CN115959999A - Method for preparing hexamethylene diamine by ammoniation hydrogenation method of caprolactam - Google Patents
Method for preparing hexamethylene diamine by ammoniation hydrogenation method of caprolactam Download PDFInfo
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- CN115959999A CN115959999A CN202211622309.5A CN202211622309A CN115959999A CN 115959999 A CN115959999 A CN 115959999A CN 202211622309 A CN202211622309 A CN 202211622309A CN 115959999 A CN115959999 A CN 115959999A
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- catalyst
- ammoniation
- reaction
- caprolactam
- hydrogenation
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- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 title claims abstract description 76
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 96
- 239000003054 catalyst Substances 0.000 claims abstract description 93
- 230000018044 dehydration Effects 0.000 claims abstract description 34
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 27
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical group [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 22
- KBMSFJFLSXLIDJ-UHFFFAOYSA-N 6-aminohexanenitrile Chemical compound NCCCCCC#N KBMSFJFLSXLIDJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000007259 addition reaction Methods 0.000 claims abstract description 9
- 238000007599 discharging Methods 0.000 claims abstract description 7
- 230000008016 vaporization Effects 0.000 claims abstract description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 22
- 239000005751 Copper oxide Substances 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 22
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 22
- 229910000431 copper oxide Inorganic materials 0.000 claims description 22
- 239000002808 molecular sieve Substances 0.000 claims description 21
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000012018 catalyst precursor Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000004176 ammonification Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052744 lithium Chemical class 0.000 claims description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 3
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims 3
- 239000000047 product Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 22
- 239000003795 chemical substances by application Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- LNENGWNCTMIXGD-UHFFFAOYSA-L copper cobalt(2+) nitrate sulfate Chemical compound S(=O)(=O)([O-])[O-].[Cu+2].[N+](=O)([O-])[O-].[Co+2] LNENGWNCTMIXGD-UHFFFAOYSA-L 0.000 description 5
- 239000011258 core-shell material Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 4
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 125000005219 aminonitrile group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method for preparing hexamethylene diamine by ammoniation hydrogenation of caprolactam comprises the following steps: (1) Vaporizing caprolactam and liquid ammonia, then mixing and preheating in a mixer, and then performing an ammoniation reaction in a fixed bed filled with a dehydration ammoniation catalyst to obtain a reaction material; (2) Rectifying the reaction material to separate out 6-aminocapronitrile; (3) Placing 6-aminocapronitrile in a high-pressure reaction kettle filled with a hydrogenation catalyst; the hydrogenation catalyst is a cobalt-copper based catalyst; (4) Introducing hydrogen into the high-pressure reaction kettle, and discharging air; (5) Heating the high-pressure reaction kettle, continuously introducing hydrogen into the high-pressure reaction kettle, and performing addition reaction to obtain a reaction product after the reaction is finished; and (6) distilling the reaction product to obtain the hexamethylene diamine. The invention uses the dehydration ammoniation catalyst to ammoniate caprolactam, which can improve the production capacity of the reactor in unit volume; the raw materials are easily available, the reaction process is simple, and the product purity is high.
Description
Technical Field
The invention relates to the technical field of chemical catalysts, in particular to a method for preparing hexamethylene diamine by an ammoniation hydrogenation method of caprolactam.
Background
Hexamethylene diamine is an important chemical intermediate, and is mainly used for preparing nylon 66 and nylon 610; nylon 66 is the most important downstream product of hexamethylene diamine, and has wide application in chemical fiber industry, clothing and textile industry, electronic equipment, aerospace and other industries; with the rapid development of the new energy automobile industry, the future consumption of nylon 66 will continue to increase.
The main method of the hexamethylene diamine is patent CN 112079725A, ammonia gas, hydrogen gas and caprolactam are mixed and gasified, a catalyst is added into a mixed gas to carry out catalytic ammoniation reaction and catalytic hydrogenation reaction, materials obtained by the reaction are condensed and separated to obtain a reaction solution, and the obtained reaction solution is distilled to obtain a product hexamethylene diamine; the supported active components of the catalyst are nickel, palladium, platinum and rhodium. The method has the disadvantages of high catalysis cost, complex hydrogenation reaction and inconvenient operation.
Patent CN 111995526A discloses a method for synthesizing hexamethylenediamine by fixed bed hydrogenation, which comprises introducing 6-aminocapronitrile, a solvent, an auxiliary agent and hydrogen into a fixed bed reactor, and carrying out gas-liquid separation after the reaction is finished; distilling the obtained reaction liquid to obtain a recovered solvent and a hexamethylene diamine product; under the action of a catalyst, reacting amino nitrile organic matters with hydrogen in a solvent to obtain a reaction material containing organic diamine; and refining the reacted material to obtain crude organic diamine, and adsorbing and purifying the crude organic diamine to obtain purified organic diamine. The above method is too complicated to operate and is not suitable for large-scale production.
Disclosure of Invention
The invention aims to provide a method for preparing hexamethylene diamine by ammoniation hydrogenation of caprolactam, which comprises the steps of utilizing ammoniation of caprolactam to generate 6-aminocapronitrile, and then adopting a cobalt-copper-based catalyst to perform addition reaction on the 6-aminocapronitrile and hydrogen to obtain the hexamethylene diamine.
The method of the invention comprises the following steps:
1. vaporizing caprolactam and liquid ammonia, mixing and preheating in a mixer, and then performing an ammoniation reaction in a fixed bed filled with a dehydration ammoniation catalyst to obtain a reaction material;
2. rectifying the reaction material to separate out 6-aminocapronitrile;
3. placing 6-aminocapronitrile in a high-pressure reaction kettle filled with a hydrogenation catalyst; the hydrogenation catalyst is a cobalt-copper based catalyst;
4. introducing hydrogen into the high-pressure reaction kettle, and discharging air;
5. heating the high-pressure reaction kettle, continuously introducing hydrogen into the high-pressure reaction kettle, and performing an addition reaction to obtain a reaction product;
6. and distilling the reaction product to obtain the hexamethylene diamine.
In the step 1, the dehydration ammoniation catalyst is a dehydration ammoniation molecular sieve using an alumina molecular sieve as a carrier, and is represented as follows: the method comprises the following steps of (1) calculating by mass percentage of metal simple substance in the aluminum oxide molecular sieve: a% Ag-b% L i-alumina molecular sieve, wherein: a% =3-5%, b% =3-5%.
In the step 1, the preparation method of the dehydration ammoniation catalyst comprises the following steps: dissolving silver nitrate containing 3-5% of Ag by mass of the aluminum oxide molecular sieve and lithium sulfate containing 3-5% of Li by mass of the aluminum oxide molecular sieve in deionized water to prepare a mixed solution; adding the prepared mixed solution into aluminum oxide molecular sieve powder, stirring, standing, filtering and drying to obtain a catalyst precursor; the standing time is 10-12h; the drying is drying for 4-6h at 100-120 ℃ in an oven; roasting the catalyst precursor at 550 +/-10 ℃ for 4-6h to obtain the dehydration ammoniation catalyst; the silver and lithium metal salts are dissolved in deionized water according to the liquid-solid mass ratio of 10-12.
In the step 1, the preheating temperature is 270-350 ℃; the reaction is carried out in a fixed bed filled with a dehydration ammoniation catalyst, and the top pressure of the fixed bed filled with the dehydration ammoniation catalyst is 0.01-0.1KPa; the reaction temperature is 360-450 ℃.
In the step 1, the molar ratio of the caprolactam to the liquid ammonia is 1.
In the step 1, the amination reaction has the reaction formula:
in the step 5, the reaction formula of the addition reaction is:
in the step 3, the cobalt-copper based catalyst is a supported catalyst; the carrier of the catalyst is silicon dioxide, and the supported active components of the catalyst are cobalt oxide and copper oxide; the molar ratio of cobalt oxide to copper oxide is 1: (1-10).
In the step 5, the temperature is increased to 100-135 ℃ in the high-pressure reaction kettle.
In the step 5, hydrogen is introduced into the high-pressure reaction kettle, and the pressure in the high-pressure reaction kettle is 1-4MPa.
In the step 5, when the reaction time reaches 20-24h, the reaction is completed.
In the step 6, the purity of the obtained hexamethylene diamine is more than or equal to 99 percent.
In the step 6, after the distillation is finished, the yield of the hexamethylene diamine is more than or equal to 90 percent.
The invention uses the dehydration ammoniation catalyst to ammoniate caprolactam, which can improve the production capacity of the reactor in unit volume; using cobalt-copper catalyst, reacting 6-aminocapronitrile at high temperature and high pressure to generate hexamethylene diamine; the raw materials are easily available, the reaction process is simple, and the product purity is high; the catalyst adopted by the method is low in cost and suitable for industrial large-scale production.
Detailed Description
In the description of the present invention, it is to be noted that those whose specific conditions are not specified in the examples are carried out according to the conventional conditions or the conditions recommended by the manufacturers. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the embodiment of the present invention, the dehydration ammoniation catalyst is a dehydration ammoniation molecular sieve using an alumina molecular sieve as a carrier, and is represented as follows: the method comprises the following steps of (1) calculating by mass percentage of metal simple substance in the aluminum oxide molecular sieve: a% Ag-b% L i-alumina molecular sieve, wherein: a% =4%, b% =4%.
In the embodiment of the invention, the preparation method of the dehydration ammoniation catalyst comprises the following steps: dissolving silver nitrate containing Ag in an amount of 4% by mass of the aluminum oxide molecular sieve and lithium sulfate containing Li in an amount of 4% by mass of the aluminum oxide molecular sieve in deionized water to prepare a mixed solution; adding the prepared mixed solution into aluminum oxide molecular sieve powder, stirring, standing, filtering and drying to obtain a catalyst precursor; the standing time is 11h; the drying is carried out for 5 hours in an oven at 110 ℃; roasting the catalyst precursor at 550 +/-10 ℃ for 5 hours to obtain the dehydration ammoniation catalyst; the silver and lithium metal salts are dissolved in deionized water according to the liquid-solid mass ratio of 11.
In the cobalt-copper catalyst of the present invention: the carrier is silicon dioxide; the shell layer of the core-shell structure is a porous structure and comprises cobalt oxide and copper oxide; the molar ratio of cobalt oxide to copper oxide is 1: (1-10); the thickness of the shell layer is 10-100nm; the steps are carried out in the following way: mixing the shell forming solution and the carrier to obtain a mixture; the molar ratio of the shell forming solution to the positive elements of the carrier is 0.5-2; the shell forming solution is a copper nitrate-cobalt sulfate mixed solution with the concentration of 25-35%, wherein the molar ratio of cobalt to copper is 1: (1-10); the mixing temperature is 20-100 ℃, and the mixing time is 1-6h; adjusting the pH value of the mixture to coat the carrier, wherein the pH regulator is hydrochloric acid to obtain a coated system; carrying out solid-liquid separation on the coated system, drying the separated solid phase, and roasting at 450-550 ℃ for 1-40h to obtain an intermediate; mixing the intermediate, a binder, a peptizing agent and water for molding, wherein the peptizing agent is a sulfuric acid solution with the mass concentration of 20-30%, and the binder is polyvinyl alcohol; wherein the mass ratio of water to the intermediate is 0.4-0.9, the mass ratio of water to the peptizing agent is 1; drying the formed material, and roasting for the second time at the roasting temperature of 560-650 ℃ for 6-8h to obtain the cobalt-copper catalyst.
Example 1
Vaporizing caprolactam (2 mol) and liquid ammonia, preheating, mixing in a mixer, and then performing an ammoniation reaction in a fixed bed filled with a dehydration ammoniation catalyst (1 g of loaded active components in total) to obtain a reaction material; the preheating temperature is 270 ℃; the reaction is carried out in a fixed bed filled with a dehydration ammoniation catalyst, and the top pressure of the fixed bed filled with the dehydration ammoniation catalyst is 0.01KPa; the reaction temperature is 360 ℃; the molar ratio of caprolactam to liquid ammonia is 1;
rectifying the reaction material to separate out 6-aminocapronitrile;
placing 6-aminocapronitrile in a high-pressure reaction kettle filled with a hydrogenation catalyst; the hydrogenation catalyst is a cobalt-copper based catalyst; the cobalt-copper based catalyst is a supported catalyst; the carrier of the catalyst is silicon dioxide, and the supported active components of the catalyst are cobalt oxide and copper oxide; the molar ratio of cobalt oxide to copper oxide is 1:1; cobalt-copper catalyst: the carrier is silicon dioxide; the shell layer of the core-shell structure is a porous structure and comprises cobalt oxide and copper oxide; the molar ratio of cobalt oxide to copper oxide is 1:1; the thickness of the shell layer is 10-100nm; the steps are carried out in the following way: mixing the shell forming solution and the carrier to obtain a mixture; the molar ratio of the shell forming solution to the positive elements of the carrier is 0.5; the shell forming solution is a 30% copper nitrate-cobalt sulfate mixed solution, wherein the molar ratio of cobalt to copper is 1:1; the mixing temperature is 20 ℃, and the mixing time is 6 hours; adjusting the pH value of the mixture to coat the carrier, wherein the pH regulator is hydrochloric acid to obtain a coated system; carrying out solid-liquid separation on the coated system, drying the separated solid phase, and roasting at 450 ℃ for 8h to obtain an intermediate; mixing and molding the intermediate, a binder, a peptizing agent and water, wherein the peptizing agent is a sulfuric acid solution with the mass concentration of 20%, and the binder is polyvinyl alcohol; wherein the mass ratio of water to the intermediate is 0.4; drying the formed material, and then roasting for the second time, wherein the roasting temperature is 560 ℃, and the roasting time is 8 hours, so as to obtain a cobalt-copper catalyst;
introducing hydrogen into the high-pressure reaction kettle, and discharging air;
heating the high-pressure reaction kettle, continuously introducing hydrogen into the high-pressure reaction kettle, and performing an addition reaction to obtain a reaction product; heating to 100 ℃ of the high-pressure reaction kettle; introducing hydrogen into the high-pressure reaction kettle, wherein the pressure in the high-pressure reaction kettle is 1MPa; when the reaction time reaches 24h, the reaction is finished;
distilling the reaction product to obtain hexamethylene diamine;
the purity of hexamethylene diamine is 99.2%; the yield of hexamethylenediamine was 93% (216 g).
Example 2
Vaporizing caprolactam (4 mol) and liquid ammonia, preheating, mixing in a mixer, and then performing an ammoniation reaction in a fixed bed filled with a dehydration ammoniation catalyst (loaded with 2g of active components) to obtain a reaction material; the preheating temperature is 300 ℃; the reaction is carried out in a fixed bed filled with a dehydration ammoniation catalyst, and the top pressure of the fixed bed filled with the dehydration ammoniation catalyst is 0.05KPa; the reaction temperature is 380 ℃; the molar ratio of caprolactam to liquid ammonia is 1;
rectifying the reaction material to separate out 6-aminocapronitrile;
placing 6-aminocapronitrile in a high-pressure reaction kettle filled with a hydrogenation catalyst; the hydrogenation catalyst is a cobalt-copper based catalyst; the cobalt-copper based catalyst is a supported catalyst; the carrier of the catalyst is silicon dioxide, and the supported active components of the catalyst are cobalt oxide and copper oxide; the molar ratio of cobalt oxide to copper oxide is 1:3; cobalt-copper catalyst: the carrier is silicon dioxide; the shell layer of the core-shell structure is a porous structure and comprises cobalt oxide and copper oxide; the molar ratio of cobalt oxide to copper oxide is 1:3; the thickness of the shell layer is 10-100nm; the steps are carried out in the following way: mixing the shell forming solution and the carrier to obtain a mixture; the molar ratio of the shell forming solution to the positive valence elements of the carrier is 1; the shell forming solution is a copper nitrate-cobalt sulfate mixed solution with the concentration of 25%, wherein the molar ratio of cobalt to copper is 1:3; the mixing temperature is 40 ℃, and the mixing time is 4 hours; adjusting the pH value of the mixture to coat the carrier, wherein the pH regulator is hydrochloric acid to obtain a coated system; carrying out solid-liquid separation on the coated system, drying the separated solid phase, and roasting at 500 ℃ for 6h to obtain an intermediate; mixing the intermediate, a binder, a peptizing agent and water for molding, wherein the peptizing agent is a sulfuric acid solution with the mass concentration of 25%, and the binder is polyvinyl alcohol; wherein the mass ratio of water to the intermediate is 0.5; drying the formed material, and then roasting for the second time at 580 ℃ for 6 hours to obtain a cobalt-copper catalyst;
introducing hydrogen into the high-pressure reaction kettle, and discharging air;
heating the high-pressure reaction kettle, continuously introducing hydrogen into the high-pressure reaction kettle, and performing addition reaction to obtain a reaction product after the reaction is finished; heating to 115 ℃ of the high-pressure reaction kettle; introducing hydrogen into the high-pressure reaction kettle, wherein the pressure in the high-pressure reaction kettle is 2MPa; when the reaction time reaches 23h, the reaction is finished;
distilling the reaction product to obtain hexamethylene diamine;
the purity of the hexamethylene diamine is 99.5 percent; the yield of hexamethylenediamine was 92% (428 g).
Example 3
Vaporizing caprolactam (5 mol) and liquid ammonia, preheating, mixing in a mixer, and then performing an ammoniation reaction in a fixed bed filled with a dehydration ammoniation catalyst (loaded with 3g of active components) to obtain a reaction material; the preheating temperature is 350 ℃; the reaction is carried out in a fixed bed filled with a dehydration ammoniation catalyst, and the top pressure of the fixed bed filled with the dehydration ammoniation catalyst is 0.1KPa; the reaction temperature is 450 ℃; the molar ratio of caprolactam to liquid ammonia is 1;
rectifying the reaction material to separate out 6-aminocapronitrile;
placing 6-aminocapronitrile in a high-pressure reaction kettle filled with a hydrogenation catalyst; the hydrogenation catalyst is a cobalt-copper based catalyst; the cobalt-copper based catalyst is a supported catalyst; the carrier of the catalyst is silicon dioxide, and the loaded active components of the catalyst are cobalt oxide and copper oxide; the molar ratio of cobalt oxide to copper oxide is 1:5; cobalt-copper catalyst: the carrier is silicon dioxide; the shell layer of the core-shell structure is a porous structure and comprises cobalt oxide and copper oxide; the molar ratio of cobalt oxide to copper oxide is 1:5; the thickness of the shell layer is 10-100nm; the steps are carried out in the following way: mixing the shell forming solution and the carrier to obtain a mixture; the molar ratio of the shell forming solution to the positive elements of the carrier is 1.5; the shell forming solution is a 35% copper nitrate-cobalt sulfate mixed solution, wherein the molar ratio of cobalt to copper is 1:5; the mixing temperature is 60 ℃, and the mixing time is 3h; adjusting the pH value of the mixture to coat the carrier, wherein the pH regulator is hydrochloric acid to obtain a coated system; carrying out solid-liquid separation on the coated system, drying the separated solid phase, and roasting at 550 ℃ for 3 hours to obtain an intermediate; mixing and molding the intermediate, a binder, a peptizing agent and water, wherein the peptizing agent is a sulfuric acid solution with the mass concentration of 30%, and the binder is polyvinyl alcohol; wherein the mass ratio of water to the intermediate is 0.6; drying the formed material, and then roasting for the second time at the roasting temperature of 620 ℃ for 7 hours to obtain a cobalt-copper catalyst;
introducing hydrogen into the high-pressure reaction kettle, and discharging air;
heating the high-pressure reaction kettle, continuously introducing hydrogen into the high-pressure reaction kettle, and performing an addition reaction to obtain a reaction product; heating to 125 deg.c in the high pressure reactor; introducing hydrogen into the high-pressure reaction kettle, wherein the pressure in the high-pressure reaction kettle is 3MPa; when the reaction time reaches 22h, the reaction is finished;
distilling the reaction product to obtain hexamethylene diamine;
the purity of the hexamethylene diamine is 99.7 percent; the yield of hexamethylenediamine was 91% (529 g).
Example 4
Vaporizing caprolactam (7 mol) and liquid ammonia, preheating, mixing in a mixer, and then performing an ammoniation reaction in a fixed bed filled with a dehydration ammoniation catalyst (3.2 g of loaded active components in total) to obtain a reaction material; the preheating temperature is 300 ℃; the reaction is carried out in a fixed bed filled with a dehydration ammoniation catalyst, and the top pressure of the fixed bed filled with the dehydration ammoniation catalyst is 0.08KPa; the reaction temperature is 400 ℃; the molar ratio of caprolactam to liquid ammonia is 1;
rectifying the reaction material to separate out 6-aminocapronitrile;
placing 6-aminocapronitrile in a high-pressure reaction kettle filled with a hydrogenation catalyst; the hydrogenation catalyst is a cobalt-copper based catalyst; the cobalt-copper based catalyst is a supported catalyst; the carrier of the catalyst is silicon dioxide, and the loaded active components of the catalyst are cobalt oxide and copper oxide; the molar ratio of cobalt oxide to copper oxide is 1:10; cobalt-copper catalyst: the carrier is silicon dioxide; the shell layer of the core-shell structure is a porous structure and comprises cobalt oxide and copper oxide; the molar ratio of cobalt oxide to copper oxide is 1:10; the thickness of the shell layer is 10-100nm; the steps are carried out in the following way: mixing the shell forming solution and the carrier to obtain a mixture; the molar ratio of the shell forming solution to the positive valence elements of the carrier is 2; the shell forming solution is a copper nitrate-cobalt sulfate mixed solution with the concentration of 35%, wherein the molar ratio of cobalt to copper is 1:10; the mixing temperature is 100 ℃, and the mixing time is 1h; adjusting the pH value of the mixture to coat the carrier, wherein the pH regulator is hydrochloric acid to obtain a coated system; carrying out solid-liquid separation on the coated system, drying the separated solid phase, and roasting at 550 ℃ for 3h to obtain an intermediate; mixing the intermediate, a binder, a peptizing agent and water for molding, wherein the peptizing agent is a sulfuric acid solution with the mass concentration of 30%, and the binder is polyvinyl alcohol; wherein the mass ratio of water to the intermediate is 0.9; drying the formed material, and then roasting for the second time at the roasting temperature of 650 ℃ for 6 hours to obtain a cobalt-copper catalyst;
introducing hydrogen into the high-pressure reaction kettle, and discharging air;
heating the high-pressure reaction kettle, continuously introducing hydrogen into the high-pressure reaction kettle, and performing an addition reaction to obtain a reaction product; heating to 135 ℃ of the high-pressure reaction kettle; introducing hydrogen into the high-pressure reaction kettle, wherein the pressure in the high-pressure reaction kettle is 4MPa; when the reaction time reaches 20h, the reaction is finished;
distilling the reaction product to obtain hexamethylene diamine;
the purity of the hexamethylene diamine is 99.8 percent; the yield of hexamethylenediamine was 90% (732 g).
Example 5
Carrying out a scale-up test according to the protocol of example 1; caprolactam (28000 mol) and liquid ammonia are vaporized, preheated, mixed in a mixer, and then put into a fixed bed filled with a dehydration and ammoniation catalyst (100 g of loaded active components) for ammoniation reaction, wherein the reaction mode is the same as that of example 1; the purity of hexamethylene diamine is 99.3%; the yield of hexamethylenediamine was 91% (2961 kg).
While the foregoing description shows and describes several preferred embodiments of the invention, it is to be understood, as noted above, that the invention is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the inventive concept as expressed herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. A method for preparing hexamethylene diamine by ammoniation hydrogenation of caprolactam is characterized by comprising the following steps:
(1) Vaporizing caprolactam and liquid ammonia, then mixing and preheating in a mixer, and then performing an ammoniation reaction in a fixed bed filled with a dehydration ammoniation catalyst to obtain a reaction material;
(2) Rectifying the reaction material to separate out 6-aminocapronitrile;
(3) Placing 6-aminocapronitrile in a high-pressure reaction kettle filled with a hydrogenation catalyst; the hydrogenation catalyst is a cobalt-copper based catalyst;
(4) Introducing hydrogen into the high-pressure reaction kettle, and discharging air;
(5) Heating the high-pressure reaction kettle, continuously introducing hydrogen into the high-pressure reaction kettle, and performing addition reaction to obtain a reaction product after the reaction is finished;
(6) And distilling the reaction product to obtain the hexamethylene diamine.
2. The method for preparing hexamethylene diamine by ammoniation hydrogenation of caprolactam according to claim 1, wherein in the step (1), the dehydration and ammoniation catalyst is a dehydration and ammoniation molecular sieve using an alumina molecular sieve as a carrier, and is represented as follows: the method comprises the following steps of (1) calculating by mass percentage of metal simple substance in the aluminum oxide molecular sieve: a% Ag-b% Li-alumina molecular sieve, wherein: a% =3-5%, b% =3-5%.
3. The method for preparing hexamethylene diamine by ammoniation hydrogenation of caprolactam as claimed in claim 1, wherein in the step (1), the dehydration and ammoniation catalyst is prepared by the following steps: dissolving silver nitrate containing Ag with the mass being 3-5% of that of the aluminum oxide molecular sieve and lithium sulfate containing Li with the mass being 3-5% of that of the aluminum oxide molecular sieve in deionized water to prepare a mixed solution; adding the prepared mixed solution into aluminum oxide molecular sieve powder, stirring, standing, filtering and drying to obtain a catalyst precursor; the standing time is 10-12h; the drying is drying for 4-6h at 100-120 ℃ in an oven; roasting the catalyst precursor at 550 +/-10 ℃ for 4-6h to obtain the dehydration ammoniation catalyst; the silver and lithium metal salts are dissolved in deionized water according to the liquid-solid mass ratio of 10-12.
4. The method for preparing hexamethylene diamine by ammoniation hydrogenation of caprolactam according to claim 1, wherein the preheating temperature in step (1) is 270-350 ℃; the reaction is carried out in a fixed bed filled with a dehydration ammoniation catalyst, and the top pressure of the fixed bed filled with the dehydration ammoniation catalyst is 0.01-0.1KPa; the reaction temperature is 360-450 ℃.
5. The method for preparing hexamethylene diamine by ammoniation hydrogenation of caprolactam according to claim 1, wherein in step (1), the molar ratio of caprolactam to liquid ammonia is 1.
6. The method for preparing hexamethylene diamine by ammoniation hydrogenation of caprolactam according to claim 1, wherein in the step (3), the cobalt-copper based catalyst is a supported catalyst; the carrier of the catalyst is silicon dioxide, and the loaded active components of the catalyst are cobalt oxide and copper oxide; the molar ratio of cobalt oxide to copper oxide is 1: (1-10).
7. The method for preparing hexanediamine by ammonification and hydrogenation of caprolactam as claimed in claim 1, wherein the temperature in the step (5) is raised to 100-135 ℃ in the autoclave.
8. The method for preparing hexanediamine by ammonification and hydrogenation of caprolactam as claimed in claim 1, wherein in the step (5), hydrogen is introduced into the high-pressure reactor, and the pressure in the high-pressure reactor is 1-4MPa.
9. The method for preparing hexanediamine by ammonification and hydrogenation of caprolactam as claimed in claim 1, wherein the reaction is completed in the step (5) when the reaction time reaches 20-24 h.
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| CN111574400A (en) * | 2020-06-10 | 2020-08-25 | 江苏扬农化工集团有限公司 | Separation method of ammoniated and dehydrated product of caprolactam and synthesis method of hexamethylene diamine |
| CN112079725A (en) * | 2020-09-22 | 2020-12-15 | 江苏扬农化工集团有限公司 | Method for producing hexamethylene diamine |
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| CN112812020A (en) * | 2021-02-08 | 2021-05-18 | 陈天然 | Method and device for producing hexamethylene diamine from caprolactam |
| CN113461539A (en) * | 2021-08-02 | 2021-10-01 | 江苏扬农化工集团有限公司 | Method for preparing organic diamine from amino nitrile organic matter |
| CN113582853A (en) * | 2021-08-02 | 2021-11-02 | 江苏扬农化工集团有限公司 | Method and device for preparing organic diamine from organic amide |
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| CN111574400A (en) * | 2020-06-10 | 2020-08-25 | 江苏扬农化工集团有限公司 | Separation method of ammoniated and dehydrated product of caprolactam and synthesis method of hexamethylene diamine |
| CN112079725A (en) * | 2020-09-22 | 2020-12-15 | 江苏扬农化工集团有限公司 | Method for producing hexamethylene diamine |
| CN112110832A (en) * | 2020-09-22 | 2020-12-22 | 江苏扬农化工集团有限公司 | Method for efficiently synthesizing hexamethylene diamine key intermediate |
| CN112812020A (en) * | 2021-02-08 | 2021-05-18 | 陈天然 | Method and device for producing hexamethylene diamine from caprolactam |
| CN113461539A (en) * | 2021-08-02 | 2021-10-01 | 江苏扬农化工集团有限公司 | Method for preparing organic diamine from amino nitrile organic matter |
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