CN110511149B - Method for directly preparing dimethylamine from synthesis gas - Google Patents
Method for directly preparing dimethylamine from synthesis gas Download PDFInfo
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- CN110511149B CN110511149B CN201910536137.1A CN201910536137A CN110511149B CN 110511149 B CN110511149 B CN 110511149B CN 201910536137 A CN201910536137 A CN 201910536137A CN 110511149 B CN110511149 B CN 110511149B
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- catalyst
- methanol
- molecular sieve
- reaction
- dimethylamine
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- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 41
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 210
- 239000003054 catalyst Substances 0.000 claims abstract description 115
- 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 84
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000002808 molecular sieve Substances 0.000 claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 239000011258 core-shell material Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 17
- 239000006229 carbon black Substances 0.000 claims description 16
- 229910017119 AlPO Inorganic materials 0.000 claims description 15
- 239000012266 salt solution Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000004570 mortar (masonry) Substances 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 230000008569 process 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
- 229910001593 boehmite Inorganic materials 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 9
- 239000005457 ice water Substances 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 7
- 150000001879 copper Chemical class 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- 230000000171 quenching effect Effects 0.000 claims description 5
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 5
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- 239000007788 liquid Substances 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
- 239000011734 sodium Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 230000001376 precipitating effect Effects 0.000 claims 2
- 238000001308 synthesis method Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 12
- 239000010703 silicon Substances 0.000 description 12
- 238000001228 spectrum Methods 0.000 description 10
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 239000012494 Quartz wool Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 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 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 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 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000005216 hydrothermal crystallization Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid 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
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 1
- 229910016523 CuKa Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach 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
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000002288 cocrystallisation 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
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 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
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 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
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- 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
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- 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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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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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- 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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- 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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Abstract
The invention relates to a method for directly preparing dimethylamine from synthesis gas, which is characterized by comprising the following steps: the method comprises two series reactions of reaction for preparing methanol from synthesis gas and methanol ammoniation reaction, wherein the reaction catalyst consists of a methanol catalyst and a methylamine catalyst, the method is carried out in a continuous fixed bed reactor, the reaction temperature is 200-400 ℃, the pressure is 0.1-5MPa, and the volume ratio of the raw material gas is H 2 /CO/NH 3 The invention realizes the reaction of directly preparing dimethylamine by synthesis gas one-step method by coupling a methanol catalyst and a methylamine catalyst, wherein the mass ratio of the methanol catalyst to the methylamine catalyst is 1: 3:1:1-3, and the mass ratio of the methanol catalyst to the methylamine catalyst is 1: 0.5-5. The serial catalyst composed of CuZnAl and the core-shell structure composite molecular sieve has the advantages of simple synthesis, low catalyst cost, low equipment investment and the like, and the selectivity of dimethylamine in the product is obviously improved.
Description
Technical Field
The invention belongs to the field of chemical synthesis, relates to a series catalytic synthesis reaction technology, in particular to a multifunctional composite catalyst, and particularly relates to a method for directly preparing dimethylamine from synthesis gas.
Background
Methylamine is an important organic chemical raw material, is widely applied to industries such as medicines, pesticides, solvents, template agents and the like, and has wide application. Currently, methanol is mostly adopted in industry to synthesize methylamine by a gas phase catalysis method of ammonia, but because of thermodynamic equilibrium control, the equilibrium composition of monomethylamine/dimethylamine/trimethylamine is 23/27/50 (mass ratio), wherein the market demand of dimethylamine is the largest, and accounts for more than 80%, and the dimethylamine is an important raw material for generating a dimethylformamide solvent.
China is rich in coal resources, and the preparation of methanol from synthesis gas with coal as a source is an important energy development approach. Early US patent US2821537 reported that methylamine (CO + H) can be directly prepared from mixed syngas and ammonia gas 2 +NH 3 → CH 3 NH 2 +CH 3 -NH-CH 3 +(CH 3 ) 3 N), the route adopts a one-stage method to directly synthesize the methylamine, and the economic benefit and the environmental protection significance are very important. The route comprises the following two steps: (1) synthesis of methanol, CO + H from synthesis gas 2 →CH 3 OH, a catalyst CuZnAl for industrially synthesizing methanol is well developed; (2) synthesis of methylamine, CH by gas phase ammoniation of methanol 3 OH+NH 3 →(CH 3 ) 1-3 NH 0-2 +H 2 O, this step is a dehydration reaction and is currently predominantly a molecular sieve catalyst.
Baiker et Al uses Cu/Al 2 O 3 The catalyst is at 0.6MPa, 200 ℃ and 300 ℃ and CO/H 2 /NH 3 Under the reaction condition of 1/1/3, methylamine may be synthesized directly, where Cu is catalyst for hydrogenating synthetic gas to prepare methanol and acidic Al 2 O 3 As a catalyst for catalyzing the amination of methanol (Journal of the Chemical Society, Chemical Communications,1995,1,73-74), but because of Al 2 O 3 Due to the disordered property of the pore channel, the product has no shape-selective catalysis, so that the proportion of trimethylamine in the product is obviously higher, and the selectivity of dimethylamine is lower. In 1978, Mobil corporation developed ZSM series molecular sieves by utilizing the shape-selective catalytic action of pore channels of the molecular sieves, and greatly improved the selectivity of dimethylamine.
The work of high-selectivity dimethylamine synthesis by modified MOR molecular sieve catalyst by Nissan chemical company in 1984 has been industrialized, wherein the selectivity of dimethylamine is as high as 60%. However, MOR is a 12-membered ring and 8-membered ring channel structure, the dynamic diameter of trimethylamine is 0.39nm, and the trimethylamine can freely diffuse in the 12-membered ring molecular sieve channel, so that the pore diameter of the molecular sieve is reduced, the entrance and the exit of the trimethylamine in the molecular sieve channel can be inhibited, and the shape selective catalysis is realized. When the pore diameter of the molecular sieve is less than or equal to the molecular diameter of trimethylamine, the trimethylamine is not easily generated. The literature (Chinese Journal of Catalysis,2017,38, 574-582; Chemical Reviews,2018, 118,5265-5329) reports that the small-pore 8-membered ring molecular sieve effectively inhibits the generation of trimethylamine, wherein the RHO molecular sieve has the highest dimethylamine selectivity and the lowest trimethylamine selectivity.
In summary, both reactions have been industrialized, whether the reaction is a reaction for preparing methanol from synthesis gas or a reaction for preparing methylamine through methanol ammoniation. However, as mentioned above, if the synthesis gas and ammonia gas are used as raw materials, and methanol synthesis and methanol ammoniation reaction are coupled to directly produce dimethylamine, the energy consumption can be effectively reduced, the reaction process can be simplified, and the method is an industrially and economically advantageous process. Therefore, although there are various catalysts for this reaction, there is still a need to find a highly efficient catalyst which simultaneously satisfies:
(1) the two reaction process conditions of methanol synthesis and methanol ammoniation are matched, such as temperature, pressure and other conditions;
(2) compounding the catalyst, such as physical mixing, two-stage process or core-shell structure catalyst;
(3) the shape-selective catalytic effect of the molecular sieve controls the pore channel structure of the molecular sieve, and the selectivity of dimethylamine is realized to the maximum extent.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for directly preparing dimethylamine from synthesis gas. In addition, the invention provides a method for directly preparing the catalyst of dimethylamine by synthesis gas, the composite molecular sieve synthesized by the solid-phase synthesis method of the catalyst is a molecular sieve catalyst with a core-shell structure, the catalytic efficiency is high, the preparation of the catalyst is simple and easy to operate, the energy consumption is low, and the catalyst cost is further reduced.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
a process for directly preparing dimethylamine from synthetic gas includes two serial reactions of reaction for preparing methanol from synthetic gas and ammoniation reaction of methanol, in which the reaction catalyst is composed of methanol catalyst and methylamine catalyst, and is carried out in a continuous fixed-bed reactor at 200-400 deg.C and 0.1-5MPa in volume ratio of raw material gas (H) 2 /CO/NH 3 The mass ratio of the methanol catalyst to the methylamine catalyst is 1:0.5-5, wherein the reaction for preparing methanol from synthesis gas is CO +2H 2 →CH 3 OH, methanol ammoniation reaction to CH 3 OH+NH 3 →(CH 3 ) 1-3 NH 0-2 +H 2 O。
Moreover, the methanol catalyst is CuZnAl catalyst, and the weight percentage of the CuO catalyst is 30-60%, the ZnO catalyst is 30-60%, and the Al catalyst is 2 O 3 5-10%, and the catalyst is prepared by coprecipitation method.
And the catalyst is formed into tablets and sieved to have the granularity of 20-80 meshes.
Moreover, the preparation method of the methanol catalyst comprises the following steps:
(1) copper salt, zinc salt and aluminum salt are added according to the proportion of CuO 30-60%, ZnO 30-60% and Al 2 O 3 Preparing a mixed salt solution by using a metal molar ratio of 5-10%, wherein the copper salt solution and the zinc salt solution are one or more of a hydrochloric acid salt solution, a nitric acid salt solution and an acetic acid salt solution;
(2) reacting the mixed salt solution with a precipitant, wherein the pH value of the solution is 8-10, the precipitation temperature is 40-80 ℃, and the precipitant is Na 2 CO 3 、NaHCO 3 One or more of NaOH and urea;
(3) and after separating the precipitate from the mother liquor, repeatedly cleaning the precipitate by using deionized water at the temperature of 40-60 ℃, and then drying and roasting in the air at the drying temperature of 90-120 ℃ for 12-24h at the roasting temperature of 300-500 ℃ for 5-10h to obtain the methanol catalyst.
Moreover, the methylamine catalyst is a composite molecular sieve material with a core-shell structure, wherein the core is one or two of ZSM-5 and ZSM-35, and the shell is SAPO-34 and AlPO 4 -25 in a form comprising at least one of a physically mixed, co-crystallized structure.
The methylamine catalyst is a molecular sieve catalyst and is prepared by a solid-phase synthesis method, the structure of the methylamine catalyst is a core-shell structure of the molecular sieve coated with the molecular sieve, wherein the shell is a molecular sieve with an 8-membered ring topological structure, and SAPO-34 and AlPO can be selected 4 -25, the core is a molecular sieve with 10-membered ring topology, and one or two of ZSM-5 and ZSM-35 can be selected.
Moreover, the preparation method of the methylamine catalyst comprises the following steps:
(1) adding a solid silicon source, an aluminum source, a phosphorus source and a template agent into an agate mortar, grinding for 5-60min, putting into a hydrothermal kettle, crystallizing at 100-250 ℃ for 16-240h, washing and drying a product to obtain a molecular sieve core;
(2) in the step (1), the molecular sieve core is taken as a crystal nucleus, a secondary crystallization method is adopted to grow a molecular sieve shell on the crystal nucleus, the molecular sieve core, a silicon source and a template agent are mixed in an agate mortar, the mixture is ground for 5-60min at room temperature, hydrothermal crystallization is carried out for 24-72h at the temperature of 100-250 ℃, and the product is washed, dried and roasted for 5-10h at the temperature of 300-600 ℃ to obtain the methylamine catalyst.
And the drying temperature in the step (2) is 80-120 ℃, and the drying time is 6-24 h.
Moreover, the selected silicon source is white carbon black and SiO 2 One or more of gel, silicic acid and sodium silicate, wherein the selected aluminum source is one or more of pseudo-boehmite, aluminum nitrate, sodium aluminate, aluminum sulfate and kaolin, the selected phosphorus source is one or two of phosphoric acid and ammonium dihydrogen phosphate, and the molar ratio of the silicon source, the aluminum source, the phosphorus source and the template is 1-50:0.1-1:0-1: 0.1-1.
Moreover, the mole ratio of the silicon source to the template agent is 1-50:0.1-1, and the mass ratio of the molecular sieve shell to the silicon source is 10-100: 1.
The invention has the advantages and positive effects that:
1. the invention couples the reaction of preparing methanol by CO hydrogenation and the reaction of preparing methylamine by methanol ammoniation, fills a methanol catalyst and a methylamine catalyst in a fixed bed reactor, realizes the matching of the two reaction process conditions of methanol synthesis and methanol ammoniation and the reaction of directly preparing dimethylamine by synthesis gas.
2. The invention adopts a solid-phase synthesis method to prepare the composite molecular sieve catalyst with the core-shell structure, and realizes the high-selectivity synthesis of dimethylamine by methanol ammoniation by controlling the pore channel structure of the molecular sieve and utilizing the shape-selective catalytic effect of the molecular sieve.
3. The invention realizes the reaction of directly preparing dimethylamine by one step of synthesis gas by coupling a methanol catalyst and a methylamine catalyst. The serial catalyst composed of CuZnAl and the core-shell structure composite molecular sieve has the advantages of simple synthesis, low catalyst cost, low equipment investment and the like, and the selectivity of dimethylamine in the product is obviously improved.
Drawings
FIG. 1 is a process diagram of one-step preparation of dimethylamine from synthesis gas;
FIG. 2 is an XRD spectrum of a CuZnAl methanol catalyst;
FIG. 3 is an XRD spectrum of a ZSM-5 molecular sieve;
FIG. 4 is an XRD spectrum of a ZSM-35 molecular sieve;
FIG. 5 is an XRD spectrum of an AlPO4-25 molecular sieve;
FIG. 6 is an XRD spectrum of a SAPO-34 molecular sieve;
FIG. 7 is an XRD spectrum of an HZSM-35@ SAPO-34 molecular sieve;
FIG. 8 is an XRD spectrum of HZSM-5@ SAPO-34 molecular sieve;
FIG. 9 is an XRD spectrum of the HZSM-5@ AlPO4-25 molecular sieve.
Detailed Description
The present invention will be described in more detail below with reference to the following embodiments, which are provided by way of illustration only and are not intended to limit the scope of the present invention.
A method for directly preparing dimethylamine from synthesis gas, as shown in figure1, the method comprises two series reactions of reaction for preparing methanol from synthesis gas and methanol ammoniation reaction, wherein the reaction catalyst consists of a methanol catalyst and a methylamine catalyst, the method is carried out in a continuous fixed bed reactor, the reaction temperature is 200-400 ℃, the pressure is 0.1-5MPa, and the volume ratio of the raw material gas is H 2 /CO/NH 3 1-3:1:1-3, wherein the mass ratio of the methanol catalyst to the methylamine catalyst is 1:0.5-5, and the reaction for preparing methanol from synthesis gas is CO +2H 2 →CH 3 OH, methanol ammoniation reaction to CH 3 OH+NH 3 →(CH 3 ) 1-3 NH 0-2 +H 2 O。
Moreover, the methanol catalyst is a CuZnAl catalyst which comprises 30 to 60 weight percent of CuO, 30 to 60 weight percent of ZnO and Al 2 O 3 5-10%, and the catalyst is prepared by coprecipitation method.
And the catalyst is formed into tablets and sieved to have the granularity of 20-80 meshes.
Moreover, the preparation method of the methanol catalyst comprises the following steps:
(1) copper salt, zinc salt and aluminum salt are added according to the proportion of 30-60 percent of CuO, 30-60 percent of ZnO and Al 2 O 3 Preparing a mixed salt solution by using 5-10% of metal in a molar ratio, wherein the copper salt solution and the zinc salt solution are one or more of a hydrochloride solution, a nitrate solution and an acetate solution;
(2) reacting the mixed salt solution with a precipitant, wherein the pH value of the solution is 8-10, the precipitation temperature is 40-80 ℃, and the precipitant is Na 2 CO 3 、NaHCO 3 One or more of NaOH and urea;
(3) and after separating the precipitate from the mother liquor, repeatedly cleaning the precipitate by using deionized water at the temperature of 40-60 ℃, and then drying and roasting in the air at the drying temperature of 90-120 ℃ for 12-24h at the roasting temperature of 300-500 ℃ for 5-10h to obtain the methanol catalyst.
Moreover, the methylamine catalyst is a composite molecular sieve material with a core-shell structure, wherein the core is one or two of ZSM-5 and ZSM-35, and the shell is SAPO-34 and AlPO 4 One of-25And one or two of the composite molecular sieve materials exist in a form including at least one of physical mixing and a cocrystallization structure.
Moreover, the methylamine catalyst is a molecular sieve catalyst and is prepared by adopting a solid-phase synthesis method, the structure of the methylamine catalyst is a core-shell structure of the molecular sieve coated with the molecular sieve, wherein the shell is a molecular sieve with an 8-membered ring topological structure, and SAPO-34 and AlPO can be selected 4 25, the core is a molecular sieve with 10-membered ring topological structure, and one or two of ZSM-5 and ZSM-35 can be selected.
Moreover, the preparation method of the methylamine catalyst comprises the following steps:
(1) adding a solid silicon source, an aluminum source, a phosphorus source and a template agent into an agate mortar, grinding for 5-60min, putting into a hydrothermal kettle, crystallizing at 100-250 ℃ for 16-240h, washing and drying a product to obtain a molecular sieve core;
(2) in the step (1), the molecular sieve core is taken as a crystal nucleus, a secondary crystallization method is adopted to grow a molecular sieve shell on the crystal nucleus, the molecular sieve core, a silicon source and a template agent are mixed in an agate mortar, the mixture is ground for 5-60min at room temperature, hydrothermal crystallization is carried out for 24-72h at the temperature of 100-250 ℃, and the product is washed, dried and roasted for 5-10h at the temperature of 300-600 ℃ to obtain the methylamine catalyst.
And the drying temperature in the step (2) is 80-120 ℃, and the drying time is 6-24 h.
Moreover, the selected silicon source is white carbon black and SiO 2 The aluminum source is one or more of pseudo-boehmite, aluminum nitrate, sodium aluminate, aluminum sulfate and kaolin, the phosphorus source is one or two of phosphoric acid and ammonium dihydrogen phosphate, and the molar ratio of the silicon source, the aluminum source, the phosphorus source and the template agent is 1-50:0.1-1:0-1: 0.1-1.
And the molar ratio of the silicon source to the template agent is 1-50:0.1-1, and the mass ratio of the molecular sieve shell to the silicon source is 10-100: 1.
The molecular sieve crystal form prepared in the embodiment of the invention is determined by a Nippon pharmacological Ultima type IV X-ray diffractometer (XRD), and the experimental conditions are as follows: CuKa radiation, tube voltage 40kV and tube current 40 mA.
Example 1
Synthesizing a methanol catalyst CuZnAl: 10.87g of copper nitrate trihydrate, 13.38g of zinc nitrate hexahydrate and 3.75g of aluminum nitrate nonahydrate were weighed and added to a beaker containing 200mL of the solution, and the temperature was maintained at 60 ℃ to obtain a solution A. 9.54g of sodium carbonate solution was dissolved in 100mL of deionized water, and the solution was defined as solution B. Slowly dripping the solution B into the solution A while vigorously stirring, maintaining the temperature at 60 ℃, and controlling the pH value in the system to be about 8.6 by the dripping speed of the sodium carbonate solution. And after the precipitation is finished, aging at room temperature overnight, filtering, repeatedly washing the precipitate for 5 times by using deionized water at 60 ℃ until the filtrate is neutral, finally drying at 120 ℃ for 6h, and roasting in a muffle furnace at 350 ℃ for 5h to obtain the CuZnAl methanol catalyst, wherein the CuZnAl molar ratio is 45:45:10, and the XRD spectrogram of a CuZnAl sample is shown in figure 2.
Example 2
HZSM-5 catalyst synthesis: weighing 4.87g of white carbon black, 0.48g of boehmite, 0.28g of sodium hydroxide and 0.25g of tetrapropyl ammonium bromide, adding the white carbon black, the boehmite, the sodium hydroxide and the tetrapropyl ammonium bromide into an agate mortar, grinding for 5-10min, then adding the ground boehmite, the tetrapropyl ammonium bromide into a hydrothermal kettle, crystallizing for 16h at 200 ℃, after crystallization is finished, rapidly cooling the mixture to room temperature in an ice water bath, repeatedly washing the mixture to be neutral by deionized water, and drying the mixture overnight at 120 ℃ to obtain the NaZSM-5 molecular sieve. Adding NaZSM-5 powder into 1M ammonium nitrate aqueous solution with the solid-liquid mass ratio of 1:10, violently stirring, carrying out ion exchange at 80 ℃, repeating the process for 3 times, drying the powder at 120 ℃ for 6h after filtering, and finally roasting in the air at 500 ℃ for 5h to obtain the HZSM-5 molecular sieve, wherein an XRD spectrogram of a ZSM-5 sample is shown in figure 3.
Example 3
Synthesizing an HZSM-35 molecular sieve: weighing 4.4g of white carbon black, 2.08g of aluminum nitrate, 1.6g of sodium hydroxide and 2.8g of ethylenediamine, adding the white carbon black, the aluminum nitrate, the sodium hydroxide and the ethylenediamine into an agate mortar, grinding for 5-10min, then adding the mixture into a hydrothermal kettle, crystallizing for 24h at 200 ℃, after crystallization is finished, rapidly cooling to room temperature in an ice water bath, repeatedly washing to be neutral by deionized water, and drying at 120 ℃ overnight to obtain the NaZSM-35 molecular sieve. Adding NaZSM-35 powder into 1M ammonium nitrate aqueous solution with the solid-liquid mass ratio of 1:10, violently stirring, carrying out ion exchange at 80 ℃, repeating the process for 3 times, drying the powder at 120 ℃ for 6h after filtering, and finally roasting in air at 500 ℃ for 5h to obtain the HZSM-35 molecular sieve, wherein an XRD spectrogram of a ZSM-35 sample is shown in native 4.
Example 4
AlPO 4 -25 molecular sieve synthesis: weighing 0.40g of white carbon black, 4.18g of aluminum isopropoxide, 2.36g of phosphoric acid and 1.35g of dimethylamine (40 wt%), adding the white carbon black into an agate mortar, grinding for 15-25min, then adding the mixture into a hydrothermal kettle, crystallizing for 24h at 200 ℃, quenching the mixture to room temperature in an ice water bath after crystallization is finished, repeatedly washing the mixture to be neutral by deionized water, drying at 120 ℃ overnight, and finally roasting for 5h in air at 500 ℃ to obtain AlPO 4 -25 molecular sieves, AlPO 4 The XRD spectrum of the-25 sample is shown in FIG. 5.
Example 5
SAPO-34 molecular sieve synthesis: weighing 0.15g of white carbon black, 0.58g of boehmite, 0.52g of ammonium dihydrogen phosphate and 1.30g of morpholine, adding the white carbon black, the boehmite, the ammonium dihydrogen phosphate and the morpholine into an agate mortar, grinding for 5-10min, then adding the obtained product into a hydrothermal kettle, crystallizing for 24h at 200 ℃, after crystallization is finished, carrying out ice water bath quenching to room temperature, repeatedly washing the product with deionized water to neutrality, drying the product overnight at 120 ℃, and finally roasting the product for 5h in air at 500 ℃ to obtain the SAPO-34 molecular sieve, wherein an XRD spectrogram of an SAPO-34 sample is shown in figure 6.
Example 6
Synthesis of HZSM-35@ SAPO-34 composite molecular sieve: weighing 1.0g of the HZSM-35 molecular sieve prepared in example 3, filling the weighed molecular sieve into agate, weighing 0.15g of white carbon black, 0.58g of boehmite, 0.52g of ammonium dihydrogen phosphate and 1.30g of morpholine, adding the weighed molecular sieve into an agate mortar filled with the HZSM-35 molecular sieve, grinding for 5-10min, adding the weighed molecular sieve into a hydrothermal kettle, crystallizing for 24h at 200 ℃, quenching to room temperature in an ice water bath after crystallization is finished, repeatedly washing the molecular sieve to be neutral by deionized water, drying overnight at 120 ℃, and finally roasting for 5h in air at 500 ℃ to obtain the HZSM-35@ SAPO-34 methylamine catalyst, wherein an XRD spectrogram of the HZSM-35@ SAPO-34 molecular sieve is shown in figure 7.
Example 7
Synthesizing an HZSM-5@ SAPO-34 composite molecular sieve: weighing 1.0g of the HZSM-5 molecular sieve prepared in example 2, filling the weighed molecular sieve into agate, weighing 0.15g of white carbon black, 0.58g of boehmite, 0.52g of ammonium dihydrogen phosphate and 1.30g of morpholine, adding the mixture into an agate mortar filled with the HZSM-5 molecular sieve, grinding for 5-10min, adding the mixture into a hydrothermal kettle, crystallizing for 24h at 200 ℃, rapidly cooling to room temperature in an ice water bath after crystallization is finished, repeatedly washing with deionized water to be neutral, drying at 120 ℃ overnight, and finally roasting for 5h in air at 500 ℃ to obtain the HZSM-5@ SAPO-34 methylamine catalyst, wherein an XRD spectrogram of the HZSM-5@ SAPO-34 molecular sieve is shown in figure 8.
Example 8
HZSM-5@AlPO 4 -25 composite molecular sieve synthesis: weighing 2.0g of the HZSM-5 molecular sieve prepared in example 2, putting the molecular sieve into agate, weighing 0.40g of white carbon black, 4.18g of aluminum isopropoxide, 2.36g of phosphoric acid and 1.35g of dimethylamine (40 wt%), adding the mixture into an agate mortar, grinding for 15-25min, adding the mixture into a hydrothermal kettle, crystallizing for 24h at 200 ℃, quenching to room temperature in an ice water bath after crystallization is finished, repeatedly washing with deionized water to be neutral, drying at 120 ℃ overnight, and finally roasting for 5h in air at 500 ℃ to obtain HZSM-5@ AlPO 4 -25 molecular sieves, HZSM-5@ AlPO 4 The XRD spectrum of the-25 molecular sieve is shown in figure 9.
Example 9
0.5g of CuZnAl methanol catalyst is filled, the particle size of the catalyst is 20-40 meshes, the catalyst is filled into a micro-reaction single tube, and the upper end and the lower end of the catalyst are fixed by quartz wool. The reaction conditions of the catalyst are as follows: 250 ℃, 0.5MPa, H 2 /CO/NH 3 The molar ratio of 2/1/1, the mixed gas flow rate is 20 mL/min. The reaction results are shown in table 1, the CO conversion is 8.1%, and the methanol selectivity reaches 99%, indicating that the CuZnAl methanol catalyst has very high selectivity.
Example 10
0.5g of CuZnAl methanol catalyst, 0.5g of HZSM-5@ SAPO-34 methylamine catalyst and methanol catalyst are all granulated into 20-40 meshes and are sequentially filled into a micro-reaction single tube, and the upper end and the lower end of each catalyst are fixed by quartz wool. The reaction conditions of the catalyst are as follows: 250 ℃, 0.5MPa, H 2 /CO/NH 3 The molar ratio of 2/1/1, the mixed gas flow rate is 20 mL/min. The reaction results are shown in table 1, with a CO conversion of 9.5% and a dimethylamine selectivity of 38%. The molecular sieve catalyst has stronger dehydration capability, and compared with the example 1, the dimethylamine selection type is obviously improved, and a small amount of dimethyl ether byproducts are generated.
Example 11
0.5g of CuZnAl methanol catalyst was charged0.5g of HZSM-35@ SAPO-34 methylamine catalyst, methanol and methanol catalyst are all granulated into 20-40 meshes and are sequentially filled into a micro-reverse single tube, and the upper end and the lower end of each catalyst are fixed by quartz wool. The reaction conditions of the catalyst are as follows: 250 ℃, 0.5MPa, H 2 /CO/NH 3 The molar ratio is 2/1/1, and the mixed gas flow rate is 20 mL/min. As shown in Table 1, the CO conversion rate was slightly lowered in comparative example 10. Because the HZSM-35 hole is smaller than that of ZSM-5, the selectivity of monomethylamine is obviously improved, and the selectivity of trimethylamine is inhibited.
Example 12
0.5g of CuZnAl methanol catalyst, 0.5g of HZSM-5@ AlPO were charged 4 The-25 methylamine catalyst, the methanol and the methanol catalyst are all granulated into 20-40 meshes and are sequentially filled into a micro-reaction single tube, and the upper end and the lower end of each catalyst are fixed by quartz wool. The reaction conditions of the catalyst are as follows: 250 ℃, 0.5MPa, H 2 The mol ratio of/CO/NH 3 is 2/1/1, and the flow rate of the mixed gas is 20 mL/min. The reaction results are shown in Table 1, where the CO conversion was 10.2%, and in comparative example 10, dimethylamine was significantly increased, indicating AlPO 4 -25 has strong shape-selective catalytic performance.
Example 13
0.5g of CuZnAl methanol catalyst, 0.5g of HZSM-5@ AlPO were charged 4 -25 parts of methylamine catalyst, methanol and methanol catalyst are all granulated into 20-40 meshes, mixed and then put into a micro-reverse single tube, and the upper end and the lower end of the catalyst are fixed by quartz wool. The reaction conditions of the catalyst are as follows: 250 ℃, 0.5MPa, H 2 /CO/NH 3 The molar ratio of 2/1/1, the mixed gas flow rate is 20 mL/min. As shown in Table 1, in comparative example 12, the CO conversion rate was further increased to 13.6%, the dimethylamine selectivity was 53%, and the trimethylamine selectivity was significantly decreased.
TABLE 1 catalytic reaction Activity and product Selectivity
Although the embodiments of the present invention and the accompanying drawings are disclosed for illustrative purposes, those skilled in the art will appreciate that: various substitutions, changes and modifications are possible without departing from the spirit and scope of the invention and the appended claims, and therefore the scope of the invention is not limited to the disclosure of the embodiments and the accompanying drawings.
Claims (6)
1. A method for directly preparing dimethylamine from synthesis gas is characterized in that: the method comprises two series reactions of reaction for preparing methanol from synthesis gas and methanol ammoniation reaction, wherein the reaction catalyst consists of a methanol catalyst and a methylamine catalyst, the method is carried out in a continuous fixed bed reactor, the reaction temperature is 200-400 ℃, the pressure is 0.1-5MPa, and the volume ratio of the raw material gas is H 2 /CO/NH 3 1-3:1:1-3, wherein the mass ratio of the methanol catalyst to the methylamine catalyst is 1:0.5-5, and the reaction for preparing methanol from synthesis gas is CO +2H 2 →CH 3 OH, methanol ammoniation reaction to CH 3 OH+NH 3 →(CH 3 ) 1-3 NH 0-2 +H 2 O, the methanol catalyst is CuZnAl catalyst which comprises 30 to 60 weight percent of CuO, 30 to 60 weight percent of ZnO and Al 2 O 3 5-10%, the catalyst is prepared by coprecipitation method, the methylamine catalyst is a composite molecular sieve material with core-shell structure, wherein the core is ZSM-5, and the shell is AlPO 4 -25。
2. The process of claim 1 for the direct production of dimethylamine from synthesis gas, wherein: the preparation method of the methanol catalyst comprises the following steps:
(1) copper salt, zinc salt and aluminum salt are added according to the proportion of 30-60 percent of CuO, 30-60 percent of ZnO and Al 2 O 3 Preparing a mixed salt solution by using 5-10% of metal in a molar ratio, wherein the copper salt solution and the zinc salt solution are one or more of a hydrochloride solution, a nitrate solution and an acetate solution;
(2) reacting the mixed salt solution with a precipitating agent, wherein the pH value of the solution is 8-10, the precipitation temperature is 40-80 ℃, and the precipitation is carried outThe precipitating agent is Na 2 CO 3 、NaHCO 3 One or more of NaOH and urea;
and after separating the precipitate from the mother liquor, repeatedly cleaning the precipitate by using deionized water at the temperature of 40-60 ℃, and then drying and roasting in the air at the drying temperature of 90-120 ℃ for 12-24h at the roasting temperature of 300-500 ℃ for 5-10h to obtain the methanol catalyst.
3. The method of claim 1, wherein the method comprises the steps of: the methylamine catalyst is prepared by a solid-phase synthesis method.
4. The process for producing dimethylamine directly from synthesis gas according to claim 1 or 3, wherein: the preparation method of the methylamine catalyst comprises the following steps: weighing 2.0g of HZSM-5 molecular sieve, putting the weighed molecular sieve into agate, weighing 0.40g of white carbon black, 4.18g of aluminum isopropoxide, 2.36g of phosphoric acid and 1.35g of 40 wt% dimethylamine, adding the mixture into an agate mortar, grinding for 15-25min, then adding the mixture into a hydrothermal kettle, crystallizing for 24h at 200 ℃, quenching the mixture to room temperature in an ice water bath after crystallization is finished, repeatedly washing the mixture to be neutral with deionized water, drying the mixture overnight at 120 ℃, and finally roasting the mixture for 5h in air at 500 ℃ to obtain HZSM-5@ AlPO 4 -25 molecular sieves.
5. The process of claim 4 for the direct production of dimethylamine from synthesis gas, wherein: the synthesis method of the HZSM-5 catalyst comprises the following steps: weighing 4.87g of white carbon black, 0.48g of boehmite, 0.28g of sodium hydroxide and 0.25g of tetrapropylammonium bromide, adding the white carbon black, the boehmite, the sodium hydroxide and the tetrapropylammonium bromide into an agate mortar, grinding for 5-10min, then adding the boehmite, the hydrothermally heated kettle, crystallizing for 16h at 200 ℃, after crystallization, rapidly cooling to room temperature in an ice water bath, repeatedly washing to be neutral by deionized water, drying overnight at 120 ℃ to obtain a NaZSM-5 molecular sieve, adding NaZSM-5 powder into a 1M ammonium nitrate aqueous solution with a solid-liquid mass ratio of 1:10, violently stirring, carrying out ion exchange at 80 ℃, repeating the process for 3 times, drying the powder at 120 ℃ for 6h after filtration, and finally roasting for 5h in air at 500 ℃ to obtain the HZSM-5 molecular sieve.
6. The process of claim 1 for the direct production of dimethylamine from synthesis gas, wherein: the catalyst is formed into tablets and sieved until the granularity is 20-80 meshes.
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CN111056948B (en) * | 2019-12-16 | 2021-03-30 | 中国科学院大连化学物理研究所 | Process for preparing hexamethylenediamine |
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 |
CN114426488B (en) * | 2020-10-10 | 2024-06-28 | 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 |
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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