CN113831250B - Method, device and catalyst for preparing 1, 2-butanediamine - Google Patents
Method, device and catalyst for preparing 1, 2-butanediamine Download PDFInfo
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- CN113831250B CN113831250B CN202010583479.1A CN202010583479A CN113831250B CN 113831250 B CN113831250 B CN 113831250B CN 202010583479 A CN202010583479 A CN 202010583479A CN 113831250 B CN113831250 B CN 113831250B
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- catalyst
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- butanediamine
- epoxybutane
- catalytic amination
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- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 99
- ULEAQRIQMIQDPJ-UHFFFAOYSA-N butane-1,2-diamine Chemical compound CCC(N)CN ULEAQRIQMIQDPJ-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 claims abstract description 55
- 230000003197 catalytic effect Effects 0.000 claims abstract description 53
- 239000002994 raw material Substances 0.000 claims abstract description 49
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000005576 amination reaction Methods 0.000 claims abstract description 48
- 239000007795 chemical reaction product Substances 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 29
- 238000001994 activation Methods 0.000 claims description 26
- 238000005984 hydrogenation reaction Methods 0.000 claims description 26
- 230000008569 process Effects 0.000 claims description 24
- 230000004913 activation Effects 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 22
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 17
- 230000009471 action Effects 0.000 claims description 14
- 230000001681 protective effect Effects 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 14
- 239000005995 Aluminium silicate Substances 0.000 claims description 13
- 235000012211 aluminium silicate Nutrition 0.000 claims description 13
- 238000009833 condensation Methods 0.000 claims description 13
- 230000005494 condensation Effects 0.000 claims description 13
- 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 13
- 239000000463 material Substances 0.000 claims description 12
- 229910021536 Zeolite Inorganic materials 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000010457 zeolite Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 239000000440 bentonite Substances 0.000 claims description 7
- 229910000278 bentonite Inorganic materials 0.000 claims description 7
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- 229910052680 mordenite Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000010924 continuous production Methods 0.000 abstract description 3
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 3
- 231100000053 low toxicity Toxicity 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 20
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 20
- 238000005470 impregnation Methods 0.000 description 12
- 229910052746 lanthanum Inorganic materials 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- 230000002829 reductive effect Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000005342 ion exchange Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000000975 co-precipitation Methods 0.000 description 6
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 229910052758 niobium Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- -1 aliphatic amines Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- AHLPHDHHMVZTML-BYPYZUCNSA-N L-Ornithine Chemical compound NCCC[C@H](N)C(O)=O AHLPHDHHMVZTML-BYPYZUCNSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- AHLPHDHHMVZTML-UHFFFAOYSA-N Orn-delta-NH2 Natural products NCCCC(N)C(O)=O AHLPHDHHMVZTML-UHFFFAOYSA-N 0.000 description 2
- UTJLXEIPEHZYQJ-UHFFFAOYSA-N Ornithine Natural products OC(=O)C(C)CCCN UTJLXEIPEHZYQJ-UHFFFAOYSA-N 0.000 description 2
- 102000052812 Ornithine decarboxylases Human genes 0.000 description 2
- 108700005126 Ornithine decarboxylases Proteins 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 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 2
- 230000007547 defect Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229960003104 ornithine Drugs 0.000 description 2
- 210000001322 periplasm Anatomy 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000007098 aminolysis reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000004427 diamine group Chemical group 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000005913 hydroamination reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J23/83—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 rare earths or actinides
-
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- 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
- B01J29/42—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 containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for preparing 1, 2-butanediamine, a device and a catalyst thereof, wherein the method adopts 1, 2-epoxybutane and an ammonia source to carry out catalytic amination reaction, realizes the production of 1, 2-butanediamine under milder reaction conditions, has high yield, simple operation, low toxicity and no pollution of raw materials, and has good industrial application prospect by adopting a fixed bed reactor, and is easy for large-scale continuous production; the catalyst is a supported heterogeneous catalyst, and has high catalytic performance, wherein the selectivity of 1, 2-butanediamine is high.
Description
Technical Field
The invention relates to the technical field of butanediamine, relates to the technical field of preparation of 1, 2-butanediamine, and in particular relates to a method, a device and a catalyst for preparing 1, 2-butanediamine.
Background
The organic fatty amine and the derivative thereof are important chemical raw materials, are widely applied to various fields of daily chemicals, petrochemical industry and the like, and take very important roles in national economy. The derivative has important application in the fields of medicines, oil passivating agents, epoxy resin curing accelerators, spandex chain extenders, modified coatings and the like, and the related derivative can also be used as raw materials of rubber and coatings, chelating agents, mineral processing agents and the like, so that the demand is large.
The industrial lower aliphatic amines are produced by synthetic methods, and there have been formed an amine (ammo) method using a halogenated hydrocarbon as a raw material, a reductive amine (ammo) method, a hydroamination method using an organic nitrile as a raw material, a direct amine (ammo) method using an olefin as a raw material, a reductive method using a nitroaromatic compound as a raw material, and the like, which have corresponding industrial application examples in some products.
But currently, the butanediamine is mainly 1, 4-butanediamine, and the synthesis method is mainly a biological method.
CN105925629a discloses a method for synthesizing butanediamine through microbial transformation, by constructing recombinant strain of escherichia coli to secrete and express ornithine decarboxylase into periplasm cavity of escherichia coli, then adding substrate ornithine with a certain concentration into fermentation liquor, ornithine decarboxylase in the periplasm cavity converts ornithine into butanediamine, thus solving the problem of transferring butanediamine to outside cells; but the butanediamine synthesized by microbial conversion is 1, 4-butanediamine, and the 1, 2-butanediamine is difficult to prepare.
CN101735067a discloses a synthesis method of 1, 4-butanediamine, the method adopts 40% aqueous solution of methylamine as an aminolysis reagent to prepare 1, 4-butanediamine, and compared with biological method, the method has the advantages of simple and safe operation, higher reaction yield and low production cost, but the method cannot migrate to the preparation process of 1, 2-butanediamine.
CN101006183a discloses a biochemical synthesis method of 1, 4-butanediamine, which also uses a microbial mode to prepare 1, 4-butanediamine, so that it is difficult to prepare 1, 2-butanediamine.
In summary, the preparation of Guan Ding diamine is focused on the preparation of 1, 4-butanediamine, and few reports about the synthesis of 1, 2-butanediamine are provided, but the difunctional compound with the ortho diamine structure of the 1, 2-butanediamine is relatively active in nature and easy to react, and has better reactivity than that of the 1, 4-butanediamine in molecular structure in certain occasions.
Therefore, a process for preparing 1, 2-butanediamine needs to be developed to make up for the existing synthesis gap of 1, 2-butanediamine.
Disclosure of Invention
In view of the problems existing in the prior art, the invention provides a method for preparing 1, 2-butanediamine, a device and a catalyst thereof, wherein the method adopts 1, 2-epoxybutane and an ammonia source to carry out catalytic amination reaction, realizes the production of 1, 2-butanediamine under milder reaction conditions, has simple operation, is easy for large-scale continuous production by adopting a fixed bed reactor, and has good industrial application prospect; the catalyst is a supported heterogeneous catalyst, and has high catalytic performance, wherein the selectivity of 1, 2-butanediamine is high.
To achieve the purpose, the invention adopts the following technical scheme:
In a first aspect, the present invention provides a process for preparing 1, 2-butanediamine, the process comprising: and (3) carrying out catalytic amination reaction on an ammonia source and 1, 2-epoxybutane under the action of a catalyst to obtain the 1, 2-butanediamine.
The invention provides a method for preparing 1, 2-butanediamine by using an ammonia source and 1, 2-epoxybutane to catalyze amination reaction, which overcomes the defects that the existing butanediamine preparation focuses on the 1, 4-butanediamine preparation, the preparation of 1, 2-butanediamine is less involved, the reaction condition is mild, and the selectivity and the yield of the 1, 2-butanediamine are high.
The source of the 1, 2-epoxybutane is not particularly limited in the present invention, and sources of 1, 2-epoxybutane known to those skilled in the art may be used, and there is no limit to the number of pages.
Preferably, the 1, 2-butylene oxide is derived from the byproduct recovery of propylene oxide.
The industrial production of the 1, 2-epoxybutane mainly comes from the recovery of the byproduct of epoxypropane, and the comprehensive utilization of the part of 1, 2-epoxybutane can improve the added value of the product.
Preferably, the catalyst comprises a support, an active component and an adjunct supported on the support.
Preferably, the active component comprises Ni and/or Co, preferably Ni and Co.
Preferably, the auxiliary comprises a simple metal or an oxide of the simple metal.
Preferably, the elemental metal is selected from any one or a combination of at least two of Cu, zn, fe, nb, mo, ta, W, la, ce or Nd, wherein typical non-limiting combinations are combinations of Cu and Nb, combinations of Cu and La, combinations of La and Nb, combinations of Zn and Mo, combinations of Mo and Ta.
Preferably, the support comprises any one or a combination of at least two of SiO 2、Al2O3、ZrO2, kaolin, bentonite, montmorillonite, ZSM-5, zeolite X, zeolite Y, zeolite B, or mordenite, wherein typical non-limiting combinations are combinations of SiO 2 and Al 2O3, combinations of SiO 2 and kaolin, combinations of Al 2O3 and kaolin, combinations of Al 2O3 and bentonite, combinations of kaolin and bentonite, combinations of ZSM-5 and Al 2O3, combinations of ZSM-5 and ZrO 2, combinations of ZrO 2 and Al 2O3, preferably combinations of at least two, further preferably combinations of ZSM-5 and Al 2O3.
Preferably, the mass of the active component is 5-40% of the total mass of the catalyst, for example, 5%, 10%, 15%, 20%, 25%, 30%, 35% or 40%, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the mass of the auxiliary agent accounts for 0.5-10% of the total mass of the catalyst, for example, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, but is not limited to the recited values, and other non-recited values in the range of the values are equally applicable.
The particle size of the catalyst is preferably 0.1 to 15mm, and may be, for example, 0.1mm, 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm, 10mm, 11mm, 12mm, 13mm, 14mm or 15mm, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The method for preparing the catalyst is not particularly limited, and any method for preparing a supported catalyst, which is well known to those skilled in the art, may be used, and is not particularly limited.
Preferably, the catalyst is prepared by any one or a combination of at least two of an ion exchange method, an impregnation method, a co-precipitation method, and a mixing method, wherein the typical non-limiting combination is a combination of an ion exchange method and a co-precipitation method, a combination of an impregnation method and a co-precipitation method, a combination of an ion exchange method and an impregnation method, and a combination of an ion exchange method and a mixing method.
Preferably, the ammonia source comprises ammonia water or liquid ammonia, preferably liquid ammonia.
In the invention, liquid ammonia is preferably adopted, so that the energy consumption of subsequent separation can be reduced. The synthesis of the 1, 2-butanediamine which is an emerging diamine product by taking the 1, 2-epoxybutane and the liquid ammonia as raw materials is a relatively green and environment-friendly path, has great significance for the industrial production of the butanediamine and the derivatives thereof, and has good application prospect.
Preferably, the molar ratio of the liquid ammonia to the 1, 2-butylene oxide is (1 to 30): 1, which may be 1:1、2:1、3:1、4:1、5:1、6:1、7:1、8:1、9:1、10:1、11:1、12:1、13:1、14:1、15:1、16:1、17:1、18:1、19:1、20:1、21:1、22:1、23:1、24:1、25:1、26:1、27:1、28:1、29:1 or 30:1, for example, but is not limited to the values recited, and other values not recited in the range are equally applicable, preferably (2 to 20): 1.
The pressure of the catalytic amination reaction is preferably 0.1 to 20MPa, and may be, for example, 0.1MPa, 1MPa, 2MPa, 3MPa, 4MPa, 5MPa, 6MPa, 7MPa, 8MPa, 9MPa, 10MPa, 11MPa, 12MPa, 13MPa, 14MPa, 15MPa, 16MPa, 17MPa or 20MPa, but is not limited to the values recited, and other values not recited in the range are similarly applicable, and preferably 0.1 to 15MPa.
The temperature of the catalytic amination reaction is preferably 50 to 270 ℃, and may be, for example, 50 ℃, 70 ℃, 90 ℃,110 ℃, 130 ℃, 150 ℃, 170 ℃, 190 ℃, 210 ℃, 230 ℃, 250 ℃, or 270 ℃, but is not limited to the values recited, and other values not recited in the range are applicable, and preferably 70 to 250 ℃.
Preferably, the weight hourly space velocity of the 1, 2-epoxybutane is 0.1-6 h -1, for example 0.1h-1、1h-1、1.5h-1、2h-1、2.5h-1、3h-1、3.5h-1、4h-1、4.5h-1、5h-1、5.5h-1 or 6h -1, but is not limited to the values listed, and other values not listed in the range are equally applicable, preferably 0.3-3 h -1.
Preferably, the method comprises: and (3) carrying out catalytic amination reaction on an ammonia source and 1, 2-epoxybutane under the action of protective gas and a catalyst to obtain the 1, 2-butanediamine.
Preferably, the protective gas is hydrogen.
Preferably, the protective gas comprises 1 to 15% of the mole fraction of the reaction mass, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15%, but is not limited to the recited values, and other non-recited values within the range are equally applicable, preferably 1 to 10%.
Preferably, the reaction mass comprises a protective gas, 1, 2-butylene oxide and a source of ammonia.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) Preheating and mixing an ammonia source and 1, 2-epoxybutane in protective gas to obtain a preheated reaction raw material;
(2) And (3) carrying out catalytic amination reaction on the preheated reaction raw material in the step (1) under the action of a catalyst to obtain a reaction product, and carrying out condensation and gas-liquid separation on the reaction product to obtain the 1, 2-butanediamine.
The temperature of the preheating in the step (1) is preferably 65 to 300 ℃, and may be 65 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃, 240 ℃, 260 ℃, 280 ℃, or 300 ℃, for example, but is not limited to the values listed, and other values not listed in the range of the values are equally applicable.
Preferably, the preheating is performed in a preheater.
Preferably, the catalytic amination reaction in step (2) is carried out in a fixed bed reactor.
Preferably, the catalyst is subjected to hydrogenation activation and then catalytic amination reaction.
The hydrogenation activation temperature is preferably 400 to 500 ℃, and may be 400 ℃, 420 ℃, 440 ℃, 460 ℃, 480 ℃, or 500 ℃, for example, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the volume space velocity of the hydrogen in the hydrogenation activation process is 200-500 h -1, for example, 200h -1、250h-1、300h-1、350h-1、400h-1、450h-1 or 500h -1, but is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the hydrogenation activation treatment time is 2 to 5 hours, and may be, for example, 2.0 hours, 2.5 hours, 3.0 hours, 3.5 hours, 4.0 hours, 4.5 hours or 5.0 hours, but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the condensing temperature is-20 to 10 ℃, for example, -20 ℃, -10 ℃,0 ℃, 10 ℃ or 20 ℃, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) After the catalyst is hydrogenated and activated for 2 to 5 hours at the temperature of 400 to 500 ℃, the volume airspeed of hydrogen in the hydrogenation and activation process is 200 to 500 hours -1;
Preheating liquid ammonia and 1, 2-epoxybutane in protective gas to 65-300 ℃ for preheating and mixing to obtain a preheated reaction raw material;
Wherein, the mol ratio of the liquid ammonia to the 1, 2-epoxybutane is (1-30) 1, and the protective gas accounts for 1-15% of the mol fraction of the reaction materials;
(2) The preheated reaction raw material is subjected to catalytic amination reaction under the condition of 50-270 ℃ and 0.1-20 MPa under the action of a catalyst to obtain a reaction product, and the reaction product is subjected to condensation and gas-liquid separation to obtain 1, 2-butanediamine;
Wherein the weight hourly space velocity of the 1, 2-epoxybutane in the catalytic amination reaction process is 0.1-6 h -1.
In a second aspect, the present invention provides an apparatus for preparing 1, 2-butanediamine for performing the method for preparing 1, 2-butanediamine according to the first aspect. The device comprises a reaction unit, wherein the inlet end of the reaction unit is respectively and independently connected with a raw material conveying pipeline and a gas conveying pipeline.
The device for preparing the 1, 2-butanediamine can realize continuous production and has high industrial application prospect.
Preferably, the reaction unit comprises a preheater and a reactor which are sequentially connected, and the inlet end of the preheater is respectively and independently connected with the raw material conveying pipeline and the gas conveying pipeline.
Preferably, the reactor is a fixed bed reactor.
Preferably, the system further comprises a collection unit connected to the reaction unit.
Preferably, the collecting unit comprises a condenser and a gas-liquid separator connected in sequence.
Preferably, the condenser is connected to the reactor of the reaction unit.
In a third aspect, the present invention provides a catalyst for preparing 1, 2-butanediamine, the catalyst comprising a support, and an active component and an adjunct supported on the support; the active component comprises Ni and/or Co; the auxiliary agent comprises a metal simple substance or an oxide of the metal simple substance; the metal simple substance is selected from any one or at least two of Cu, zn, fe, nb, mo, ta, W, la, ce or Nd, wherein typical non-limiting combinations are combinations of Cu and Nb, combinations of Cu and La, combinations of La and Nb, combinations of Zn and Mo, and combinations of Mo and Ta.
The catalyst provided by the invention comprises a carrier, an active component and an auxiliary agent which are loaded on the carrier, has high catalytic performance, can be obtained by adopting various preparation methods, and has good application prospect.
Preferably, the support comprises any one or a combination of at least two of SiO 2、Al2O3、ZrO2, kaolin, bentonite, montmorillonite, ZSM-5, zeolite X, zeolite Y, zeolite B, or mordenite, wherein typical non-limiting combinations are combinations of SiO 2 and Al 2O3, combinations of SiO 2 and kaolin, combinations of Al 2O3 and kaolin, combinations of Al 2O3 and bentonite, combinations of kaolin and bentonite, combinations of ZSM-5 and Al 2O3, combinations of ZSM-5 and ZrO 2, combinations of ZrO 2 and Al 2O3, preferably combinations of at least two, further preferably combinations of ZSM-5 and Al 2O3.
Compared with other catalysts, the catalyst provided by the invention is preferably prepared by adopting at least two carriers, so that the catalytic effect of the catalyst can be further improved relatively.
Preferably, the active components are preferably Ni and Co.
The active component of the invention is preferably a combination of Ni and Co, and the catalytic effect is better.
Preferably, the mass of the active component is 5-40% of the total mass of the catalyst, for example, 5%, 10%, 15%, 20%, 25%, 30%, 35% or 40%, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the mass of the auxiliary agent accounts for 0.5-10% of the total mass of the catalyst, for example, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, but is not limited to the recited values, and other non-recited values in the range of the values are equally applicable.
The particle size of the catalyst is preferably 0.1 to 15mm, and may be, for example, 0.1mm, 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm, 10mm, 11mm, 12mm, 13mm, 14mm or 15mm, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The method for preparing the catalyst is not particularly limited, and any method for preparing a supported catalyst, which is well known to those skilled in the art, may be used, and is not particularly limited.
Preferably, the catalyst is prepared by any one or a combination of at least two of an ion exchange method, an impregnation method, a co-precipitation method, and a mixing method, wherein the typical non-limiting combination is a combination of an ion exchange method and a co-precipitation method, a combination of an impregnation method and a co-precipitation method, a combination of an ion exchange method and an impregnation method, and a combination of an ion exchange method and a mixing method.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The method for preparing the 1, 2-butanediamine provided by the invention can realize the catalytic amination of the 1, 2-butanediamine under milder reaction conditions, the conversion rate of the 1, 2-butanediamine is more than 60wt%, the selectivity of the 1, 2-butanediamine is more than 70wt%, under better conditions, the conversion rate of the 1, 2-butanediamine is more than 88wt%, the selectivity of the 1, 2-butanediamine is more than 90wt%, and the method is simple to operate, low in toxicity and pollution-free;
(2) The method for preparing the 1, 2-butanediamine adopts the fixed bed reactor, and the 1, 2-butanediamine can be continuously produced, so that the production efficiency is improved;
(3) The catalyst for preparing the 1, 2-butanediamine is a heterogeneous catalyst, is stable and efficient, and is easy to recycle; the preparation method is applied to the preparation process of the 1, 2-butanediamine, and has a good industrialized prospect.
Drawings
FIG. 1 is a schematic diagram of an apparatus used in the method for preparing 1, 2-butanediamine according to example 1 of the present invention.
In the figure: 1-a reactor; 2-a preheater; 201-a raw material conveying pipeline; 202-a gas delivery line; a 3-condenser; 301-a condensing medium inlet pipe; 302-condensing medium outlet pipe; 4-a gas-liquid separator; 401-a product discharge pipe; 402-backpressure-regulating assembly.
Detailed Description
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings.
The present invention will be described in further detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
1. Catalyst
Catalyst I
Catalyst I: 10% Ni-5% Co-1% La/(70% Al 2O3+14％ZrO2)
The preparation method of the catalyst I specifically comprises the following steps:
(1) 6.9g of nickel nitrate hexahydrate, 3.5g of cobalt nitrate hexahydrate and 0.43g of lanthanum nitrate hexahydrate are weighed and dissolved in 21.5g of water to obtain an impregnating solution;
(2) Dividing the prepared impregnating solution into 5 parts by weight, and then impregnating 11.7g of carrier Al 2O3 and ZrO 2 (40-60 meshes, 5 parts of Al 2O3 and 1 part of ZrO 2) with one part; drying the impregnated carrier particles at 110 ℃ for 12 hours, and roasting at 500 ℃ for 3 hours;
(3) Repeating the impregnation process of the step (2), and repeating the same treatment process for 4 times by using the rest four parts of impregnation liquid to finally obtain the supported catalyst with the composition of 10% Ni-5% Co-1% La (70% Al 2O3+14％ZrO2).
Catalyst II
Catalyst II: 10% Ni-5% Co-1% Cu/(64% Al 2O3 +20% ZSM-5)
The preparation method of the catalyst II specifically comprises the following steps:
(1) Weighing 6.9 of nickel nitrate hexahydrate and 3.5g of cobalt nitrate hexahydrate to dissolve in 16.5g of water to obtain an impregnating solution;
(2) Dividing the prepared impregnating solution into 5 parts by weight, impregnating 8.9g of carrier Al 2O3 powder with one part, drying the impregnated carrier at 110 ℃ for 12 hours, and roasting at 500 ℃ for 3 hours;
(3) Repeating the dipping process of the step (2), and repeating the same treatment process for 4 times by using the rest 4 parts of dipping liquid, wherein the obtained solid is marked as A;
(4) 0.53g of copper nitrate trihydrate and 2.8gZSM-5 powder are weighed and dispersed in 10g of water, then the mixture is reacted for 6 hours in a water bath at 90 ℃ under the condition of stirring, then the mixture is distilled and dried in a rotary way in a water bath at 80 ℃ to obtain a solid, and the solid is dried for 12 hours at 110 ℃, and the obtained solid is marked as B;
(5) Mixing the solid A and the solid B uniformly, granulating and screening the catalyst with 40-60 meshes for standby, thus obtaining the supported catalyst with the composition of 10 percent Ni-5 percent Co-1 percent Cu/(64 percent Al 2O3 +20 percent ZSM-5)
Catalyst III
Catalyst III: 10% Ni-5% Co-1% Cu/(70% Al 2O3 +14% Kaolin)
The preparation method of the catalyst III specifically comprises the following steps:
(1) 6.9g of nickel nitrate hexahydrate, 3.5g of cobalt nitrate hexahydrate and 0.53g of copper nitrate trihydrate are weighed and dissolved in 21.5g of water to obtain a salt solution; 11.7g of carrier Al 2O3 and kaolin (powder, al 2O3 accounting for 5 parts, kaolin accounting for 1 part) are dispersed in 60g of water to obtain a carrier suspension; 6g sodium hydroxide is dissolved in 100g water to obtain a precipitant solution;
(2) Then the precipitant solution and the salt solution are added into the suspension containing the carrier in parallel flow and drop way, and the pH value of the solution is controlled at 10; then filtering and washing, and drying the filter cake at 110 ℃ for 12 hours to obtain a catalyst precursor;
(3) The catalyst precursor is crushed and screened into 40-80 mesh particles, then the particles are uniformly mixed with 0.5 weight percent of graphite, and the particles are sintered for 3 hours at 500 ℃ after tabletting and molding, so as to obtain the supported catalyst with the composition of 10 percent Ni-5 percent Co-1 percent Cu/(70 percent Al 2O3 +14 percent kaolin).
Catalyst IV
Catalyst IV: 10% Ni-5% Co-1% Mo/Al 2O3
The preparation method of the catalyst IV specifically comprises the following steps:
12.7g of nickel oxide, 7.0g of cobalt oxide, 1.95g of molybdenum oxide, 84.0g of carrier Al 2O3 and 0.5g of graphite are weighed, uniformly mixed, granulated (40-80 meshes) in sequence, pressed into tablets, and baked for 3 hours at 500 ℃ to obtain the supported catalyst with the composition of 10% Ni-5% Co-1% Mo/Al 2O3.
Catalyst V
Catalyst V: 10% Ni-5% Co-1% La/(84% Al 2O3)
The preparation process of the catalyst V is the same as that of the catalyst I except that ZrO 2 is not added in the step (2) and Al 2O3 is adopted.
Catalyst VI
Catalyst VI: 15% Ni-1% La/(70% Al 2O3+14％ZrO2)
The preparation step of the catalyst VI is the same as the preparation method of the catalyst I except that cobalt nitrate hexahydrate is not added in the step (1) and correspondingly replaced by nickel nitrate hexahydrate.
Catalyst VII
Catalyst VII: 20% Ni-12% Co-0.5% La/(60% Al 2O3+7.5％ZrO2)
The preparation method of the catalyst VII specifically comprises the following steps:
(1) 13.8g of nickel nitrate hexahydrate, 8.4g of cobalt nitrate hexahydrate and 0.22g of lanthanum nitrate hexahydrate are weighed and dissolved in 18.0g of water to obtain an impregnating solution;
(2) Dividing the prepared impregnating solution into 5 parts by weight, and then impregnating 9.4g of carrier Al 2O3 and ZrO 2 (40-60 meshes, 8 parts of Al 2O3 and 1 part of ZrO 2) with one part; drying the impregnated carrier particles at 110 ℃ for 12 hours, and roasting at 500 ℃ for 3 hours;
(3) Repeating the impregnation process of the step (2), and repeating the same treatment process for 4 times by using the rest four parts of impregnation liquid to finally obtain the supported catalyst with the composition of 5% Ni-2% Co-0.5% La/(80% Al 2O3+12.5％ZrO2).
Catalyst VIII
Catalyst VIII: 2% Ni-5% Co-5% La/(80% Al 2O3+8％ZrO2)
The preparation method of the catalyst VIII specifically comprises the following steps:
(1) 1.4g of nickel nitrate hexahydrate, 3.5g of cobalt nitrate hexahydrate and 2.2g of lanthanum nitrate hexahydrate are weighed and dissolved in 22.5g of water to obtain an impregnating solution;
(2) Dividing the prepared impregnating solution into 5 parts by weight, and then impregnating 12.3g of carrier Al 2O3 and ZrO 2 (40-60 meshes, 10 parts of Al 2O3 and 1 part of ZrO 2) with one part; drying the impregnated carrier particles at 110 ℃ for 12 hours, and roasting at 500 ℃ for 3 hours;
(3) Repeating the impregnation process of the step (2), and repeating the same treatment process for 4 times by using the rest four parts of impregnation liquid to finally obtain the supported catalyst with the composition of 2% Ni-5% Co-5% La/(80% Al 2O3+8％ZrO2).
The percentage content of the catalyst is mass percentage content.
2. Examples
Example 1
The embodiment provides a method for preparing 1, 2-butanediamine, which specifically comprises the following steps:
(1) 4.2g (about 5 mL) of catalyst I was weighed and charged into a fixed bed reactor having a length of 1000mm and an inner diameter of 10.0 mm;
Before the catalytic amination reaction starts, carrying out hydrogenation activation on the supported catalyst, wherein the hydrogenation activation treatment conditions are as follows: hydrogen reduction treatment is carried out for 3h at 400 ℃ at a volume space velocity of 300h -1 under normal pressure;
The raw materials with the molar ratio of liquid ammonia to 1, 2-epoxybutane of 10:1 are conveyed to a preheater at the temperature of 90 ℃ for preheating and mixing, and the preheated reaction raw materials are obtained; wherein, the hydrogen in the reaction system accounts for 3 percent of the mole fraction of the reaction materials;
(2) When the temperature in the reactor is reduced to 100 ℃, the pressure is increased to 5MPa, the preheated reaction raw material enters the reactor to perform catalytic amination reaction under the action of a catalyst to obtain a reaction product, the reaction product enters a condenser to be condensed, the condensation temperature is minus 10 ℃, and the condensed reaction product enters a gas-liquid separator to perform gas-liquid separation to obtain 1, 2-butanediamine;
Wherein the weight hourly space velocity of the 1, 2-epoxybutane in the catalytic amination reaction process is 0.5h -1.
The apparatus used in the method for preparing 1, 2-butanediamine provided in example 1 is shown in fig. 1, the apparatus comprises a reaction unit, the reaction unit comprises a preheater 2 and a reactor 1 which are sequentially connected, the inlet end of the preheater 2 is respectively and independently connected with a raw material conveying pipeline 201 and a gas conveying pipeline 202, liquid ammonia and 1, 2-epoxybutane are respectively conveyed into the preheater 2 by the raw material conveying pipeline 201, and protective gas is conveyed into the preheater 2 by the gas conveying pipeline 202.
The device also comprises a collecting unit connected with the reaction unit, the collecting unit comprises a condenser 3 and a gas-liquid separator 4 which are sequentially connected along the discharging direction of the product, the condenser 3 is connected with the reactor 1, a condensing medium inlet pipe 301 and a condensing medium outlet pipe 302 are arranged on the condenser 3, and a product discharging pipe 401 and a back pressure adjusting component 402 are arranged on the gas-liquid separator 4.
Example 2
The embodiment provides a method for preparing 1, 2-butanediamine, which specifically comprises the following steps:
(1) 4.2g (about 5 mL) of catalyst I was weighed and charged into a fixed bed reactor having a length of 1000mm and an inner diameter of 10.0 mm;
Before the catalytic amination reaction starts, carrying out hydrogenation activation on the supported catalyst, wherein the hydrogenation activation treatment conditions are as follows: hydrogen reduction treatment is carried out for 3h at 400 ℃ at a volume space velocity of 300h -1 under normal pressure;
The raw materials with the molar ratio of liquid ammonia to 1, 2-epoxybutane of 10:1 are conveyed to a preheater at the temperature of 90 ℃ for preheating and mixing, and the preheated reaction raw materials are obtained; wherein, the hydrogen in the reaction system accounts for 3 percent of the mole fraction of the reaction materials;
(2) When the temperature in the reactor is reduced to 100 ℃, the pressure is increased to 8MPa, the preheated reaction raw material enters the reactor to perform catalytic amination reaction under the action of a catalyst to obtain a reaction product, the reaction product enters a condenser to be condensed, the condensation temperature is minus 10 ℃, and the condensed reaction product enters a gas-liquid separator to perform gas-liquid separation to obtain 1, 2-butanediamine;
Wherein the weight hourly space velocity of the 1, 2-epoxybutane in the catalytic amination reaction process is 0.5h -1.
Example 3
The embodiment provides a method for preparing butanediamine, which specifically comprises the following steps:
(1) 4.2g (about 5 mL) of catalyst I was weighed and charged into a fixed bed reactor having a length of 1000mm and an inner diameter of 10.0 mm;
Before the catalytic amination reaction starts, carrying out hydrogenation activation on the supported catalyst, wherein the hydrogenation activation treatment conditions are as follows: hydrogen reduction treatment is carried out for 3h at 400 ℃ at a volume space velocity of 300h -1 under normal pressure;
The raw materials with the molar ratio of liquid ammonia to 1, 2-epoxybutane of 10:1 are conveyed to a preheater at the temperature of 90 ℃ for preheating and mixing, and the preheated reaction raw materials are obtained; wherein, the hydrogen in the reaction system accounts for 3 percent of the mole fraction of the reaction materials;
(2) When the temperature in the reactor is reduced to 150 ℃, the pressure is increased to 8MPa, the preheated reaction raw material enters the reactor to perform catalytic amination reaction under the action of a catalyst to obtain a reaction product, the reaction product enters a condenser to be condensed, the condensation temperature is minus 10 ℃, and the condensed reaction product enters a gas-liquid separator to perform gas-liquid separation to obtain 1, 2-butanediamine;
Wherein the weight hourly space velocity of the 1, 2-epoxybutane in the catalytic amination reaction process is 0.5h -1.
Example 4
The embodiment provides a method for preparing 1, 2-butanediamine, which specifically comprises the following steps:
(1) 4.2g (about 5 mL) of catalyst I was weighed and charged into a fixed bed reactor having a length of 1000mm and an inner diameter of 10.0 mm;
Before the catalytic amination reaction starts, carrying out hydrogenation activation on the supported catalyst, wherein the hydrogenation activation treatment conditions are as follows: hydrogen reduction treatment is carried out for 3h at 400 ℃ at a volume space velocity of 300h -1 under normal pressure;
The raw materials with the molar ratio of liquid ammonia to 1, 2-epoxybutane of 10:1 are conveyed to a preheater at the temperature of 90 ℃ for preheating and mixing, and the preheated reaction raw materials are obtained; wherein, the hydrogen in the reaction system accounts for 3 percent of the mole fraction of the reaction materials;
(2) When the temperature in the reactor is reduced to 100 ℃, the pressure is increased to 5MPa, the preheated reaction raw material enters the reactor to perform catalytic amination reaction under the action of a catalyst to obtain a reaction product, the reaction product enters a condenser to be condensed, the condensation temperature is minus 10 ℃, and the condensed reaction product enters a gas-liquid separator to perform gas-liquid separation to obtain 1, 2-butanediamine;
wherein the weight hourly space velocity of the 1, 2-epoxybutane in the catalytic amination reaction process is 1h -1.
Example 5
The embodiment provides a method for preparing 1, 2-butanediamine, which specifically comprises the following steps:
(1) 4.2g (about 5 mL) of catalyst I was weighed and charged into a fixed bed reactor having a length of 1000mm and an inner diameter of 10.0 mm;
Before the catalytic amination reaction starts, carrying out hydrogenation activation on the supported catalyst, wherein the hydrogenation activation treatment conditions are as follows: hydrogen reduction treatment is carried out for 3h at 400 ℃ at a volume space velocity of 300h -1 under normal pressure;
the raw materials with the molar ratio of liquid ammonia to 1, 2-epoxybutane of 15:1 are conveyed to a preheater at the temperature of 90 ℃ for preheating and mixing, and the preheated reaction raw materials are obtained; wherein, the hydrogen in the reaction system accounts for 3 percent of the mole fraction of the reaction materials;
(2) When the temperature in the reactor is reduced to 100 ℃, the pressure is increased to 5MPa, the preheated reaction raw material enters the reactor to perform catalytic amination reaction under the action of a catalyst to obtain a reaction product, the reaction product enters a condenser to be condensed, the condensation temperature is minus 10 ℃, and the condensed reaction product enters a gas-liquid separator to perform gas-liquid separation to obtain 1, 2-butanediamine;
Wherein the weight hourly space velocity of the 1, 2-epoxybutane in the catalytic amination reaction process is 0.5h -1.
Example 6
The embodiment provides a method for preparing 1, 2-butanediamine, which specifically comprises the following steps:
(1) 4.2g (about 5 mL) of catalyst IV is weighed and put into a fixed bed reactor with the length of 1000mm and the inner diameter of 10.0 mm;
Before the catalytic amination reaction starts, carrying out hydrogenation activation on the supported catalyst, wherein the hydrogenation activation treatment conditions are as follows: hydrogen reduction treatment is carried out for 3h at 400 ℃ at a volume space velocity of 300h -1 under normal pressure;
The raw materials with the molar ratio of liquid ammonia to 1, 2-epoxybutane of 10:1 are conveyed to a preheater at the temperature of 90 ℃ for preheating and mixing, and the preheated reaction raw materials are obtained; wherein, hydrogen in the reaction system accounts for 5 percent of the mole fraction of the reaction materials;
(2) When the temperature in the reactor is reduced to 100 ℃, the pressure is increased to 5MPa, the preheated reaction raw material enters the reactor to perform catalytic amination reaction under the action of a catalyst to obtain a reaction product, the reaction product enters a condenser to be condensed, the condensation temperature is minus 20 ℃, and the condensed reaction product enters a gas-liquid separator to perform gas-liquid separation to obtain 1, 2-butanediamine;
Wherein the weight hourly space velocity of the 1, 2-epoxybutane in the catalytic amination reaction process is 0.5h -1.
Example 7
The embodiment provides a method for preparing 1, 2-butanediamine, which specifically comprises the following steps:
(1) 6.3g (about 8 mL) of catalyst II was weighed and charged into a fixed bed reactor having a length of 1200mm and an inner diameter of 15.0 mm;
Before the catalytic amination reaction starts, carrying out hydrogenation activation on the supported catalyst, wherein the hydrogenation activation treatment conditions are as follows: hydrogen reduction treatment is carried out for 5h at 500 ℃ and a volume space velocity of 500h -1 under normal pressure;
the raw materials with the molar ratio of liquid ammonia to 1, 2-epoxybutane of 30:1 are conveyed to a preheater with the temperature of 65 ℃ for preheating and mixing, and the preheated reaction raw materials are obtained; wherein, the hydrogen in the reaction system accounts for 10 percent of the mole fraction of the reaction materials;
(2) When the temperature in the reactor is reduced to 50 ℃, the pressure is increased to 10MPa, the preheated reaction raw material enters the reactor to perform catalytic amination reaction under the action of a catalyst to obtain a reaction product, the reaction product enters a condenser to be condensed, the condensation temperature is minus 10 ℃, and the condensed reaction product enters a gas-liquid separator to perform gas-liquid separation to obtain 1, 2-butanediamine;
Wherein the weight hourly space velocity of the 1, 2-epoxybutane in the catalytic amination reaction process is 0.1h -1.
Example 8
The embodiment provides a method for preparing 1, 2-butanediamine, which specifically comprises the following steps:
(1) 6.3g (about 8 mL) of catalyst III was weighed and charged into a fixed bed reactor having a length of 1200mm and an inner diameter of 15.0 mm;
before the catalytic amination reaction starts, carrying out hydrogenation activation on the supported catalyst, wherein the hydrogenation activation treatment conditions are as follows: hydrogen reduction treatment at 450 ℃ at a volume space velocity of 200h -1 for 2h under 102.5 kPa;
The raw materials with the molar ratio of liquid ammonia to 1, 2-epoxybutane of 5:1 are conveyed to a preheater at 270 ℃ for preheating and mixing, and the preheated reaction raw materials are obtained; wherein, hydrogen in the reaction system accounts for 1 percent of the mole fraction of the reaction materials;
(2) When the temperature in the reactor is 270 ℃, the pressure is increased to 1MPa, the preheated reaction raw material enters the reactor to perform catalytic amination reaction under the action of a catalyst to obtain a reaction product, the reaction product enters a condenser to be condensed, the condensation temperature is minus 10 ℃, and the condensed reaction product enters a gas-liquid separator to perform gas-liquid separation to obtain 1, 2-butanediamine;
Wherein the weight hourly space velocity of the 1, 2-epoxybutane in the catalytic amination reaction process is 6h -1.
Example 9
This example provides a process for preparing 1, 2-butanediamine which is the same as example 1 except that the liquid ammonia in step (1) is replaced with aqueous ammonia and the molar ratio of ammonia to 1, 2-butylene oxide in aqueous ammonia is maintained at 10:1.
Examples 10 to 13
Examples 10 to 13 provide a process for preparing 1, 2-butanediamine, which is the same as example 1, except that catalysts V to VIII are used, respectively.
3. Testing and results
The 1, 2-butanediamine obtained by gas-liquid separation in the above example was stabilized for 48 hours, then sampled and detected, and the mass content of 1, 2-butanediamine in the product was detected by gas chromatography, and the conversion rate of 1, 2-butylene oxide and the selectivity of 1, 2-butanediamine were calculated from the total sample amount, and the results are shown in table 1.
From table 1, the following points can be seen:
(1) It can be seen from comprehensive examples 1 to 12 that the method for preparing 1, 2-butanediamine provided in examples 1 to 12 uses 1, 2-epoxybutane as a raw material to perform catalytic amination reaction with an ammonia source, wherein the conversion rate of 1, 2-epoxybutane is more than 60wt%, the selectivity of 1, 2-butanediamine is more than 70wt%, under the preferred condition, the conversion rate of 1, 2-epoxybutane is more than 88wt%, and the selectivity of 1, 2-butanediamine is more than 90wt%, so that the method has good reaction effect and good industrial application prospect;
(2) As can be seen from the combination of example 1 and example 9, in example 1, liquid ammonia was used as the reaction raw material, and compared with the use of ammonia water as the reaction raw material in example 9, the conversion of 1, 2-butylene oxide in example 1 was 90wt%, the selectivity of 1, 2-butylene oxide was 95wt%, and the conversion of 1, 2-butylene oxide in example 9 was only 65wt% and the selectivity of 1, 2-butylene oxide was 78wt%, thus indicating that the preferred use of liquid ammonia in the present invention not only can reduce the subsequent waste water discharge, but also can improve the conversion and selectivity of the reaction;
(3) It can be seen from the combination of examples 1 and 10 to 11 that only Al 2O3 is used as the carrier in example 10 and only Ni is used as the active component in example 11, and that the selectivity and conversion in examples 10 and 11 are lower than those in examples when a combination of 70% Al 2O3+14％ZrO2 is used as the carrier and a combination of Ni and Co is used as the active component, thereby indicating that the catalytic amination effect is improved and the conversion of 1, 2-butylene oxide and the selectivity of 1, 2-butylene oxide are improved by preferably using a combination of Ni and Co as the active component and a combination of at least two of the carriers.
In summary, the method for preparing the 1, 2-butanediamine provided by the invention takes the 1, 2-epoxybutane and an ammonia source as reaction materials, can prepare the 1, 2-butanediamine under milder conditions, overcomes the defect that the existing market basically adopts 1, 4-butanediamine in preparation of the butanediamine, has high yield, simple operation, low toxicity and no pollution of raw materials, ensures that the conversion rate of the 1, 2-epoxybutane is more than 60wt%, and the selectivity of the 1, 2-butanediamine is more than 70wt%, and has good industrial application prospect; the catalyst provided by the invention has the advantages that the active components and the auxiliary agent are loaded on the carrier, so that the catalytic efficiency and selectivity are improved, and the catalyst has a good application prospect.
The applicant states that the detailed structural features of the present invention are described by the above embodiments, but the present invention is not limited to the above detailed structural features, i.e. it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
Claims (14)
1. A method of preparing 1, 2-butanediamine, the method comprising:
(1) Preheating and mixing liquid ammonia and 1, 2-epoxybutane in protective gas to obtain a preheated reaction raw material;
(2) The preheated reaction raw materials undergo catalytic amination reaction under the action of a catalyst to obtain a reaction product, and the reaction product is subjected to condensation and gas-liquid separation to obtain 1, 2-butanediamine;
wherein the protective gas is hydrogen; the protective gas accounts for 3-10% of the mole fraction of the reaction materials;
The molar ratio of the liquid ammonia to the 1, 2-epoxybutane is (10-30): 1; the pressure of the catalytic amination reaction is 0.1-20 MPa; the catalytic amination reaction is carried out in a fixed bed reactor; the weight hourly space velocity of the 1, 2-epoxybutane is 0.1-0.5 h -1;
The catalyst comprises a carrier, an active component and an auxiliary agent, wherein the active component and the auxiliary agent are loaded on the carrier;
The active components are Ni and Co;
The auxiliary agent comprises a metal simple substance; the metal simple substance is selected from any one or a combination of at least two of Cu, zn, fe, nb, mo, ta, W, la, ce and Nd;
The carrier comprises at least two of SiO 2、Al2O3、ZrO2, kaolin, bentonite, montmorillonite, ZSM-5, X-type zeolite, Y-type zeolite, B-type zeolite or mordenite;
the mass of the active component accounts for 15-32% of the total mass of the catalyst;
The mass of the auxiliary agent accounts for 0.5-1% of the total mass of the catalyst.
2. The process of claim 1, wherein the catalyst has a particle size of 0.1 to 15mm.
3. The process according to claim 1, wherein the pressure of the catalytic amination reaction is between 0.1 and 15MPa.
4. The process according to claim 1, wherein the temperature of the catalytic amination reaction is 50 to 270 ℃.
5. The process of claim 4, wherein the temperature of the catalytic amination reaction is 70 to 250 ℃.
6. The method of claim 1, wherein the reaction mass comprises a protective gas, 1, 2-butylene oxide, and liquid ammonia.
7. The method according to claim 1, wherein the preheating in step (1) is at a temperature of 65 to 300 ℃.
8. The method of claim 1, wherein the preheating is performed in a preheater.
9. The method of claim 1, wherein the catalyst is subjected to hydrogenation activation prior to catalytic amination.
10. The process according to claim 9, wherein the temperature of the hydrogenation activation is 400-500 ℃.
11. The method of claim 9, wherein the volumetric space velocity of hydrogen during the hydrogenation activation is from 200 to 500h -1.
12. The method according to claim 9, wherein the treatment time for the hydrogenation activation is 2 to 5 hours.
13. The method according to claim 1, wherein the temperature of condensation is-20 to 10 ℃.
14. The method according to claim 1, characterized in that it comprises the steps of:
(1) After the catalyst is hydrogenated and activated for 2 to 5 hours at the temperature of 400 to 500 ℃, the volume airspeed of hydrogen in the hydrogenation and activation process is 200 to 500 hours -1;
Preheating liquid ammonia and 1, 2-epoxybutane in protective gas to 65-300 ℃ for preheating and mixing to obtain a preheated reaction raw material;
wherein, the mol ratio of the liquid ammonia to the 1, 2-epoxybutane is (10-30) 1, and the protective gas accounts for 3-10% of the mol fraction of the reaction materials;
(2) The preheated reaction raw material is subjected to catalytic amination reaction under the condition of 50-270 ℃ and 0.1-20 MPa under the action of a catalyst to obtain a reaction product, and the reaction product is subjected to condensation and gas-liquid separation to obtain 1, 2-butanediamine;
Wherein the weight hourly space velocity of the 1, 2-epoxybutane in the catalytic amination reaction process is 0.1-0.5 h -1.
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