CN112341339A - Method and device for synthesizing 1, 4-butanediamine - Google Patents
Method and device for synthesizing 1, 4-butanediamine Download PDFInfo
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- CN112341339A CN112341339A CN202011381327.XA CN202011381327A CN112341339A CN 112341339 A CN112341339 A CN 112341339A CN 202011381327 A CN202011381327 A CN 202011381327A CN 112341339 A CN112341339 A CN 112341339A
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- butyrolactone
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- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 25
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims abstract description 146
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 97
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims abstract description 74
- XGYKKVTZDQDYJQ-UHFFFAOYSA-N 4-aminobutanenitrile Chemical compound NCCCC#N XGYKKVTZDQDYJQ-UHFFFAOYSA-N 0.000 claims abstract description 62
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000005915 ammonolysis reaction Methods 0.000 claims abstract description 38
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000002808 molecular sieve Substances 0.000 claims abstract description 15
- 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 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 7
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 6
- 239000010941 cobalt Substances 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000003860 storage Methods 0.000 claims description 77
- 239000007788 liquid Substances 0.000 claims description 57
- 229910021529 ammonia Inorganic materials 0.000 claims description 26
- 238000007670 refining Methods 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000009776 industrial production Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 description 37
- 239000000047 product Substances 0.000 description 30
- 239000007789 gas Substances 0.000 description 9
- 239000012071 phase Substances 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 6
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 4
- 230000000813 microbial effect Effects 0.000 description 4
- AHLPHDHHMVZTML-UHFFFAOYSA-N Ornithine Chemical compound NCCCC(N)C(O)=O AHLPHDHHMVZTML-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical compound CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 229920003189 Nylon 4,6 Polymers 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004176 ammonification Methods 0.000 description 2
- 238000006114 decarboxylation reaction Methods 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- SSMHQPSHEZKUOM-UHFFFAOYSA-N 1,4-dibromobutan-1-amine Chemical compound BrC(CCCBr)N SSMHQPSHEZKUOM-UHFFFAOYSA-N 0.000 description 1
- 239000004475 Arginine Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- AHLPHDHHMVZTML-BYPYZUCNSA-N L-Ornithine Chemical compound NCCC[C@H](N)C(O)=O AHLPHDHHMVZTML-BYPYZUCNSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- UTJLXEIPEHZYQJ-UHFFFAOYSA-N Ornithine Natural products OC(=O)C(C)CCCN UTJLXEIPEHZYQJ-UHFFFAOYSA-N 0.000 description 1
- 108700005126 Ornithine decarboxylases Proteins 0.000 description 1
- 239000005700 Putrescine Substances 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000007098 aminolysis reaction Methods 0.000 description 1
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 1
- NHJPVZLSLOHJDM-UHFFFAOYSA-N azane;butanedioic acid Chemical compound [NH4+].[NH4+].[O-]C(=O)CCC([O-])=O NHJPVZLSLOHJDM-UHFFFAOYSA-N 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- MJGFBOZCAJSGQW-UHFFFAOYSA-N mercury sodium Chemical compound [Na].[Hg] MJGFBOZCAJSGQW-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229960003104 ornithine Drugs 0.000 description 1
- FYRHIOVKTDQVFC-UHFFFAOYSA-M potassium phthalimide Chemical compound [K+].C1=CC=C2C(=O)[N-]C(=O)C2=C1 FYRHIOVKTDQVFC-UHFFFAOYSA-M 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910001023 sodium amalgam Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000011426 transformation method Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/24—Oxygen or sulfur atoms
- C07D207/26—2-Pyrrolidones
- C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
- C07D207/267—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method and a device for synthesizing 1, 4-butanediamine, which are characterized in that 1, 4-butanediol raw material is sent into a cyclization reactor and is subjected to dehydrocyclization under the condition of a copper-based catalyst at the temperature of 200-250 ℃ to obtain gamma-butyrolactone; rectifying the gamma-butyrolactone, sending the rectified gamma-butyrolactone into an ammoniation reactor, reacting the rectified gamma-butyrolactone with liquid ammonia for a certain time at a set temperature, and finishing the reaction at 250 ℃ under the condition of 5-10MPa to obtain gamma-butyrolactam; sending the gamma-butyrolactam into an ammonolysis reactor, and carrying out ammonolysis ring-opening reaction with ammonia gas under the conditions of a nitrate molecular sieve catalyst and 420-500 ℃ to obtain 4-aminobutyronitrile; and (2) feeding the dehydrated 4-aminobutyronitrile into a hydrogenation reactor, and hydrogenating to obtain the 1, 4-butanediamine under the condition of 80-100 ℃ by using a nickel and cobalt loaded molecular sieve as a catalyst, wherein the raw material is simple and easy to obtain, the conversion rate is high, and the method is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of chemical processes, in particular to a method and a device for synthesizing 1, 4-butanediamine.
Background
1, 4-butanediamine (also called putrescine) is an important chemical intermediate and biochemical precursor, can be used for pharmacy and biochemical research, and can be used for preparing surfactants and agricultural chemicals, is an important raw material for synthesizing high-quality engineering plastics, namely polytetramethyleneadipamide (commonly called nylon 46, abbreviated as PA46), and has wide market prospect. Since the industrial production technology of butanediamine is monopolized abroad for a long time, domestic 1, 4-butanediamine mainly depends on import.
The existing methods for synthesizing 1, 4-butanediamine include chemical synthesis and biological synthesis. The chemical synthesis method is mainly obtained by hydrogenating succinonitrile obtained by reacting hydrogen cyanide with succinonitrile; or pyrrole reacts with hydroxylamine hydrochloride to generate butanedioxime under the action of sodium carbonate, and then the butanedioxime is heated and reduced by absolute ethyl alcohol under the action of sodium amalgam, or the butanedione is prepared by heating and catalyzing decarboxylation of 2, 5-diaminopentanoic acid; or decarboxylation and guanidine removal of arginine. Also adopts 1, 4-dibromobutylamine to react with potassium phthalimide and then react with methylamine to obtain 1, 4-butanediamine. The biological synthesis method is mainly characterized in that the microbial fermentation is used for directly synthesizing the butanediamine or the microbial conversion method is used for expressing an ornithine decarboxylase gene by using a microbial recombinant strain, and a substrate ornithine is converted into the butanediamine. Or a mode of combining biosynthesis and a chemical method, ammonium succinate is produced by microorganisms, and the butanediamine is obtained through dehydration reaction and hydrogenation reaction.
The chemical method or the method has the problems of harsh reaction conditions, complex steps, high requirements on process operation, expensive starting raw materials and the like, and the biological synthesis method or the microbial transformation method has higher requirements on the processes of strain breeding, fermentation and post-treatment, and has limited applicable raw materials. Therefore, it is necessary to develop a synthetic route which has simple process and easily available raw materials and is suitable for industrial production.
Disclosure of Invention
The invention aims to provide a method and a device for synthesizing 1, 4-butanediamine, which are suitable for industrial production.
In order to achieve the above object, in a first aspect, the present invention provides an apparatus for synthesizing 1, 4-butanediamine, the apparatus for synthesizing 1, 4-butanediamine includes a 1, 4-butanediol raw material tank, a cyclization reactor, a γ -butyrolactone rectification column, a γ -butyrolactone temporary storage tank, a liquid ammonia tank, an ammonification reactor, a first gas-liquid separator, a γ -butyrolactam temporary storage tank, an ammonia gas buffer tank, an ammonolysis reactor, a second gas-liquid separator, an ammonia gas refining column, a 4-aminobutyronitrile rectification column, a hydrogenation reactor, a third gas-liquid separator, a 1, 4-butanediamine product rectification column and a product tank, the 1, 4-butanediol raw material tank, the cyclization reactor, the γ -butyrolactone rectification column and the γ -butyrolactone temporary storage tank are sequentially connected by pipes, the liquid ammonia tank and the γ -butyrolactone temporary storage tank are both communicated with the ammonification reactor, the ammoniation reactor, the first gas-liquid separator and the gamma-butyrolactam temporary storage tank are sequentially connected by pipelines, the first gas-liquid separator is also connected with the ammonia refining tower through a pipeline, the liquid ammonia tank, the ammonia buffer tank, the ammonolysis reactor and the second gas-liquid separator are sequentially connected through a pipeline, the gamma-butyrolactam temporary storage tank is connected with the ammonolysis reactor through a pipeline, the second gas-liquid separator is respectively connected with the ammonia refining tower and the 4-aminobutyronitrile rectifying tower through pipelines, the 4-aminobutyronitrile rectifying tower is also connected with the gamma-butyrolactam temporary storage tank through a pipeline, the ammonia refining tower is also connected with the liquid ammonia tank through a pipeline, and the 4-aminobutyronitrile rectifying tower, the hydrogenation reactor, the third gas-liquid separator, the 1, 4-butanediamine product rectifying tower and the product tank are sequentially communicated through pipelines.
The device for synthesizing the 1, 4-butanediamine further comprises a 4-aminobutyronitrile temporary storage tank, and the 4-aminobutyronitrile temporary storage tank is connected with the 4-aminobutyronitrile rectifying tower and the hydrogenation reactor through pipelines.
The device for synthesizing the 1, 4-butanediamine further comprises a hydrogen storage tank, and the hydrogen storage tank is connected with the hydrogenation reactor through a pipeline.
The device for synthesizing 1, 4-butanediamine further comprises a first preheater, a second preheater and a third preheater, wherein the first preheater is connected with the 1, 4-butanediol raw material tank and the cyclization reactor through pipelines, the second preheater is connected with the gamma-butyrolactam temporary storage tank and the ammonolysis reactor through pipelines, and the third preheater is connected with the hydrogen storage tank and the hydrogenation reactor through pipelines.
The device for synthesizing the 1, 4-butanediamine further comprises a first condenser and a second condenser, wherein the first condenser is connected with the gamma-butyrolactone rectifying tower and the gamma-butyrolactone temporary storage tank through pipelines, and the second condenser is connected with the 4-aminobutyronitrile temporary storage tank and the 1, 4-butanediamine product rectifying tower through pipelines.
The device for synthesizing the 1, 4-butanediamine further comprises a first heat exchanger and a second heat exchanger, wherein the first heat exchanger is connected with the ammonolysis reactor and the second gas-liquid separator through pipelines, and the second heat exchanger is connected with the gamma-butyrolactam temporary storage tank and the 4-aminobutyronitrile rectifying tower through pipelines.
In a second aspect, the present invention provides a method for synthesizing 1, 4-butanediamine, wherein an apparatus for synthesizing 1, 4-butanediamine as described in the first aspect is adapted to a method for synthesizing 1, 4-butanediamine, comprising the steps of:
feeding the obtained 1, 4-butanediol into a cyclization reactor, and carrying out dehydrocyclization at 200-250 ℃ in the presence of a copper-based catalyst to obtain gamma-butyrolactone;
rectifying the gamma-butyrolactone, sending the rectified gamma-butyrolactone into an ammoniation reactor, reacting with liquid ammonia for a set time at a set temperature, and finishing the reaction at 250 ℃ under the condition of 5-10MPa to obtain gamma-butyrolactam;
sending the gamma-butyrolactam into an ammonolysis reactor, and carrying out ammonolysis ring-opening reaction with ammonia gas under the conditions of a nitrate molecular sieve catalyst and 420-500 ℃ to obtain 4-aminobutyronitrile;
and (3) feeding the dehydrated 4-aminobutyronitrile into a hydrogenation reactor, and hydrogenating to obtain the 1, 4-butanediamine under the condition of 80-100 ℃ by using a molecular sieve loaded with nickel and cobalt as a catalyst.
The invention relates to a method and a device for synthesizing 1, 4-butanediamine, wherein the device for synthesizing 1, 4-butanediamine comprises a 1, 4-butanediol raw material tank, a cyclization reactor, a gamma-butyrolactone rectifying tower, a gamma-butyrolactone temporary storage tank, a liquid ammonia tank, an ammoniation reactor, a first gas-liquid separator, a gamma-butyrolactam temporary storage tank, an ammonia buffer tank, an ammonolysis reactor, a second gas-liquid separator, an ammonia gas refining tower, a 4-aminobutyronitrile rectifying tower, a hydrogenation reactor, a third gas-liquid separator, a 1, 4-butanediamine product rectifying tower and a product tank, wherein the obtained 1, 4-butanediol is sent into the cyclization reactor, and is subjected to dehydrocyclization under the conditions of a copper-based catalyst and the temperature of 200-250 ℃ to obtain gamma-butyrolactone; rectifying the gamma-butyrolactone, sending the rectified gamma-butyrolactone into an ammoniation reactor, reacting the rectified gamma-butyrolactone with liquid ammonia at a set temperature, and reacting at 250 ℃ and 5-10MPa to obtain gamma-butyrolactam; sending the gamma-butyrolactam into an ammonolysis reactor, and carrying out ammonolysis ring-opening reaction with ammonia gas under the conditions of a nitrate molecular sieve catalyst and 420-500 ℃ to obtain 4-aminobutyronitrile; and (2) feeding the dehydrated 4-aminobutyronitrile into a hydrogenation reactor, and hydrogenating to obtain the 1, 4-butanediamine under the condition of 80-100 ℃ by using a nickel and cobalt loaded molecular sieve as a catalyst, wherein the raw material is simple and easy to obtain, the conversion rate is high, and the method is suitable for industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic structural diagram of an apparatus for synthesizing 1, 4-butanediamine provided by the invention.
FIG. 2 is a schematic diagram of the steps of a method for synthesizing 1, 4-butanediamine according to the present invention.
FIG. 3 is a molecular representation of 1, 4-butanediol provided herein.
FIG. 4 is a molecular expression of gamma-butyrolactone provided by the present invention.
FIG. 5 is a molecular expression of gamma-butyrolactams provided by the present invention.
FIG. 6 is a molecular representation of 4-aminobutyronitrile provided by the present invention.
FIG. 7 is a molecular representation of 4-aminobutyronitrile after dehydration according to the present invention.
FIG. 8 shows a molecular expression of 1, 4-butanediamine provided by the present invention.
1-1, 4-butanediol raw material tank, 2-cyclization reactor, 3-gamma-butyrolactone rectifying tower, 4-gamma-butyrolactone temporary storage tank, 5-liquid ammonia tank, 6-ammoniation reactor, 7-first gas-liquid separator, 8-gamma-butyrolactam temporary storage tank, 9-ammonia buffer tank, 10-aminolysis reactor, 11-second gas-liquid separator, 12-ammonia gas refining tower, 13-4-aminobutyronitrile rectifying tower, 14-hydrogenation reactor, 15-third gas-liquid separator, 16-1, 4-butanediamine product rectifying tower, 17-product tank, 18-4-aminobutyronitrile temporary storage tank, 19-hydrogen storage tank, 20-first preheater, 21-second preheater, 22-third preheater, 23-a first condenser, 24-a second condenser, 25-a first heat exchanger, 26-a second heat exchanger, 27-a first reboiler, 28-a second reboiler, 29-a third reboiler, 301-a first discharge port, 302-a second discharge port, 701-a third discharge port, 702-a fourth discharge port, 111-a fifth discharge port, 112-a sixth discharge port, 131-a seventh discharge port, 132-an eighth discharge port, 161-a ninth discharge port, and 162-a tenth discharge port.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In the description of the present invention, it is to be understood that the terms "length", "width", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on the orientations or positional relationships illustrated in the drawings, and are used merely for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed in a particular orientation, and be operated, and thus, are not to be construed as limiting the present invention.
Referring to fig. 1, the invention provides a device for synthesizing 1, 4-butanediamine, the device for synthesizing 1, 4-butanediamine comprises a 1, 4-butanediol raw material tank 1, a cyclization reactor 2, a gamma-butyrolactone rectifying tower 3, a gamma-butyrolactone temporary storage tank 4, a liquid ammonia tank 5, an ammoniation reactor 6, a first gas-liquid separator 7, a gamma-butyrolactam temporary storage tank 8, an ammonia gas buffer tank 9, an ammonolysis reactor 10, a second gas-liquid separator 11, an ammonia refining tower 12, a 4-aminobutyronitrile rectifying tower 13, a hydrogenation reactor 14, a third gas-liquid separator 15, a 1, 4-butanediamine product rectifying tower 16 and a product tank 17, the 1, 4-butanediol raw material tank 1, the cyclization reactor 2, the gamma-butyrolactone rectifying tower 3 and the gamma-butyrolactone temporary storage tank 4 are sequentially connected by pipelines, the liquid ammonia tank 5 and the gamma-butyrolactone temporary storage tank 4 are communicated with the ammoniation reactor 6, the first gas-liquid separator 7 and the gamma-butyrolactone temporary storage tank 8 are sequentially connected by a pipeline, the first gas-liquid separator 7 is further connected with the ammonia refining tower 12 by a pipeline, the liquid ammonia tank 5, the ammonia buffer tank 9, the ammonolysis reactor 10 and the second gas-liquid separator 11 are sequentially connected by a pipeline, the gamma-butyrolactone temporary storage tank 8 is connected with the ammonolysis reactor 10 by a pipeline, the second gas-liquid separator 11 is respectively connected with the ammonia refining tower 12 and the 4-aminobutyronitrile rectifying tower 13 by a pipeline, the 4-aminobutyronitrile rectifying tower 13 is further connected with the gamma-butyrolactone temporary storage tank 8 by a pipeline, the ammonia refining tower 12 is further connected with the liquid ammonia tank 5 by a pipeline, the 4-aminobutyronitrile rectifying tower 13, the hydrogenation reactor 14, the third gas-liquid separator 15, the 1, 4-butanediamine product rectifying tower 16 and the product tank 17 are sequentially communicated through pipelines.
In the present embodiment, the γ -butyrolactone rectification column 3 comprises a first discharge port 301 and a second discharge port 302, the first discharge port 301 is connected to the γ -butyrolactone temporary storage tank 4 by a pipeline, and the second discharge port 302 is connected to the cyclization reactor 2 by a pipeline; the first gas-liquid separator 7 comprises a third discharge port 701 and a fourth discharge port 702, the third discharge port 701 is connected with the ammonia gas refining tower 12 through a pipeline, the fourth discharge port 702 is connected with the gamma-butyrolactam temporary storage tank 8 through a pipeline, the second gas-liquid separator 11 comprises a fifth discharge port 111 and a sixth discharge port 112, the fifth discharge port 111 is connected with the ammonia gas refining tower 12 through a pipeline, the sixth discharge port 112 is connected with the 4-aminobutyronitrile rectifying tower 13 through a pipeline, the 4-aminobutyronitrile rectifying tower 13 comprises a seventh discharge port 131 and an eighth discharge port 132, the seventh discharge port 131 is connected with the hydrogenation reactor 14 through a pipeline, the eighth discharge port 132 is connected with the gamma-butyrolactam temporary storage tank 8 through a pipeline, the 1, 4-butanediamine product rectifying tower 16 comprises a ninth discharge port 161 and a tenth discharge port 162, the ninth discharge hole 161 is connected to the product tank 17 through a pipe, and the tenth discharge hole 162 is connected to the hydrogenation reactor 14 through a pipe.
Specifically, 1, 4-butanediol is preheated to 200-250 ℃ from a 14-butanediol raw material tank 1 by a raw material pump, then is sent into a dehydrocyclization reactor 2 (a fixed bed reactor) for dehydrocyclization reaction, the discharged gas-phase material is directly sent into a feed inlet positioned at the upper part of a gamma-butyrolactone rectifying tower 3, the prepared gamma-butyrolactone is sent into a temporary storage tank 4 of the gamma-butyrolactone through a first discharge port 301 of the gamma-butyrolactone rectifying tower 3, the unreacted raw material collected at the bottom of the tower returns to the cyclization reactor 2, the gamma-butyrolactone in the temporary storage tank 4 of the gamma-butyrolactone is sent into an ammoniation reactor 6 by an intermediate pump, liquid ammonia in a liquid ammonia tank 5 is sent into the ammoniation reactor 6 by a pump for pressurized reaction with the gamma-butyrolactone, the material after the reaction is decompressed and then is sent into a first gas-liquid separator 7, the third discharge port 701 of the first gas-liquid separator 7 directly feeds gas-phase discharge materials into the ammonia refining tower 12, the fourth discharge port 702 of the first gas-liquid separator 7 feeds liquid-phase discharge gamma-butyrolactam into the gamma-butyrolactam temporary storage tank 8, materials in the gamma-butyrolactam temporary storage tank 8 are preheated by a pump and then fed into the ammonolysis reactor 10, ammonia is preheated by the ammonia buffer tank 9 and then fed into the ammonolysis reactor 10, the reacted materials in the ammonolysis reactor 10 are cooled by heat exchange and then fed into the second gas-liquid separator 11, the gas phase discharged from the fifth discharge port 111 of the second gas-liquid separator 11 is fed into the ammonia refining tower 12, and the gas discharged from the ammonia refining tower 12 is liquefied by a compressor and then fed into the liquid ammonia tank 5. The liquid phase discharged from the sixth discharge port 112 of the second gas-liquid separator 11 is pumped into the 4-aminobutyronitrile rectifying tower 13, a seventh discharge hole 131 of the 4-aminobutyronitrile rectifying tower 13 preheats a material pump extracted from the tower top and then sends the preheated material into the hydrogenation reactor 14, the eighth discharge hole 132 of the 4-aminobutyronitrile rectifying tower 13 exchanges heat and cools the tower bottom material, and then returns the tower bottom material to the gamma-butyrolactam temporary storage tank 8, the hydrogen also enters the hydrogenation reactor 14 through preheating, the material reacted in the hydrogenation reactor 14 is cooled by the heat exchanger and then enters the third gas-liquid separator 15, the gas phase of the third gas-liquid separator 15 is discharged as tail gas, the liquid phase of the third gas-liquid separator 15 is pumped into the rectifying tower 16 of the 1, 4-butanediamine product, and a ninth discharge hole 161 of the 1, 4-butanediamine product rectifying tower 16 cools the discharged material at the bottom of the tower through a heat exchanger and then sends the cooled material into the product tank 17. And a tenth discharge hole 162 of the 1, 4-butanediamine product rectifying tower 16 condenses the materials at the top of the tower and returns the condensed materials to the hydrogenation reactor 14.
Further, the device for synthesizing 1, 4-butanediamine further comprises a first reboiler 27, a second reboiler 28 and a third reboiler 29, wherein the first reboiler 27 is connected with the gamma-butyrolactone rectifying tower 3 through a pipeline, the second reboiler 28 is connected with the 4-aminobutyronitrile rectifying tower 13 through a pipeline, and the third reboiler 29 is connected with the 1, 4-butanediamine product rectifying tower 16 through a pipeline.
In the present embodiment, the γ -butyrolactone rectification column 3 is heated and vaporized again through the second discharge port 302 by the first reboiler 27, and the 4-aminobutyronitrile rectification column 13 is heated and vaporized again through the eighth discharge port 132 by the second reboiler 28; the third reboiler 29 is used for heating and vaporizing the 1, 4-butanediamine product rectifying tower 16 again through the ninth discharge hole 161, so that the rectifying efficiency and effect of the gamma-butyrolactone rectifying tower 3, the 4-aminobutyronitrile rectifying tower 13 and the 1, 4-butanediamine product rectifying tower 16 are improved.
Further, the device for synthesizing 1, 4-butanediamine further comprises a 4-aminobutyronitrile temporary storage tank 18, and the 4-aminobutyronitrile temporary storage tank 18 is connected with the 4-aminobutyronitrile rectifying tower 13 and the hydrogenation reactor 14 through pipelines.
In this embodiment, the 4-aminobutyronitrile temporary storage tank 18 is used to store the material collected by the top condenser at the seventh discharge port 131 of the 4-aminobutyronitrile rectifying tower 13, and receive the condensed material from the tenth discharge port 162, so as to realize the recycling of resources and reduce the cost.
Further, the device for synthesizing 1, 4-butanediamine further comprises a hydrogen storage tank 19, and the hydrogen storage tank 19 is connected with the hydrogenation reactor 14 through a pipeline.
In the present embodiment, the hydrogen storage tank 19 is used to store hydrogen gas required for production.
Further, the device for synthesizing 1, 4-butanediamine further comprises a first preheater 20, a second preheater 21 and a third preheater 22, wherein the first preheater 20 is in pipeline connection with the 1, 4-butanediol raw material tank 1 and the cyclization reactor 2, the second preheater 21 is in pipeline connection with the gamma-butyrolactam temporary storage tank 8 and the ammonolysis reactor 10, and the third preheater 22 is in pipeline connection with the hydrogen storage tank 19 and the hydrogenation reactor 14.
In this embodiment, the first preheater 20 is used to preheat the 1, 4-butanediol transferred from the 1, 4-butanediol raw material tank 1 to 200-250 ℃, the second preheater 21 is used to preheat the ammonia gas transferred from the ammonia buffer tank 9 and the material in the gamma-butyrolactam temporary storage tank 8, and then the preheated ammonia gas is transferred to the ammonolysis reactor 10, and the third preheater 22 is used to preheat the material in the 4-aminobutyronitrile temporary storage tank 18 and the ammonia gas in the hydrogen storage tank 19, and then the preheated material is transferred to the hydrogenation reactor 14 for reaction, so that all the materials to be subjected to heating reaction are preheated in advance, the reaction time of the corresponding device is reduced, and the reaction rate is increased.
Further, the device for synthesizing 1, 4-butanediamine further comprises a first condenser 23 and a second condenser 24, wherein the first condenser 23 is connected with the gamma-butyrolactone rectifying tower 3 and the gamma-butyrolactone temporary storage tank 4 through pipelines, and the second condenser 24 is connected with the 4-aminobutanenitrile temporary storage tank 18 and the 1, 4-butanediamine product rectifying tower 16 through pipelines.
In this embodiment, the γ -butyrolactone extracted from the first condenser 23 at the top of the γ -butyrolactone rectifying tower 3 is condensed and sent to the γ -butyrolactone temporary storage tank 4, the material at the top of the 1, 4-butanediamine product rectifying tower 16 is returned to the 4-aminobutanenitrile temporary storage tank 18 through the second condenser 24, and the apparatus for synthesizing 1, 4-butanediamine further includes a plurality of condensers, which are not shown in fig. 1.
Further, the device for synthesizing 1, 4-butanediamine further comprises a first heat exchanger 25 and a second heat exchanger 26, wherein the first heat exchanger 25 is connected with the ammonolysis reactor 10 and the second gas-liquid separator 11 through pipelines, and the second heat exchanger 26 is connected with the gamma-butyrolactam temporary storage tank 8 and the 4-aminobutyronitrile rectifying tower 13 through pipelines.
In this embodiment, the reacted material in the ammonolysis reactor 10 is cooled by the first heat exchanger 25 and then enters the second gas-liquid separator 11, the material at the bottom of the 4-aminobutyronitrile rectifying tower 13 is cooled by the second heat exchanger 26 and then returns to the temporary storage tank 8 for gamma-butyrolactam, and the apparatus for synthesizing 1, 4-butanediamine further comprises a plurality of heat exchangers, and the high-temperature material is stored or processed in the next step after being subjected to heat exchange and cooling, so as to avoid generating by-products and influencing the service time of the apparatus. The apparatus for synthesizing 1, 4-butanediamine further comprises a plurality of heat exchangers, not shown in fig. 1.
Referring to fig. 2, the present invention provides a method for synthesizing 1, 4-butanediamine, and the apparatus for synthesizing 1, 4-butanediamine is suitable for a method for synthesizing 1, 4-butanediamine, comprising the following steps:
s101, feeding the obtained 1, 4-butanediol into a cyclization reactor 2, and carrying out dehydrocyclization at 200-250 ℃ in the presence of a copper-based catalyst to obtain gamma-butyrolactone.
Specifically, 1, 4-butanediol shown in fig. 3 is preheated to 200-250 ℃ from the 1, 4-butanediol raw material tank 1 by a first preheater 20 by a raw material pump, then is sent to a dehydrocyclization reactor 2 (fixed bed reactor), a copper-based catalyst (copper oxide or copper ferrochromate) is used as the catalyst, dehydrocyclization reaction is carried out at 200-250 ℃, the obtained gas-phase material is directly sent to a feed inlet at the upper part of a gamma-butyrolactone rectifying tower 3, the prepared gamma-butyrolactone shown in fig. 4 is sent to the gamma-butyrolactone temporary storage tank 4 through a first discharge port 301 of the gamma-butyrolactone rectifying tower 3, and unreacted raw materials collected at the bottom of the tower are returned to the cyclization reactor 2.
S102, rectifying the gamma-butyrolactone, sending the rectified gamma-butyrolactone into an ammoniation reactor 6, reacting with liquid ammonia for a set time at a set temperature, and finishing the reaction at 250 ℃ under the condition of 5-10MPa to obtain the gamma-butyrolactam.
Specifically, the gamma-butyrolactone in the gamma-butyrolactone temporary storage tank 4 is pumped into the ammoniation reactor 6 by an intermediate pump, the liquid ammonia in the liquid ammonia tank 5 is pumped into the ammoniation reactor 6 by a pump to react with the gamma-butyrolactone and the liquid ammonia at a set temperature below (-15 ℃) for a certain time, the temperature is raised to 250 ℃, the pressure reaction is carried out under the condition of 5-10MPa, the pressure of the reacted material is relieved, the reacted material is sent into the first gas-liquid separator 7, the gas phase discharged material is directly sent into the ammonia refining tower 12 through a third discharge port 701 of the first gas-liquid separator 7, and the liquid phase discharged material such as the gamma-butyrolactone shown in fig. 5 enters the gamma-butyrolactone temporary storage tank 8 through a fourth discharge port 702 of the first gas-liquid separator 7.
S103, sending the gamma-butyrolactam into an ammonolysis reactor 10, and carrying out ammonolysis ring-opening reaction with ammonia gas under the conditions of a nitrate molecular sieve catalyst and a temperature of 420-500 ℃ to obtain the 4-aminobutyronitrile.
Specifically, the materials in the gamma-butyrolactam temporary storage tank 8 are preheated by a pump and then sent into the ammonolysis reactor 10, the ammonia gas is preheated by the ammonia buffer tank 9 and then sent into the ammonolysis reactor 10, and the ammonia gas and the molecular sieve loaded with nitrates of magnesium, aluminum and nickel are subjected to ammonolysis ring-opening reaction at the temperature of 420-500 ℃ by taking the molecular sieve as a catalyst to obtain the 4-aminobutyronitrile shown in figure 6; the reacted material in the ammonolysis reactor 10 is cooled by the first heat exchanger 25 and then enters the second gas-liquid separator 11, the gas phase from the fifth discharge port 111 of the second gas-liquid separator 11 is sent to the ammonia refining tower 12, and the gas from the ammonia refining tower 12 is liquefied by a compressor and then sent to the liquid ammonia tank 5.
And S104, feeding the dehydrated 4-aminobutyronitrile into a hydrogenation reactor 14, and hydrogenating to obtain the 1, 4-butanediamine under the condition of 80-100 ℃ by using a molecular sieve loaded with nickel and cobalt as a catalyst.
Specifically, 4-aminobutyronitrile shown in figure 7 is obtained after 4-aminobutyronitrile shown in figure 6 is dehydrated; the liquid phase from the sixth discharge port 112 of the second gas-liquid separator 11 is pumped into the 4-aminobutyronitrile rectifying tower 13, the material extracted from the tower top is preheated by a pump and then sent into the hydrogenation reactor 14 through the seventh discharge port 131 of the 4-aminobutyronitrile rectifying tower 13, the material at the bottom of the tower is cooled by heat exchange and then returned to the gamma-butyrolactam temporary storage tank 8 through the eighth discharge port 132 of the 4-aminobutyronitrile rectifying tower 13, and hydrogen enters the hydrogenation reactor 14 through preheating, and is hydrogenated under the conditions of 80-100 ℃ and 2-6MPa by taking a nickel-cobalt-loaded molecular sieve as a catalyst to obtain the 1, 4-butanediamine shown in fig. 8. The material reacted in the hydrogenation reactor 14 enters the third gas-liquid separator 15 after heat exchange and temperature reduction, the gas phase of the third gas-liquid separator 15 is discharged as tail gas, the liquid phase of the third gas-liquid separator 15 is pumped into the 1, 4-butanediamine product rectifying tower 16, and the discharged material at the bottom of the 1, 4-butanediamine product rectifying tower 16 is sent into the product tank 17 after heat exchange and temperature reduction through a ninth discharge hole 161. And a tenth discharge hole 162 of the 1, 4-butanediamine product rectifying tower 16 condenses the materials at the top of the tower and returns the condensed materials to the hydrogenation reactor 14.
The invention relates to a method and a device for synthesizing 1, 4-butanediamine, wherein the device for synthesizing 1, 4-butanediamine comprises a 1, 4-butanediol raw material tank 1, a cyclization reactor 2, a gamma-butyrolactone rectifying tower 3, a gamma-butyrolactone temporary storage tank 4, a liquid ammonia tank 5, an ammoniation reactor 6, a first gas-liquid separator 7, a gamma-butyrolactam temporary storage tank 8, an ammonia gas buffer tank 9, an ammonolysis reactor 10, a second gas-liquid separator 11, an ammonia refining tower 12, a 4-aminobutyronitrile rectifying tower 13, a hydrogenation reactor 14, a third gas-liquid separator 15, a 1, 4-butanediamine product rectifying tower 16 and a product tank 17, the obtained 1, 4-butanediol is fed into a cyclization reactor 2, dehydrocyclization is carried out under the condition of 200-250 ℃ in the presence of a copper-based catalyst to obtain gamma-butyrolactone; rectifying the gamma-butyrolactone, sending the rectified gamma-butyrolactone into an ammoniation reactor 6, reacting with liquid ammonia for a certain time at a set temperature, and continuing to react at 250 ℃ under the condition of 5-10MPa to obtain gamma-butyrolactam; sending the gamma-butyrolactam into an ammonolysis reactor 10, and carrying out ammonolysis ring-opening reaction with ammonia gas under the conditions of a nitrate molecular sieve catalyst and a temperature of 420-500 ℃ to obtain 4-aminobutyronitrile; and (2) feeding the dehydrated 4-aminobutyronitrile into a hydrogenation reactor 14, and hydrogenating to obtain the 1, 4-butanediamine under the condition of 80-100 ℃ by using a nickel and cobalt loaded molecular sieve as a catalyst, wherein the raw material is simple and easy to obtain, the conversion rate is high, and the method is suitable for industrial production.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. A device for synthesizing 1, 4-butanediamine is characterized in that,
the device for synthesizing the 1, 4-butanediamine comprises a 1, 4-butanediol raw material tank, a cyclization reactor, a gamma-butyrolactone rectifying tower, a gamma-butyrolactone temporary storage tank, a liquid ammonia tank, an ammoniation reactor, a first gas-liquid separator, a gamma-butanelactam temporary storage tank, an ammonia gas buffer tank, an ammonolysis reactor, a second gas-liquid separator, an ammonia gas refining tower, a 4-aminobutyronitrile rectifying tower, a hydrogenation reactor, a third gas-liquid separator, a 1, 4-butanediamine product rectifying tower and a product tank, wherein the 1, 4-butanediol raw material tank, the cyclization reactor, the gamma-butyrolactone rectifying tower and the gamma-butyrolactone temporary storage tank are sequentially connected through pipelines, the liquid ammonia tank and the gamma-butyrolactone temporary storage tank are communicated with the ammoniation reactor, the first gas-liquid separator and the gamma-butanelactam temporary storage tank are sequentially connected through pipelines, the first gas-liquid separator is further connected with the ammonia refining tower through a pipeline, the liquid ammonia tank, the ammonia buffer tank, the ammonolysis reactor and the second gas-liquid separator are sequentially connected through a pipeline, the gamma-butyrolactam temporary storage tank is connected with the ammonolysis reactor through a pipeline, the second gas-liquid separator is respectively connected with the ammonia refining tower and the 4-aminobutyronitrile rectifying tower through a pipeline, the 4-aminobutyronitrile rectifying tower is further connected with the gamma-butyrolactam temporary storage tank through a pipeline, the ammonia refining tower is further connected with the liquid ammonia tank through a pipeline, and the 4-aminobutyronitrile rectifying tower, the hydrogenation reactor, the third gas-liquid separator, the 1, 4-butanediamine product rectifying tower and the product tank are sequentially communicated through a pipeline.
2. The apparatus for synthesizing 1, 4-butanediamine according to claim 1,
the device for synthesizing the 1, 4-butanediamine further comprises a 4-aminobutyronitrile temporary storage tank, and the 4-aminobutyronitrile temporary storage tank is connected with the 4-aminobutyronitrile rectifying tower and the hydrogenation reactor through pipelines.
3. The apparatus for synthesizing 1, 4-butanediamine according to claim 1,
the device for synthesizing the 1, 4-butanediamine further comprises a hydrogen storage tank, and the hydrogen storage tank is connected with the hydrogenation reactor through a pipeline.
4. A device for the synthesis of 1, 4-butanediamine according to claim 3,
the device for synthesizing the 1, 4-butanediamine further comprises a first preheater, a second preheater and a third preheater, wherein the first preheater is connected with the 1, 4-butanediol raw material tank and the cyclization reactor through pipelines, the second preheater is connected with the gamma-butyrolactam temporary storage tank and the ammonolysis reactor through pipelines, and the third preheater is connected with the hydrogen storage tank and the hydrogenation reactor through pipelines.
5. The apparatus for synthesizing 1, 4-butanediamine according to claim 2,
the device for synthesizing the 1, 4-butanediamine further comprises a first condenser and a second condenser, wherein the first condenser is connected with the gamma-butyrolactone rectifying tower and the gamma-butyrolactone temporary storage tank through pipelines, and the second condenser is connected with the 4-aminobutyronitrile temporary storage tank and the 1, 4-butanediamine product rectifying tower through pipelines.
6. The apparatus for synthesizing 1, 4-butanediamine of claim 5,
the device for synthesizing the 1, 4-butanediamine further comprises a first heat exchanger and a second heat exchanger, wherein the first heat exchanger is connected with the ammonolysis reactor and the second gas-liquid separator through pipelines, and the second heat exchanger is connected with the gamma-butyrolactam temporary storage tank and the 4-aminobutyronitrile rectifying tower through pipelines.
7. A method for synthesizing 1, 4-butanediamine, a device for synthesizing 1, 4-butanediamine according to any one of claims 1 to 6 being adapted to a method for synthesizing 1, 4-butanediamine, comprising the steps of:
feeding the obtained 1, 4-butanediol into a cyclization reactor, and carrying out dehydrocyclization at 200-250 ℃ in the presence of a copper-based catalyst to obtain gamma-butyrolactone;
rectifying the gamma-butyrolactone, sending the rectified gamma-butyrolactone into an ammoniation reactor, reacting with liquid ammonia for a set time at a set temperature, and finishing the reaction at 250 ℃ under the condition of 5-10MPa to obtain gamma-butyrolactam;
sending the gamma-butyrolactam into an ammonolysis reactor, and carrying out ammonolysis ring-opening reaction with ammonia gas under the conditions of a nitrate molecular sieve catalyst and 420-500 ℃ to obtain 4-aminobutyronitrile;
and (3) feeding the dehydrated 4-aminobutyronitrile into a hydrogenation reactor, and hydrogenating to obtain the 1, 4-butanediamine under the condition of 80-100 ℃ by using a molecular sieve loaded with nickel and cobalt as a catalyst.
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| CN112979496A (en) * | 2021-03-22 | 2021-06-18 | 平顶山市普恩科技有限公司 | Method and device for preparing 4-aminobutyronitrile by adopting pyrrolidone liquid phase method |
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