CN112079725A - Method for producing hexamethylene diamine - Google Patents
Method for producing hexamethylene diamine Download PDFInfo
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- CN112079725A CN112079725A CN202010999418.3A CN202010999418A CN112079725A CN 112079725 A CN112079725 A CN 112079725A CN 202010999418 A CN202010999418 A CN 202010999418A CN 112079725 A CN112079725 A CN 112079725A
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- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 title claims abstract description 270
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 62
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 354
- 238000006243 chemical reaction Methods 0.000 claims abstract description 145
- 239000007789 gas Substances 0.000 claims abstract description 114
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 86
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 77
- 230000003197 catalytic effect Effects 0.000 claims abstract description 75
- 239000003054 catalyst Substances 0.000 claims abstract description 60
- 239000000463 material Substances 0.000 claims abstract description 59
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 43
- 238000002156 mixing Methods 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 54
- 239000000047 product Substances 0.000 claims description 51
- 238000000926 separation method Methods 0.000 claims description 34
- 238000009833 condensation Methods 0.000 claims description 33
- 230000005494 condensation Effects 0.000 claims description 33
- 229910052759 nickel Inorganic materials 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 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 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000005576 amination reaction Methods 0.000 claims 2
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 40
- 239000012071 phase Substances 0.000 description 30
- 238000011068 loading method Methods 0.000 description 15
- 238000005086 pumping Methods 0.000 description 15
- KBMSFJFLSXLIDJ-UHFFFAOYSA-N 6-aminohexanenitrile Chemical compound NCCCCCC#N KBMSFJFLSXLIDJ-UHFFFAOYSA-N 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 125000006239 protecting group Chemical group 0.000 description 3
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/22—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of other functional groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- C07C209/50—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 carboxylic acid amides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
- C07D201/16—Separation or purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
- C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings 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
- C07D223/08—Oxygen atoms
- C07D223/10—Oxygen atoms attached in position 2
Abstract
The invention relates to the technical field of organic chemical industry, in particular to a method for producing hexamethylene diamine, which comprises the following steps: mixing and gasifying ammonia gas, hydrogen gas and caprolactam to obtain mixed gas; adding a catalyst into the obtained mixed gas to perform a catalytic ammoniation reaction and a catalytic hydrogenation reaction; and then, condensing and separating the materials obtained by the reaction to obtain reaction liquid, and distilling the obtained reaction liquid to obtain the product hexamethylene diamine. The invention innovatively and optimally designs the hexamethylene diamine production process method to be finished in one step, effectively solves the problems of long and complicated process route, high energy material consumption and difficulty in industrial large-scale production commonly existing in the existing hexamethylene diamine production technology, comprehensively recycles the residue materials of the kettle after the hexamethylene diamine product is extracted, obviously reduces energy consumption, greatly reduces production cost, ensures that the reaction is safer and more stable, effectively improves product selectivity and process safety, and is suitable for industrial large-scale production, popularization and application.
Description
Technical Field
The invention relates to the technical field of organic chemical industry, in particular to a method for producing hexamethylene diamine.
Background
Hexamethylenediamine is a key raw material in the nylon industry, is usually used for synthesizing nylon 66 and nylon 610, and then is prepared into products such as nylon resin, nylon fibers, engineering plastics and the like. The industrial production method of the hexamethylene diamine is mainly a adiponitrile catalytic hydrogenation method, and the method produces impurity diaminocyclohexane which has large influence on the quality of nylon products while producing the hexamethylene diamine, and is difficult to separate. At present, with the increasing expansion of caprolactam production capacity and the decreasing price, the caprolactam method is expected to be popularized industrially. The caprolactam method takes caprolactam as a raw material to prepare 6-aminocapronitrile through catalytic ammoniation, and then the 6-aminocapronitrile is further subjected to catalytic hydrogenation to obtain the hexamethylene diamine.
In the prior art, patent CN107739318A discloses a method and a device for preparing 6-aminocapronitrile by a caprolactam liquid phase method, wherein the method for preparing 6-aminocapronitrile by the caprolactam liquid phase method takes caprolactam as a raw material, and caprolactam reacts with ammonia under the catalysis of phosphoric acid or phosphate to prepare 6-aminocapronitrile, the caprolactam conversion rate is only 48% -65%, and the catalyst is not easy to recover. Patent CN110423201A provides a method for synthesizing hexamethylenediamine from caprolactam as a raw material, which comprises mixing caprolactam, alkali and water, heating and refluxing to obtain 6-aminocaproate, further introducing amino protecting groups to protect terminal amino, then adding acid to neutralize and generate aminocaproic acid with amino protecting groups, drying, adding a dehydration catalyst for amide, heating and reacting in the presence of an ammonia source to convert carboxylic acid groups into cyano groups to obtain product nitrile, extracting and purifying the product nitrile, performing catalytic hydrogenation to generate corresponding amine, and removing the protecting groups to obtain hexamethylenediamine.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a method for producing hexamethylene diamine, which can safely improve the conversion rate of raw materials and the selectivity of products by a simple process, reduce energy consumption and reduce cost.
The technical scheme for solving the problems is as follows: a process for producing hexamethylenediamine comprising the steps of: mixing and gasifying ammonia gas, hydrogen gas and caprolactam to obtain mixed gas; adding a catalyst into the obtained mixed gas to perform a catalytic ammoniation reaction and a catalytic hydrogenation reaction; and then, condensing and separating the materials obtained by the reaction to obtain reaction liquid, and distilling the obtained reaction liquid to obtain the product hexamethylene diamine.
Further, in the method for producing hexamethylenediamine, the molar ratio of ammonia to caprolactam in the mixed gas is (5-20): 1, the molar ratio of hydrogen to caprolactam is (10-30): 1.
further, in the method for producing hexamethylenediamine of the present invention, the reaction temperature of the catalytic ammoniation reaction and the catalytic hydrogenation reaction is 300 to 500 ℃, and the reaction pressure is 0.1 to 1 MPa.
Further, in the method for producing hexamethylenediamine according to the present invention, the pressure is 1kPa to 8kPa and the temperature is 75 ℃ to 180 ℃ when distilling the reaction solution.
Further, in the method for producing hexamethylenediamine according to the present invention, the catalyst is a supported catalyst, wherein a carrier of the catalyst is any one or a combination of any two or more of alkaline earth metal oxide, transition metal oxide, silica and activated alumina, a supported active component of the catalyst is any one or a combination of any two or more of nickel, palladium, platinum and rhodium, and a supported amount is 0.5% to 20%.
Further, in the method for producing hexamethylenediamine of the present invention, the catalyst is a supported catalyst, wherein a carrier of the catalyst is any one or a combination of two of silicon dioxide and aluminum oxide, a supported active component of the catalyst is nickel, and a supporting amount is 5% to 10%.
Further, the method for producing hexamethylenediamine according to the present invention further comprises the step of redistilling the residual material after distilling the reaction solution to obtain the product hexamethylenediamine to recover caprolactam.
Preferably, in the method for producing hexamethylenediamine according to the present invention, the temperature at which the residual material is redistilled is higher than the temperature at which the reaction liquid is distilled.
Preferably, in the method for producing hexamethylenediamine according to the present invention, the reaction liquid is obtained by condensation and separation of the reaction product, and the obtained non-condensable gas and the recovered caprolactam are fed to a reactor as initial reaction materials, and then catalytic ammoniation reaction and catalytic hydrogenation reaction are performed.
Further, the method for producing hexamethylenediamine according to the present invention further comprises a step of preheating ammonia gas and hydrogen gas, wherein the preheated ammonia gas and hydrogen gas are mixed with caprolactam to gasify the caprolactam, such that a mixed gas containing ammonia gas, hydrogen gas, and gaseous caprolactam is obtained.
Compared with the prior art, the invention has the beneficial effects that: the invention innovatively and optimally designs a hexamethylenediamine production process method, which is finished in one step, effectively solves the problems of long and complicated process route, high energy and material consumption and difficulty in industrial large-scale production commonly existing in the conventional hexamethylenediamine production technology, comprehensively recycles the residue materials of a kettle after the hexamethylenediamine product is extracted, remarkably reduces energy consumption, greatly reduces production cost, ensures that the reaction is safer and more stable, effectively improves product selectivity and process safety, and is suitable for industrial large-scale production, popularization and application.
Detailed Description
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, the raw materials and reagents in the examples of the present invention were all purchased from commercial sources.
The invention relates to a method for producing hexamethylene diamine, which comprises the following steps: mixing and gasifying ammonia gas, hydrogen gas and caprolactam to obtain mixed gas; adding a catalyst into the obtained mixed gas to perform a catalytic ammoniation reaction and a catalytic hydrogenation reaction; and then, condensing and separating the materials obtained by the reaction to obtain reaction liquid, and distilling the obtained reaction liquid to obtain the product hexamethylene diamine.
In the method for producing the hexamethylene diamine, the production process of the hexamethylene diamine is innovatively and optimally designed, the traditional method for producing the hexamethylene diamine by catalyzing, ammoniating and dehydrating caprolactam to synthesize 6-aminocapronitrile and catalyzing and hydrogenating the 6-aminocapronitrile to prepare the hexamethylene diamine is organically integrated, and a method for producing the hexamethylene diamine in one step is created, in the method, the heat which is released by the catalytic hydrogenation reaction is utilized to supplement the heat which needs to be absorbed by the catalytic ammoniation reaction, thereby avoiding the energy consumption generated by the ammoniation reaction and the energy discharge loss of the hydrogenation reaction when the reactions are respectively independent, avoiding the instability of the reaction system caused by heat release or heat absorption, the method skillfully realizes the comprehensive utilization of energy, improves the energy utilization efficiency, reduces the energy consumption, the reaction tends to be safe and stable, so that the production cost can be greatly reduced, and the production process is more convenient to control; and the links such as extraction and transfer of the intermediate 6-aminocapronitrile are reduced, so that loss is avoided, the selectivity and the productivity of products are greatly improved, in addition, the materials left in the kettle are fully recycled, the environmental pollution is reduced, and the green and safe production is realized.
In the method for producing hexamethylenediamine, in order to ensure sufficient reaction materials and effectively improve the conversion rate of raw materials and the selectivity of products, the molar ratio of ammonia to caprolactam in the mixed gas is preferably (5-20): 1, the molar ratio of hydrogen to caprolactam is preferably (10-30): 1; in order to enhance the guarantee of the reaction stability, preferably, the reaction temperature of the catalytic ammoniation reaction and the catalytic hydrogenation reaction is 300-500 ℃, and the reaction pressure is 0.1-1 MPa; in order to reduce time consumption and improve reaction efficiency, the catalyst is preferably a supported catalyst, wherein a carrier of the catalyst is any one or a combination of any two or more of alkaline earth metal oxide, transition metal oxide, silicon dioxide and activated alumina, a supported active component of the catalyst is any one or a combination of any two or more of nickel, palladium, platinum and rhodium, and the supporting amount is 0.5-20%, namely the amount of the active component supported on the carrier is 0.5-20%; preferably, the carrier of the catalyst is any one or a combination of two of silicon dioxide and aluminum oxide, the supported active component of the catalyst is nickel, and the supported amount is 5-10%. In order to ensure the sufficient collection of the product hexamethylenediamine, the pressure is preferably 1kPa to 8kPa and the temperature is preferably 75 ℃ to 180 ℃ when the reaction solution is distilled.
In the method for producing hexamethylenediamine, in order to improve the reaction efficiency and ensure the smooth proceeding of the catalytic reaction, activated molecules of each reaction material are combined with a catalyst for high-efficiency catalysis, so as to realize high-efficiency ammoniation and hydrogenation, preferably, ammonia gas and hydrogen gas are preheated, the preheated ammonia gas and hydrogen gas are mixed with caprolactam, the caprolactam is gasified by using the heat carried by the preheated ammonia gas and hydrogen gas, a mixed gas containing the ammonia gas, the hydrogen gas and gaseous caprolactam is obtained, and then the mixed gas is mixed with the catalyst for catalytic ammoniation reaction and catalytic hydrogenation reaction; preferably, in order to make the catalytic reaction more efficiently, the ammonia gas and the hydrogen gas are mixed and then preheated to reach the temperature of preferably 400-500 ℃, so as to be beneficial to improving the conversion rate of the raw materials and the selectivity of the target product.
In the method for producing hexamethylenediamine, in order to save materials and avoid the emission of reaction residual materials to pollute the environment, preferably, the reaction solution is distilled again to obtain the product hexamethylenediamine, the residual materials are distilled again to recover caprolactam, the recovered caprolactam is conveyed to a reactor of the reaction materials, and is mixed with ammonia gas and hydrogen gas to carry out catalytic ammoniation and catalytic hydrogenation reaction again, so that system circulation is formed, pollution is effectively avoided, and the guarantee is provided for green production; in the distillation process, in order to ensure the quality of the target product hexamethylenediamine and avoid mixing impurities, the temperature for redistilling the residual materials is preferably higher than the temperature for distilling the reaction liquid, wherein the hexamethylenediamine fraction is preferably collected at the temperature of 75-135 ℃, the caprolactam fraction is preferably recovered at the temperature of 120-180 ℃, and the collection temperature ranges of the two fractions in actual operation are set according to specific working conditions. Preferably, after the mixed gas is subjected to catalytic ammoniation reaction and catalytic hydrogenation reaction, the conversion rate of raw materials is different, the obtained material is condensed and separated to obtain reaction liquid, and simultaneously non-condensable gas is obtained, so that the non-condensable gas of the residual material is prevented from entering air to cause pollution, the non-condensable gas is an incomplete reaction material, the obtained non-condensable gas and the recovered caprolactam are preferably conveyed to a reactor to serve as initial reaction materials, and then catalytic ammoniation reaction and catalytic hydrogenation reaction are carried out, so that self circulation of a reaction system is realized, no reactant, reaction intermediate and reaction separation residue are discharged, the environment is effectively protected, a large amount of materials are saved while green and safe production is realized, loss is reduced, cost is reduced, and economic benefit is improved. Therefore, the method realizes the near-one-step production of the hexamethylene diamine, is environment-friendly and efficient, simplifies the system reactor device and reaction materials, greatly reduces the cost investment compared with the prior art, greatly improves the product quality, and is suitable for large-scale industrial production, popularization and application.
The present invention will be further described in more detail with reference to more specific application examples, but the present invention is not limited to any examples.
Example 1
The invention relates to a method for producing hexamethylene diamine, which comprises the following steps:
mixing ammonia gas and hydrogen gas, preheating, mixing the preheated ammonia gas and hydrogen gas with caprolactam, and gasifying the caprolactam to obtain a mixed gas containing the ammonia gas, the hydrogen gas and gaseous caprolactam, wherein the molar ratio of the ammonia gas to the caprolactam is 10: 1, molar ratio of hydrogen to caprolactam of 20: 1;
pumping the obtained mixed gas into a fixed bed reactor, and carrying out catalytic ammoniation reaction and catalytic hydrogenation reaction at 400 ℃ and 0.5MPa, wherein the fixed bed reactor is pre-filled with a catalyst, the catalyst is aluminum oxide loaded with metallic nickel, and the nickel loading is 5%;
condensing and separating the materials obtained after the catalytic ammoniation and catalytic hydrogenation reactions to obtain reaction liquid and non-condensable gas; wherein, the non-condensable gas obtained by condensation separation can be used as a reaction raw material, conveyed into the fixed bed reactor, and then continuously subjected to catalytic ammoniation reaction and catalytic hydrogenation reaction;
distilling the reaction liquid obtained by condensation separation under 5kPa, and collecting fractions with the gas phase temperature of 110-120 ℃ to obtain a product of hexamethylenediamine; and then, distilling the residual material after distilling and collecting the product hexamethylene diamine under 2kPa again, collecting fractions with the gas phase temperature of 140-150 ℃ to obtain caprolactam, conveying the recovered caprolactam serving as a reaction raw material into the fixed bed reactor, and continuing to perform catalytic ammoniation reaction and catalytic hydrogenation reaction.
The results show that in this example, the caprolactam conversion per pass was 96.3%, the hexamethylenediamine selectivity was 98.1%, the hexamethylenediamine content was 99.9% and the recovered caprolactam content was 99.5%, based on the fractions.
Example 2
The invention relates to a method for producing hexamethylene diamine, which comprises the following steps:
mixing ammonia gas and hydrogen gas according to a molar ratio of 1:2, preheating, mixing the preheated ammonia gas and hydrogen gas with caprolactam, and gasifying the caprolactam to obtain a mixed gas containing the ammonia gas, the hydrogen gas and gaseous caprolactam, wherein the molar ratio of the ammonia gas to the caprolactam is 10: 1, the caprolactam recovered in example 1 is used as the whole caprolactam;
pumping the obtained mixed gas into a fixed bed reactor, and carrying out catalytic ammoniation reaction and catalytic hydrogenation reaction at 400 ℃ and 0.5MPa, wherein the fixed bed reactor is pre-filled with a catalyst, the catalyst is aluminum oxide loaded with metallic nickel, and the nickel loading is 5%;
condensing and separating the materials obtained after the catalytic ammoniation and catalytic hydrogenation reactions to obtain reaction liquid and non-condensable gas; wherein, the non-condensable gas obtained by condensation separation can be used as a reaction raw material, conveyed into the fixed bed reactor, and then continuously subjected to catalytic ammoniation reaction and catalytic hydrogenation reaction;
distilling the reaction liquid obtained by condensation separation under 5kPa, and collecting fractions with the gas phase temperature of 110-120 ℃ to obtain a product of hexamethylenediamine; and then, distilling the residual material after distilling and collecting the product hexamethylene diamine under 2kPa again, collecting fractions with the gas phase temperature of 140-150 ℃ to obtain caprolactam, conveying the recovered caprolactam serving as a reaction raw material into the fixed bed reactor, and continuing to perform catalytic ammoniation reaction and catalytic hydrogenation reaction.
The results show that in this example, the caprolactam conversion per pass was 96.2%, the hexamethylenediamine selectivity was 98.0%, the hexamethylenediamine content was 99.9% and the recovered caprolactam content was 99.5%, based on the fractions.
Example 3
The invention relates to a method for producing hexamethylene diamine, which comprises the following steps:
mixing ammonia gas and hydrogen gas, preheating, mixing the preheated ammonia gas and hydrogen gas with caprolactam, and gasifying the caprolactam to obtain a mixed gas containing the ammonia gas, the hydrogen gas and gaseous caprolactam, wherein the molar ratio of the ammonia gas to the caprolactam is 10: 1, molar ratio of hydrogen to caprolactam of 20: 1;
pumping the obtained mixed gas into a fixed bed reactor, and carrying out catalytic ammoniation reaction and catalytic hydrogenation reaction at 400 ℃ and 0.5MPa, wherein the fixed bed reactor is pre-filled with a catalyst, the catalyst is silicon dioxide loaded with metallic nickel, and the nickel loading is 5%;
condensing and separating the materials obtained after the catalytic ammoniation and catalytic hydrogenation reactions to obtain reaction liquid and non-condensable gas; wherein, the non-condensable gas obtained by condensation separation can be used as a reaction raw material, conveyed into the fixed bed reactor, and then continuously subjected to catalytic ammoniation reaction and catalytic hydrogenation reaction;
distilling the reaction liquid obtained by condensation separation under 5kPa, and collecting fractions with the gas phase temperature of 110-120 ℃ to obtain a product of hexamethylenediamine; and then, distilling the residual material after distilling and collecting the product hexamethylene diamine under 2kPa again, collecting fractions with the gas phase temperature of 140-150 ℃ to obtain caprolactam, conveying the recovered caprolactam serving as a reaction raw material into the fixed bed reactor, and continuing to perform catalytic ammoniation reaction and catalytic hydrogenation reaction.
The results show that in this example, the caprolactam conversion per pass was 94.0%, the hexamethylenediamine selectivity was 98.5%, the hexamethylenediamine content was 99.9% and the recovered caprolactam content was 99.5%, based on the fractions.
Example 4
The invention relates to a method for producing hexamethylene diamine, which comprises the following steps:
mixing ammonia gas and hydrogen gas, preheating, mixing the preheated ammonia gas and hydrogen gas with caprolactam, and gasifying the caprolactam to obtain a mixed gas containing the ammonia gas, the hydrogen gas and gaseous caprolactam, wherein the molar ratio of the ammonia gas to the caprolactam is 10: 1, molar ratio of hydrogen to caprolactam of 20: 1;
pumping the obtained mixed gas into a fixed bed reactor, and carrying out catalytic ammoniation reaction and catalytic hydrogenation reaction at 400 ℃ and 0.5MPa, wherein the fixed bed reactor is pre-filled with a catalyst, the catalyst is aluminum oxide loaded with metal platinum, and the platinum loading capacity is 5%;
condensing and separating the materials obtained after the catalytic ammoniation and catalytic hydrogenation reactions to obtain reaction liquid and non-condensable gas; wherein, the non-condensable gas obtained by condensation separation can be used as a reaction raw material, conveyed into the fixed bed reactor, and then continuously subjected to catalytic ammoniation reaction and catalytic hydrogenation reaction;
distilling the reaction liquid obtained by condensation separation under 5kPa, and collecting fractions with the gas phase temperature of 110-120 ℃ to obtain a product of hexamethylenediamine; and then, distilling the residual material after distilling and collecting the product hexamethylene diamine under 2kPa again, collecting fractions with the gas phase temperature of 140-150 ℃ to obtain caprolactam, conveying the recovered caprolactam serving as a reaction raw material into the fixed bed reactor, and continuing to perform catalytic ammoniation reaction and catalytic hydrogenation reaction.
The results show that in this example, the caprolactam conversion per pass was 96.5%, the hexamethylenediamine selectivity was 98.9%, the hexamethylenediamine content was 99.9% and the recovered caprolactam content was 99.5%, based on the fractions.
Example 5
The invention relates to a method for producing hexamethylene diamine, which comprises the following steps:
mixing ammonia gas and hydrogen gas, preheating, mixing the preheated ammonia gas and hydrogen gas with caprolactam, and gasifying the caprolactam to obtain a mixed gas containing the ammonia gas, the hydrogen gas and gaseous caprolactam, wherein the molar ratio of the ammonia gas to the caprolactam is 10: 1, molar ratio of hydrogen to caprolactam of 20: 1;
pumping the obtained mixed gas into a fixed bed reactor, and carrying out catalytic ammoniation reaction and catalytic hydrogenation reaction at 400 ℃ and 0.5MPa, wherein the fixed bed reactor is pre-filled with a catalyst, the catalyst is aluminum oxide loaded with metallic nickel, and the nickel loading is 0.5%;
condensing and separating the materials obtained after the catalytic ammoniation and catalytic hydrogenation reactions to obtain reaction liquid and non-condensable gas; wherein, the non-condensable gas obtained by condensation separation can be used as a reaction raw material, conveyed into the fixed bed reactor, and then continuously subjected to catalytic ammoniation reaction and catalytic hydrogenation reaction;
distilling the reaction liquid obtained by condensation separation under 5kPa, and collecting fractions with the gas phase temperature of 110-120 ℃ to obtain a product of hexamethylenediamine; and then, distilling the residual material after distilling and collecting the product hexamethylene diamine under 2kPa again, collecting fractions with the gas phase temperature of 140-150 ℃ to obtain caprolactam, conveying the recovered caprolactam serving as a reaction raw material into the fixed bed reactor, and continuing to perform catalytic ammoniation reaction and catalytic hydrogenation reaction.
The results show that in this example, the caprolactam conversion per pass was 97.5%, the hexamethylenediamine selectivity was 90.3%, the hexamethylenediamine content was 99.7% and the recovered caprolactam content was 99.2%, based on the distillate.
Example 6
The invention relates to a method for producing hexamethylene diamine, which comprises the following steps:
mixing ammonia gas and hydrogen gas, preheating, mixing the preheated ammonia gas and hydrogen gas with caprolactam, and gasifying the caprolactam to obtain a mixed gas containing the ammonia gas, the hydrogen gas and gaseous caprolactam, wherein the molar ratio of the ammonia gas to the caprolactam is 10: 1, molar ratio of hydrogen to caprolactam of 20: 1;
pumping the obtained mixed gas into a fixed bed reactor, and carrying out catalytic ammoniation reaction and catalytic hydrogenation reaction at 400 ℃ and 0.5MPa, wherein the fixed bed reactor is pre-filled with a catalyst, the catalyst is aluminum oxide loaded with metallic nickel, and the nickel loading is 10%;
condensing and separating the materials obtained after the catalytic ammoniation and catalytic hydrogenation reactions to obtain reaction liquid and non-condensable gas; wherein, the non-condensable gas obtained by condensation separation can be used as a reaction raw material, conveyed into the fixed bed reactor, and then continuously subjected to catalytic ammoniation reaction and catalytic hydrogenation reaction;
distilling the reaction liquid obtained by condensation separation under 5kPa, and collecting fractions with the gas phase temperature of 110-120 ℃ to obtain a product of hexamethylenediamine; and then, distilling the residual material after distilling and collecting the product hexamethylene diamine under 2kPa again, collecting fractions with the gas phase temperature of 140-150 ℃ to obtain caprolactam, conveying the recovered caprolactam serving as a reaction raw material into the fixed bed reactor, and continuing to perform catalytic ammoniation reaction and catalytic hydrogenation reaction.
The results show that in this example, the caprolactam conversion per pass was 96.1%, the hexamethylenediamine selectivity was 98.5%, the hexamethylenediamine content was 99.9% and the recovered caprolactam content was 99.6% based on the distillate.
Example 7
The invention relates to a method for producing hexamethylene diamine, which comprises the following steps:
mixing ammonia gas and hydrogen gas, preheating, mixing the preheated ammonia gas and hydrogen gas with caprolactam, and gasifying the caprolactam to obtain a mixed gas containing the ammonia gas, the hydrogen gas and gaseous caprolactam, wherein the molar ratio of the ammonia gas to the caprolactam is 10: 1, molar ratio of hydrogen to caprolactam of 20: 1;
pumping the obtained mixed gas into a fixed bed reactor, and carrying out catalytic ammoniation reaction and catalytic hydrogenation reaction at 400 ℃ and 0.5MPa, wherein the fixed bed reactor is pre-filled with a catalyst, the catalyst is aluminum oxide loaded with metallic nickel, and the nickel loading is 20%;
condensing and separating the materials obtained after the catalytic ammoniation and catalytic hydrogenation reactions to obtain reaction liquid and non-condensable gas; wherein, the non-condensable gas obtained by condensation separation can be used as a reaction raw material, conveyed into the fixed bed reactor, and then continuously subjected to catalytic ammoniation reaction and catalytic hydrogenation reaction;
distilling the reaction liquid obtained by condensation separation under 5kPa, and collecting fractions with the gas phase temperature of 110-120 ℃ to obtain a product of hexamethylenediamine; and then, distilling the residual material after distilling and collecting the product hexamethylene diamine under 2kPa again, collecting fractions with the gas phase temperature of 140-150 ℃ to obtain caprolactam, conveying the recovered caprolactam serving as a reaction raw material into the fixed bed reactor, and continuing to perform catalytic ammoniation reaction and catalytic hydrogenation reaction.
The results show that in this example, the caprolactam conversion per pass was 92.3%, the hexamethylenediamine selectivity was 98.9%, the hexamethylenediamine content was 99.9% and the recovered caprolactam content was 99.7%, based on the fractions.
Example 8
The invention relates to a method for producing hexamethylene diamine, which comprises the following steps:
mixing ammonia gas and hydrogen gas, preheating, mixing the preheated ammonia gas and hydrogen gas with caprolactam, and gasifying the caprolactam to obtain a mixed gas containing the ammonia gas, the hydrogen gas and gaseous caprolactam, wherein the molar ratio of the ammonia gas to the caprolactam is 10: 1, molar ratio of hydrogen to caprolactam of 20: 1;
pumping the obtained mixed gas into a fixed bed reactor, and carrying out catalytic ammoniation reaction and catalytic hydrogenation reaction at 300 ℃ and 0.5MPa, wherein a catalyst is pre-filled in the fixed bed reactor, the catalyst is aluminum oxide loaded with metallic nickel, and the nickel loading is 5%;
condensing and separating the materials obtained after the catalytic ammoniation and catalytic hydrogenation reactions to obtain reaction liquid and non-condensable gas; wherein, the non-condensable gas obtained by condensation separation can be used as a reaction raw material, conveyed into the fixed bed reactor, and then continuously subjected to catalytic ammoniation reaction and catalytic hydrogenation reaction;
distilling the reaction liquid obtained by condensation separation under 5kPa, and collecting fractions with the gas phase temperature of 110-120 ℃ to obtain a product of hexamethylenediamine; and then, distilling the residual material after distilling and collecting the product hexamethylene diamine under 2kPa again, collecting fractions with the gas phase temperature of 140-150 ℃ to obtain caprolactam, conveying the recovered caprolactam serving as a reaction raw material into the fixed bed reactor, and continuing to perform catalytic ammoniation reaction and catalytic hydrogenation reaction.
The results show that in this example, the caprolactam conversion per pass was 91.0%, the hexamethylenediamine selectivity was 99.1%, the hexamethylenediamine content was 99.9% and the recovered caprolactam content was 99.6% based on the distillate.
Example 9
The invention relates to a method for producing hexamethylene diamine, which comprises the following steps:
mixing ammonia gas and hydrogen gas, preheating, mixing the preheated ammonia gas and hydrogen gas with caprolactam, and gasifying the caprolactam to obtain a mixed gas containing the ammonia gas, the hydrogen gas and gaseous caprolactam, wherein the molar ratio of the ammonia gas to the caprolactam is 10: 1, molar ratio of hydrogen to caprolactam of 20: 1;
pumping the obtained mixed gas into a fixed bed reactor, and carrying out catalytic ammoniation reaction and catalytic hydrogenation reaction at 500 ℃ and 0.5MPa, wherein the fixed bed reactor is pre-filled with a catalyst, the catalyst is aluminum oxide loaded with metallic nickel, and the nickel loading is 5%;
condensing and separating the materials obtained after the catalytic ammoniation and catalytic hydrogenation reactions to obtain reaction liquid and non-condensable gas; wherein, the non-condensable gas obtained by condensation separation can be used as a reaction raw material, conveyed into the fixed bed reactor, and then continuously subjected to catalytic ammoniation reaction and catalytic hydrogenation reaction;
distilling the reaction liquid obtained by condensation separation under 5kPa, and collecting fractions with the gas phase temperature of 110-120 ℃ to obtain a product of hexamethylenediamine; and then, distilling the residual material after distilling and collecting the product hexamethylene diamine under 2kPa again, collecting fractions with the gas phase temperature of 140-150 ℃ to obtain caprolactam, conveying the recovered caprolactam serving as a reaction raw material into the fixed bed reactor, and continuing to perform catalytic ammoniation reaction and catalytic hydrogenation reaction.
The results show that in this example, the caprolactam conversion per pass was 97.7%, the hexamethylenediamine selectivity was 93.6%, the hexamethylenediamine content was 99.2% and the recovered caprolactam content was 98.9%, based on the fractions.
Example 10
The invention relates to a method for producing hexamethylene diamine, which comprises the following steps:
mixing ammonia gas and hydrogen gas, preheating, mixing the preheated ammonia gas and hydrogen gas with caprolactam, and gasifying the caprolactam to obtain a mixed gas containing the ammonia gas, the hydrogen gas and gaseous caprolactam, wherein the molar ratio of the ammonia gas to the caprolactam is 10: 1, molar ratio of hydrogen to caprolactam of 20: 1;
pumping the obtained mixed gas into a fixed bed reactor, and carrying out catalytic ammoniation reaction and catalytic hydrogenation reaction at 400 ℃ and 0.1MPa, wherein a catalyst is pre-filled in the fixed bed reactor, the catalyst is aluminum oxide loaded with metallic nickel, and the nickel loading is 5%;
condensing and separating the materials obtained after the catalytic ammoniation and catalytic hydrogenation reactions to obtain reaction liquid and non-condensable gas; wherein, the non-condensable gas obtained by condensation separation can be used as a reaction raw material, conveyed into the fixed bed reactor, and then continuously subjected to catalytic ammoniation reaction and catalytic hydrogenation reaction;
distilling the reaction liquid obtained by condensation separation under 5kPa, and collecting fractions with the gas phase temperature of 110-120 ℃ to obtain a product of hexamethylenediamine; and then, distilling the residual material after distilling and collecting the product hexamethylene diamine under 2kPa again, collecting fractions with the gas phase temperature of 140-150 ℃ to obtain caprolactam, conveying the recovered caprolactam serving as a reaction raw material into the fixed bed reactor, and continuing to perform catalytic ammoniation reaction and catalytic hydrogenation reaction.
The results show that in this example, the caprolactam conversion per pass was 91.9%, the hexamethylenediamine selectivity was 92.1%, the hexamethylenediamine content was 98.9% and the recovered caprolactam content was 98.8%, based on the fractions.
Example 11
The invention relates to a method for producing hexamethylene diamine, which comprises the following steps:
mixing ammonia gas and hydrogen gas, preheating, mixing the preheated ammonia gas and hydrogen gas with caprolactam, and gasifying the caprolactam to obtain a mixed gas containing the ammonia gas, the hydrogen gas and gaseous caprolactam, wherein the molar ratio of the ammonia gas to the caprolactam is 10: 1, molar ratio of hydrogen to caprolactam of 20: 1;
pumping the obtained mixed gas into a fixed bed reactor, and carrying out catalytic ammoniation reaction and catalytic hydrogenation reaction at 400 ℃ and 1.0MPa, wherein the fixed bed reactor is pre-filled with a catalyst, the catalyst is aluminum oxide loaded with metallic nickel, and the nickel loading is 5%;
condensing and separating the materials obtained after the catalytic ammoniation and catalytic hydrogenation reactions to obtain reaction liquid and non-condensable gas; wherein, the non-condensable gas obtained by condensation separation can be used as a reaction raw material, conveyed into the fixed bed reactor, and then continuously subjected to catalytic ammoniation reaction and catalytic hydrogenation reaction;
distilling the reaction liquid obtained by condensation separation under 5kPa, and collecting fractions with the gas phase temperature of 110-120 ℃ to obtain a product of hexamethylenediamine; and then, distilling the residual material after distilling and collecting the product hexamethylene diamine under 2kPa again, collecting fractions with the gas phase temperature of 140-150 ℃ to obtain caprolactam, conveying the recovered caprolactam serving as a reaction raw material into the fixed bed reactor, and continuing to perform catalytic ammoniation reaction and catalytic hydrogenation reaction.
The results show that in this example, the caprolactam conversion per pass was 97.9%, the hexamethylenediamine selectivity was 95.5%, the hexamethylenediamine content was 99.3% and the recovered caprolactam content was 99.1%, based on the fractions.
Example 12
The invention relates to a method for producing hexamethylene diamine, which comprises the following steps:
mixing ammonia gas and hydrogen gas, preheating, mixing the preheated ammonia gas and hydrogen gas with caprolactam, and gasifying the caprolactam to obtain a mixed gas containing the ammonia gas, the hydrogen gas and gaseous caprolactam, wherein the molar ratio of the ammonia gas to the caprolactam is 10: 1, molar ratio of hydrogen to caprolactam of 20: 1;
pumping the obtained mixed gas into a fixed bed reactor, and carrying out catalytic ammoniation reaction and catalytic hydrogenation reaction at 400 ℃ and 0.5MPa, wherein the fixed bed reactor is pre-filled with a catalyst, the catalyst is aluminum oxide loaded with metallic nickel, and the nickel loading is 5%;
condensing and separating the materials obtained after the catalytic ammoniation and catalytic hydrogenation reactions to obtain reaction liquid and non-condensable gas; wherein, the non-condensable gas obtained by condensation separation can be used as a reaction raw material, conveyed into the fixed bed reactor, and then continuously subjected to catalytic ammoniation reaction and catalytic hydrogenation reaction;
distilling the reaction liquid obtained by condensation separation under 1kPa, and collecting fractions with the gas phase temperature of 75-85 ℃ to obtain a product, namely hexamethylenediamine; and then, distilling the residual material after distilling and collecting the product hexamethylene diamine under 2kPa again, collecting the fraction with the gas phase temperature of 120-130 ℃ to obtain caprolactam, conveying the recovered caprolactam serving as a reaction raw material into the fixed bed reactor, and continuing to perform catalytic ammoniation reaction and catalytic hydrogenation reaction.
The results show that in this example, the caprolactam conversion per pass was 96.1%, the hexamethylenediamine selectivity was 98.3%, the hexamethylenediamine content was 99.8% and the recovered caprolactam content was 99.5%, based on the fractions.
Example 13
The invention relates to a method for producing hexamethylene diamine, which comprises the following steps:
mixing ammonia gas and hydrogen gas, preheating, mixing the preheated ammonia gas and hydrogen gas with caprolactam, and gasifying the caprolactam to obtain a mixed gas containing the ammonia gas, the hydrogen gas and gaseous caprolactam, wherein the molar ratio of the ammonia gas to the caprolactam is 10: 1, molar ratio of hydrogen to caprolactam of 20: 1;
pumping the obtained mixed gas into a fixed bed reactor, and carrying out catalytic ammoniation reaction and catalytic hydrogenation reaction at 400 ℃ and 0.5MPa, wherein the fixed bed reactor is pre-filled with a catalyst, the catalyst is aluminum oxide loaded with metallic nickel, and the nickel loading is 5%;
condensing and separating the materials obtained after the catalytic ammoniation and catalytic hydrogenation reactions to obtain reaction liquid and non-condensable gas; wherein, the non-condensable gas obtained by condensation separation can be used as a reaction raw material, conveyed into the fixed bed reactor, and then continuously subjected to catalytic ammoniation reaction and catalytic hydrogenation reaction;
distilling the reaction liquid obtained by condensation separation under 8kPa, and collecting fractions with the gas phase temperature of 125-135 ℃ to obtain a product, namely hexamethylenediamine; and then, distilling the residual material after distilling and collecting the product hexamethylene diamine under 2kPa again, collecting fractions with the gas phase temperature of 170-180 ℃ to obtain caprolactam, conveying the recovered caprolactam serving as a reaction raw material into the fixed bed reactor, and continuing to perform catalytic ammoniation reaction and catalytic hydrogenation reaction.
The results show that in this example, the caprolactam conversion per pass was 96.9%, the hexamethylenediamine selectivity was 97.8%, the hexamethylenediamine content was 99.9% and the recovered caprolactam content was 99.6% based on the distillate.
Example 14
The invention relates to a method for producing hexamethylene diamine, which comprises the following steps:
mixing ammonia gas and hydrogen gas, preheating, mixing the preheated ammonia gas and hydrogen gas with caprolactam, and gasifying the caprolactam to obtain a mixed gas containing the ammonia gas, the hydrogen gas and gaseous caprolactam, wherein the molar ratio of the ammonia gas to the caprolactam is 5: 1, the molar ratio of hydrogen to caprolactam is 10: 1;
pumping the obtained mixed gas into a fixed bed reactor, and carrying out catalytic ammoniation reaction and catalytic hydrogenation reaction at 400 ℃ and 0.5MPa, wherein the fixed bed reactor is pre-filled with a catalyst, the catalyst is aluminum oxide loaded with metallic nickel, and the nickel loading is 5%;
condensing and separating the materials obtained after the catalytic ammoniation and catalytic hydrogenation reactions to obtain reaction liquid and non-condensable gas; wherein, the non-condensable gas obtained by condensation separation can be used as a reaction raw material, conveyed into the fixed bed reactor, and then continuously subjected to catalytic ammoniation reaction and catalytic hydrogenation reaction;
distilling the reaction liquid obtained by condensation separation under 5kPa, and collecting fractions with the gas phase temperature of 110-120 ℃ to obtain a product of hexamethylenediamine; and then, distilling the residual material after distilling and collecting the product hexamethylene diamine under 2kPa again, collecting fractions with the gas phase temperature of 140-150 ℃ to obtain caprolactam, conveying the recovered caprolactam serving as a reaction raw material into the fixed bed reactor, and continuing to perform catalytic ammoniation reaction and catalytic hydrogenation reaction.
The results show that in this example, the conversion per pass of caprolactam was 95.5%, the selectivity to hexamethylenediamine was 97.7%, the hexamethylenediamine content was 99.3% and the recovered caprolactam content was 99.5%, based on the fractions.
Example 15
The invention relates to a method for producing hexamethylene diamine, which comprises the following steps:
mixing ammonia gas and hydrogen gas, preheating, mixing the preheated ammonia gas and hydrogen gas with caprolactam, and gasifying the caprolactam to obtain a mixed gas containing the ammonia gas, the hydrogen gas and gaseous caprolactam, wherein the molar ratio of the ammonia gas to the caprolactam is 20: 1, the molar ratio of hydrogen to caprolactam is 30: 1;
pumping the obtained mixed gas into a fixed bed reactor, and carrying out catalytic ammoniation reaction and catalytic hydrogenation reaction at 400 ℃ and 0.5MPa, wherein the fixed bed reactor is pre-filled with a catalyst, the catalyst is aluminum oxide loaded with metallic nickel, and the nickel loading is 5%;
condensing and separating the materials obtained after the catalytic ammoniation and catalytic hydrogenation reactions to obtain reaction liquid and non-condensable gas; wherein, the non-condensable gas obtained by condensation separation can be used as a reaction raw material, conveyed into the fixed bed reactor, and then continuously subjected to catalytic ammoniation reaction and catalytic hydrogenation reaction;
distilling the reaction liquid obtained by condensation separation under 5kPa, and collecting fractions with the gas phase temperature of 110-120 ℃ to obtain a product of hexamethylenediamine; and then, distilling the residual material after distilling and collecting the product hexamethylene diamine under 2kPa again, collecting fractions with the gas phase temperature of 140-150 ℃ to obtain caprolactam, conveying the recovered caprolactam serving as a reaction raw material into the fixed bed reactor, and continuing to perform catalytic ammoniation reaction and catalytic hydrogenation reaction.
The results show that in this example, the caprolactam conversion per pass was 97.5%, the hexamethylenediamine selectivity was 98.7%, the hexamethylenediamine content was 99.6% and the recovered caprolactam content was 99.5%, based on the fractions.
Generally, by applying the method, the hexamethylenediamine is produced by a one-step simple optimization process, the energy utilization efficiency is improved, the energy consumption is reduced, the reaction tends to be safe and stable, the production cost is greatly reduced, the production process is more convenient to control, the hexamethylenediamine selectivity of a product can be improved by 99.1 percent, the hexamethylenediamine content in the product reaches 99.9 percent, and the single-pass conversion rate of caprolactam serving as a raw material is improved by 97.9 percent; in addition, the non-condensable gas distillation still residue obtained by condensation separation is comprehensively recycled, and the content of the recovered caprolactam can reach 99.7 percent, so that the environment-friendly safe production is effectively protected, a large amount of materials are saved, the cost is further reduced, the economic benefit is improved, and the method is suitable for large-scale industrial production.
The present invention is not limited to the above-described embodiments, and any obvious modifications or alterations to the above-described embodiments may be made by those skilled in the art without departing from the spirit of the present invention and the scope of the appended claims.
Claims (10)
1. A method for producing hexamethylenediamine, comprising the steps of: mixing and gasifying ammonia gas, hydrogen gas and caprolactam to obtain mixed gas; adding a catalyst into the obtained mixed gas to perform a catalytic ammoniation reaction and a catalytic hydrogenation reaction; and then, condensing and separating the materials obtained by the reaction to obtain reaction liquid, and distilling the obtained reaction liquid to obtain the product hexamethylene diamine.
2. The method for producing hexamethylenediamine according to claim 1, wherein the molar ratio of ammonia to caprolactam in the mixed gas is (5-20): 1, the molar ratio of hydrogen to caprolactam is (10-30): 1.
3. the method for producing hexamethylenediamine according to claim 1, wherein the reaction temperature of the catalytic amination reaction and the catalytic hydrogenation reaction is 300 ℃ to 500 ℃ and the reaction pressure is 0.1MPa to 1 MPa.
4. The method for producing hexamethylenediamine according to claim 1, wherein the pressure is 1 to 8kPa and the temperature is 75 to 180 ℃ when distilling the reaction solution.
5. The method for producing hexamethylenediamine according to claim 1, wherein the catalyst is a supported catalyst, wherein the carrier of the catalyst is any one or a combination of any two or more of alkaline earth metal oxide, transition metal oxide, silica and activated alumina, and the supported active component of the catalyst is any one or a combination of any two or more of nickel, palladium, platinum and rhodium, and the supported amount is 0.5% to 20%.
6. The method for producing hexamethylene diamine according to claim 1, wherein the catalyst is a supported catalyst, wherein a carrier of the catalyst is any one or a combination of two of silicon dioxide and aluminum oxide, a supported active component of the catalyst is nickel, and a supporting amount of the supported active component is 5-10%.
7. The method for producing hexamethylenediamine according to claim 1, further comprising the step of redistilling and recovering caprolactam from a residual material obtained after distilling the reaction solution to obtain hexamethylenediamine as a product.
8. The process for producing hexamethylenediamine according to claim 7, wherein the temperature at which the residual material is redistilled is higher than the temperature at which the reaction solution is distilled.
9. The method for producing hexamethylenediamine according to claim 7, wherein the reaction liquid is obtained by condensation separation of the reaction product, and a non-condensable gas is obtained, and the obtained non-condensable gas and the recovered caprolactam are fed to a reactor as starting reaction materials, and then subjected to the catalytic amination reaction and the catalytic hydrogenation reaction.
10. The method for producing hexamethylenediamine according to any one of claims 1 to 9, further comprising a step of preheating ammonia gas and hydrogen gas, wherein the preheated ammonia gas and hydrogen gas are mixed with caprolactam to gasify the caprolactam to obtain a mixed gas containing ammonia gas, hydrogen gas and gaseous caprolactam.
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| CN112812020A (en) * | 2021-02-08 | 2021-05-18 | 陈天然 | Method and device for producing hexamethylene diamine from caprolactam |
| CN113694969A (en) * | 2021-04-26 | 2021-11-26 | 河南平煤神马尼龙工程技术有限公司 | Catalyst system and method for catalytically synthesizing 1, 6-hexamethylene diamine by using same |
| CN113694969B (en) * | 2021-04-26 | 2022-12-16 | 河南平煤神马尼龙工程技术有限公司 | Catalyst system and method for catalytically synthesizing 1, 6-hexamethylene diamine by using same |
| CN113461540A (en) * | 2021-06-18 | 2021-10-01 | 中触媒新材料股份有限公司 | Method for synthesizing hexamethylene diamine from caprolactam in one step |
| 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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