanol of 0.5g, catalyst particle size is 20-40 mesh, is fitted into micro- anti-single tube, urges
Agent is fixed at two ends up and down with silica wool.The reaction condition of catalyst are as follows: 250 DEG C, 0.5MPa, H2/CO/NH3Molar ratio 2/1/1,
Gaseous mixture flow velocity 20mL/min.Reaction result is as shown in table 1, and CO conversion ratio is 8.1%, and methanol selectivity has reached 99%, table
Bright CuZnAl catalyst for methanol selectivity is very high.
Embodiment 10
It is packed into the CuZnAl catalyst for methanol of 0.5g, the HZSM-5@SAPO-34 methylamine catalyst of 0.5g, methanol and methanol
Catalyst is granulated 20-40 mesh, is sequentially loaded into micro- anti-single tube, and every kind of catalyst is fixed at two ends up and down with silica wool.Catalyst
Reaction condition are as follows: 250 DEG C, 0.5MPa, H2/CO/NH3Molar ratio 2/1/1, gaseous mixture flow velocity 20mL/min.Reaction result such as table
Shown in 1, CO conversion ratio is 9.5%, and dimethylamine is selectively 38%.Show that molecular sieve catalyst has stronger water separation capability,
Comparative example 1, dimethylamine type selecting significantly improve, a small amount of dimethyl ether by-product.
Embodiment 11
It is packed into the CuZnAl catalyst for methanol of 0.5g, the HZSM-35@SAPO-34 methylamine catalyst of 0.5g, methanol and methanol
Catalyst is granulated 20-40 mesh, is sequentially loaded into micro- anti-single tube, and every kind of catalyst is fixed at two ends up and down with silica wool.Catalyst
Reaction condition are as follows: 250 DEG C, 0.5MPa, H2/CO/NH3Molar ratio 2/1/1, gaseous mixture flow velocity 20mL/min.Reaction result such as table
Shown in 1, comparative example 10, CO conversion ratio is slightly reduced.Due to the hole HZSM-35 is less than ZSM-5, monomethyl amine selectivity
It significantly improves, while also inhibiting the selectivity of trimethylamine.
Embodiment 12
It is packed into the CuZnAl catalyst for methanol of 0.5g, the HZSM-5@AlPO of 0.5g4- 25 methylamine catalysts, methanol and methanol
Catalyst is granulated 20-40 mesh, is sequentially loaded into micro- anti-single tube, and every kind of catalyst is fixed at two ends up and down with silica wool.Catalyst
Reaction condition are as follows: 250 DEG C, 0.5MPa, H2/ CO/NH3 molar ratio 2/1/1, gaseous mixture flow velocity 20mL/min.Reaction result is such as
Shown in table 1, CO conversion ratio is 10.2%, and comparative example 10, dimethylamine significantly improves, and illustrates AlPO4- 25 have stronger select
Shape catalytic performance.
Embodiment 13
It is packed into the CuZnAl catalyst for methanol of 0.5g, the HZSM-5@AlPO of 0.5g4- 25 methylamine catalysts, methanol and methanol
Catalyst is granulated 20-40 mesh, is fitted into micro- anti-single tube after mixing, and catalyst is fixed at two ends up and down with silica wool.Catalyst
Reaction condition are as follows: 250 DEG C, 0.5MPa, H2/CO/NH3Molar ratio 2/1/1, gaseous mixture flow velocity 20mL/min.Reaction result such as table 1
Shown, comparative example 12, CO conversion ratio is to further increase to 13.6%, and dimethylamine has selectively reached 53%, while three
Methylamine is selectively substantially reduced.
Each catalytic reaction activity of table 1 and selectivity of product
Although disclosing the embodiment of the present invention and attached drawing for the purpose of illustration, those skilled in the art can be managed
Solution: do not departing from the present invention and spirit and scope of the appended claims in, various substitutions, changes and modifications be all it is possible,
Therefore, the scope of the present invention is not limited to the embodiment and attached drawing disclosure of that.
Claims (10)
1. a kind of method for directly producing dimethylamine by synthesis gas, it is characterised in that: this method includes synthesising gas systeming carbinol reaction
With two tandem reactions of methanol aminating reaction, wherein catalysts are made of catalyst for methanol and methylamine catalyst, this method
It is carried out in continuous fixed bed hair reactor, reaction temperature is 200-400 DEG C, pressure 0.1-5MPa, and feed gas volume ratio is
H2/CO/NH3=1-3:1:1-3, catalyst for methanol and methylamine catalyst mass ratio are 1:0.5-5, wherein synthesising gas systeming carbinol is anti-
It should be CO+2H2→CH3OH, methanol aminating reaction are CH3OH+NH3→(CH3)1-3NH0-2+H2O。
2. a kind of method for directly producing dimethylamine by synthesis gas according to claim 1, it is characterised in that: the methanol
Catalyst is CuZnAl catalyst, weight percent composition CuO:30-60%, ZnO:30-60%, Al2O3: 5-10%, it should
Catalyst is prepared using coprecipitation.
3. a kind of method for directly producing dimethylamine by synthesis gas according to claim 1 or claim 2, it is characterised in that: described
Being shaped to beat piece, being sized to granularity for catalyst is 20-80 mesh.
4. a kind of method for directly producing dimethylamine by synthesis gas according to claim 1, it is characterised in that: the methanol
The preparation method of catalyst, comprising the following steps:
(1) by mantoquita, zinc salt and aluminium salt according to CuO:30-60%, ZnO:30-60%, Al2O3: 5-10% metal molar is than configuration
At mixing salt solution, copper salt solution and zinc solution be one of HCI solution, nitrate solution and acetate solution or
It is several；
(2) mixing salt solution and precipitating reagent are reacted, and the pH value of solution is in 8-10, and precipitation temperature is 40-80 DEG C, the precipitating
Agent is Na2CO3、NaHCO3, NaOH, one or more of urea；
(3) after sediment is separated with mother liquor, sediment is cleaned using deionized water repeatedly, deionized water temperature is 40-60 DEG C, so
Afterwards in dry in air and roasting, drying temperature is 90-120 DEG C, drying time 12-24h, and maturing temperature is 300-500 DEG C,
Calcining time 5-10h, obtains catalyst for methanol.
5. a kind of method for directly producing dimethylamine by synthesis gas according to claim 1, it is characterised in that: the methylamine is urged
Agent is the composite molecular screen material with core-shell structure, one of center ZSM-5, ZSM-35 or two kinds, and shell is
SAPO-34、AlPO4One of -25 or two kind, form existing for the composite molecular screen material includes physical mixed, cocrystallization
At least one of structure.
6. according to claim 1 or a kind of 5 methods for directly producing dimethylamine by synthesis gas, it is characterised in that: described
Methylamine catalyst is molecular sieve catalyst, is prepared using solid-phase synthesis, and structure is the nucleocapsid knot that molecular sieve coats molecular sieve
Structure, wherein shell is that can choose SAPO-34, AlPO with 8 member ring topological structure molecular sieves4One of -25 or two kind, core is
With 10 member ring topological structure molecular sieves, one of ZSM-5, ZSM-35 or two kinds can be chosen.
7. a kind of method for directly producing dimethylamine by synthesis gas according to claim 6, it is characterised in that: the methylamine
The preparation method of catalyst, comprising the following steps:
(1) solid silicon source, silicon source, phosphorus source, template are added in agate mortar and grind 5-60min, be packed into water heating kettle, In
100-250 DEG C of crystallization 16-240h, product is washed, dry, obtains molecular sieve core；
(2) molecular sieve core is nucleus in step (1), using second-crystallized method, molecule screen shell is grown on nucleus, in agate mortar
Middle mixed molecular sieve core, template, grinds 5-60min at silicon source at room temperature, then the hydrothermal crystallizing 24-72h at 100-250 DEG C,
Product is washed, dry, and 300-600 DEG C of roasting 5-10h obtains methylamine catalyst.
8. a kind of method for directly producing dimethylamine by synthesis gas according to claim 7, it is characterised in that: in step (2)
Dry temperature is 80-120 DEG C, drying time 6-24h.
9. a kind of method for directly producing dimethylamine by synthesis gas according to claim 7, it is characterised in that: selected silicon source is
White carbon black, SiO2One of gel, silicic acid, sodium metasilicate are a variety of, selected silicon source be boehmite, aluminum nitrate, sodium aluminate,
One of aluminum sulfate and kaolin are a variety of, and selected phosphorus source is one of phosphoric acid, ammonium dihydrogen phosphate or two kinds, the silicon
Source, silicon source, phosphorus source, the molar ratio of template are 1-50:0.1-1:0-1:0.1-1.
10. a kind of method for directly producing dimethylamine by synthesis gas according to claim 7, it is characterised in that: the silicon source,
The molar ratio of template is 1-50:0.1-1, and the molecule screen shell and silicon source mass ratio are 10-100:1.
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| CN111004127A (en) * | 2019-12-13 | 2020-04-14 | 宁夏大学 | Method for preparing ethylamine and coproducing methylamine by dimethyl ether, synthesis gas and ammonia gas in one step |
| CN111056948A (en) * | 2019-12-16 | 2020-04-24 | 中国科学院大连化学物理研究所 | Process for preparing hexamethylenediamine |
| CN111744488A (en) * | 2020-07-01 | 2020-10-09 | 太原理工大学 | Catalyst for preparing dimethyl ether from slurry bed synthesis gas and preparation method thereof |
| CN112844456A (en) * | 2021-01-21 | 2021-05-28 | 中国工程物理研究院核物理与化学研究所 | Preparation method and application of core-shell type metal zeolite catalyst |
| CN114426488A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Method for preparing methylamine by amination of methanol |
| CN114749191A (en) * | 2022-03-24 | 2022-07-15 | 淮阴工学院 | Ni/P-attapulgite clay catalyst and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3444203A (en) * | 1965-07-29 | 1969-05-13 | Union Carbide Corp | Production of methylamines |
| CN1356165A (en) * | 2000-12-06 | 2002-07-03 | 中国科学院大连化学物理研究所 | Cu-series catalyst for synthesizing low-carbon amines directly from synthetic gas and ammonia gas and its application |
| CN1955157A (en) * | 2002-11-26 | 2007-05-02 | 巴斯福股份公司 | Continuous methods and reactor used for the production of alkylamines |
| CN105983438A (en) * | 2015-01-28 | 2016-10-05 | 中国石油天然气股份有限公司 | Molecular sieve composite material having core-shell structure, preparation method and application thereof |
-
2019
- 2019-06-20 CN CN201910536137.1A patent/CN110511149B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3444203A (en) * | 1965-07-29 | 1969-05-13 | Union Carbide Corp | Production of methylamines |
| CN1356165A (en) * | 2000-12-06 | 2002-07-03 | 中国科学院大连化学物理研究所 | Cu-series catalyst for synthesizing low-carbon amines directly from synthetic gas and ammonia gas and its application |
| CN1955157A (en) * | 2002-11-26 | 2007-05-02 | 巴斯福股份公司 | Continuous methods and reactor used for the production of alkylamines |
| CN105983438A (en) * | 2015-01-28 | 2016-10-05 | 中国石油天然气股份有限公司 | Molecular sieve composite material having core-shell structure, preparation method and application thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111004127A (en) * | 2019-12-13 | 2020-04-14 | 宁夏大学 | Method for preparing ethylamine and coproducing methylamine by dimethyl ether, synthesis gas and ammonia gas in one step |
| CN111004127B (en) * | 2019-12-13 | 2023-10-27 | 宁夏大学 | Method for preparing ethylamine and co-producing methylamine by one-step method of dimethyl ether, synthesis gas and ammonia gas |
| CN111056948A (en) * | 2019-12-16 | 2020-04-24 | 中国科学院大连化学物理研究所 | Process for preparing hexamethylenediamine |
| CN111744488A (en) * | 2020-07-01 | 2020-10-09 | 太原理工大学 | Catalyst for preparing dimethyl ether from slurry bed synthesis gas and preparation method thereof |
| CN111744488B (en) * | 2020-07-01 | 2022-04-19 | 太原理工大学 | Catalyst for preparing dimethyl ether from slurry bed synthesis gas and preparation method thereof |
| CN114426488A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Method for preparing methylamine by amination of methanol |
| CN112844456A (en) * | 2021-01-21 | 2021-05-28 | 中国工程物理研究院核物理与化学研究所 | Preparation method and application of core-shell type metal zeolite catalyst |
| CN114749191A (en) * | 2022-03-24 | 2022-07-15 | 淮阴工学院 | Ni/P-attapulgite clay catalyst and preparation method and application thereof |
| CN114749191B (en) * | 2022-03-24 | 2023-06-30 | 淮阴工学院 | Ni/P-attapulgite clay catalyst and preparation method and application thereof |
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| CN110511149B (en) | 2022-07-26 |
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