CN218590486U - Hydrogenation device for preparing hexamethylene diamine - Google Patents
Hydrogenation device for preparing hexamethylene diamine Download PDFInfo
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- CN218590486U CN218590486U CN202222909168.7U CN202222909168U CN218590486U CN 218590486 U CN218590486 U CN 218590486U CN 202222909168 U CN202222909168 U CN 202222909168U CN 218590486 U CN218590486 U CN 218590486U
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- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 78
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 93
- 239000003054 catalyst Substances 0.000 claims abstract description 93
- 239000001257 hydrogen Substances 0.000 claims abstract description 89
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 89
- 239000007788 liquid Substances 0.000 claims abstract description 75
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 239000002994 raw material Substances 0.000 claims abstract description 19
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims description 57
- 239000011148 porous material Substances 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 29
- 238000005406 washing Methods 0.000 claims description 27
- 239000012295 chemical reaction liquid Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 239000012071 phase Substances 0.000 claims description 17
- 239000007791 liquid phase Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000012528 membrane Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- 239000002699 waste material Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 abstract description 2
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 29
- KBMSFJFLSXLIDJ-UHFFFAOYSA-N 6-aminohexanenitrile Chemical compound NCCCCCC#N KBMSFJFLSXLIDJ-UHFFFAOYSA-N 0.000 description 19
- 239000000047 product Substances 0.000 description 19
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000002904 solvent Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000004064 recycling Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- FHKPTEOFUHYQFY-UHFFFAOYSA-N 2-aminohexanenitrile Chemical compound CCCCC(N)C#N FHKPTEOFUHYQFY-UHFFFAOYSA-N 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- 239000007868 Raney catalyst Substances 0.000 description 3
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 3
- 229910000564 Raney nickel Inorganic materials 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003317 industrial substance Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000007858 starting material Substances 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
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 208000012839 conversion disease Diseases 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
- 238000001035 drying Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000002101 nanobubble Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000036632 reaction speed Effects 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
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The utility model discloses a hydrogenation unit of preparation hexamethylene diamine mainly comprises hybrid system, hydrogenation ware, and the hybrid system is connected with hydrogenation ware, and the hybrid system includes at least one second passageway and at least one first passageway, borders on the second passageway with the component of first passageway, the component is including having the hole district, there is the hole district to follow the length direction of component extends, and hydrogen passes through there is the hole district to be poured into in the raw materials mixes the liquid, the second passageway indicates the space that can hold the raw materials and mix the liquid, and the first passageway indicates the space that can hold hydrogen. The utility model has the characteristics of reaction pressure is low, the catalyst quantity is few, the conversion rate is high, the product hexane diamine selectivity is high, the accessory substance is few etc.
Description
Technical Field
The utility model belongs to the technical field of organic chemical industry, a hydrogenation device of preparation hexanediamine is related to, in particular to hexanedinitrile and/or 6-aminocapronitrile hydrogenation production hexanediamine's device.
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 fiber, 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 dehydration, and the 6-aminocapronitrile is further subjected to catalytic hydrogenation to obtain the hexamethylene diamine.
In the prior art, patent CN110423201A provides a method for synthesizing hexamethylenediamine by using caprolactam as a raw material, which comprises the steps of mixing caprolactam, alkali and water, heating and refluxing to obtain 6-aminocaproate, further introducing an amino protection group to protect a terminal amino group, then adding acid to neutralize to generate aminocaproic acid with the amino protection group, drying, adding an amide dehydration catalyst, heating and reacting in the presence of an ammonia source to convert a carboxylic acid group into a cyano group to obtain a product nitrile, extracting and purifying the product nitrile to generate corresponding amine through catalysis, and then removing the protection group to obtain the hexamethylenediamine.
Patent CN 112079725A describes a method for producing hexamethylenediamine, in which ammonia gas, hydrogen gas and caprolactam are mixed and vaporized to obtain a 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 of hexamethylene diamine. The method integrates the ammonification and the hydrogenation of the caprolactam, but has the defects of high reaction temperature and more byproducts, and has no industrial application value.
In the prior art, the adiponitrile/6-aminocapronitrile hydrogenation production method for hexamethylene diamine can be used for continuous production, but has high reaction pressure and large catalyst consumption.
Mesoscopic is a system that is intermediate between microscopic and macroscopic, and thus, mesoscopic dimensions refer to dimensions intermediate between macroscopic and microscopic, and are generally considered to be between nanometer and millimeter, i.e., micron-scale dimensions.
The industrial chemical reactions of hydrogenation, oxygenation and chlorination of gas-liquid two-phase and gas-liquid-solid three-phase generally exist, the premise of improving the reaction speed is to improve the mass transfer rate from the gas phase to the liquid phase, the industry generally applies a gas-liquid stirring paddle, a mixer or a bubble column reactor to reduce the size of gas bubbles to improve the mass transfer efficiency, most of the energy of stirring in the process is converted into heat energy, the heat energy is not converted into surface energy required for generating small bubbles, only bubbles with the size of centimeter or millimeter can be generated, and the industrial chemical reactions of the gas-liquid two-phase and the gas-liquid-solid three-phase mainly comprise low mass transfer speed and corresponding low reaction conversion rate under the macroscopic size of more than millimeter level.
The technology for preparing the hexamethylene diamine by the hydrogenation of the adiponitrile and/or the 6-aminocapronitrile with low reaction pressure and small catalyst consumption of a mesoscopic system has obvious economic benefit.
Disclosure of Invention
The defects existing in the prior art are overcome, the utility model provides a hydrogenation device for preparing hexamethylene diamine and the application of the base in preparing hexamethylene diamine, the utility model has the characteristics of low reaction pressure, less catalyst consumption, high conversion rate, high selectivity of the product hexamethylene diamine, less byproducts and the like.
The utility model adopts the technical proposal that: the utility model provides a hydrogenation unit of preparation hexane diamine mainly comprises hybrid system, hydrogenation ware, and the hybrid system is connected with hydrogenation ware, its characterized in that: the mixing system comprises at least one second channel, at least one first channel and a component adjacent to the second channel and the first channel, wherein the second channel refers to a space capable of containing raw material mixed liquid, and the first channel refers to a space capable of containing hydrogen; the member includes a porous region extending in a length direction of the member and covering the entire member, through which hydrogen gas is injected into the raw material mixture, the porous region having nano-scale fine pores.
Optionally, the member is one or a combination of two or more of a porous membrane, a porous plate and a porous pipe. The porous pipe refers to a pipe with porous pipe walls. The inner surface and/or the outer surface of the porous pipe can be attached with a porous membrane, and the pore diameter of the pores on the pipe can be adjusted by moving the porous membrane. For example: the pores on the wall of the pipe may be micropores, and the pores of the pipe of the porous film attached on the inner surface and/or the outer surface of the pipe are also regarded as nano-scale fine pores; the porous tube may be a membrane tube; the number of channels in the porous pipe is not particularly limited, and generally, the number of channels in the porous pipe may be 10 to 50.
Alternatively, the mixing system may be formed by the components being used in conjunction with a housing. The interior of the housing is provided with at least one of the members that partition the interior space of the housing into a second passage and a first passage. The shell is provided with a hydrogen inlet, a liquid inlet and a liquid outlet, two ends of the second channel are respectively communicated with the liquid inlet and the liquid outlet, and the first channel is communicated with the hydrogen inlet.
Optionally, the average pore diameter of the nano-scale fine pores is 1 to 1000 nm, preferably 30 to 800 nm.
The hydrogenation reactor is a fluidized bed reactor, a stirring reactor, a fixed bed reactor or a magnetic stabilization bed reactor.
Further, the hydrogenation reactor is connected with a gas-liquid separator, the gas-liquid separator is connected with a hydrogen washing tower, a hydrogen outlet of the hydrogen washing tower is connected with a hydrogen circulating compressor, and the hydrogen circulating compressor is connected with an inlet of the first channel of the mixing system.
Further, the gas-liquid separator is connected with the liquid-solid separator, and the gas-liquid separator is provided with an overflow channel connected with the liquid-solid separator. The liquid-solid separator is provided with a liquid phase outlet connected with an inlet of the second channel of the mixing system, and the liquid-solid separator is also provided with a hydrogenation reaction liquid outlet connected with a subsequent hydrogenation reaction liquid treatment process.
The fluidized bed reactor is a gas-liquid-solid three-phase boiling type fluidized bed reactor and consists of two or more similar reaction pipes, a gas-liquid separator and a liquid-solid separator, wherein the reaction pipes are lifted to the gas-liquid separator which is connected with the liquid-solid separator; the gas-liquid separator gas-phase outlet is connected with a hydrogen washing tower, the hydrogen washing tower gas-phase outlet is connected with a hydrogen circulating compressor, and the hydrogen washing tower liquid-phase outlet is connected with a liquid-solid separator; the liquid-solid separator is provided with a waste catalyst discharge port; the bottom of the reaction tube is connected with a material feeding tube. The top of the liquid-solid separator is provided with a waste catalyst discharge outlet. In order to maintain the concentration and activity of the catalyst in the reactor, a certain amount of catalyst is discharged from the catalyst circulation system to a discharged catalyst washing tank, the catalyst is washed in the tank by water, the washed catalyst is discharged from the bottom, a part of the washed catalyst is returned to a catalyst feeder for recycling, and a part of the washed catalyst is discharged into a catalyst deactivator for passivation treatment and then discharged.
The stirring reaction is a horizontal stirring reactor or a vertical continuous stirring reactor.
In the utility model, the connection between each device is through the pipeline, and the related affiliated facilities such as pump, jar can be established.
The hydrogenation device for preparing the hexamethylene diamine is applied to the preparation of the hexamethylene diamine and comprises the following steps:
s1: hydrogen and circulating hydrogen enter the channel through the inlet of the first channel of the mixing system, and adiponitrile and/or 6-aminocapronitrile and solvent enter the second channel through the inlet of the second channel; hydrogen of the first channel enters the second channel through the nanometer-scale pores of the pore region of the adjacent component between the first channel and the second channel to be mixed with adiponitrile and/or 6-aminocapronitrile and a solvent; the hydrogen in the gas-liquid mixed fluid is nano-scale bubbles, and the average diameter of the bubbles is 100 nm-50 mu m;
s2: mixing a catalyst and a cocatalyst in an auxiliary agent feeding tank, then conveying the mixture to a hydrogenation reactor, feeding the mixture obtained in the step S1 into a second channel material to react at the temperature of 30-120 ℃ and the pressure of 0.4-1.0 MPaG;
wherein the catalyst is one or the combination of at least two of Raney nickel, raney cobalt and Raney nickel cobalt;
wherein the cocatalyst is NaOH, KOH, CH 3 CH 2 ONa、CH 3 Any one of ONa or a combination of at least two;
wherein the mass ratio of the catalyst to the adiponitrile and/or 6-aminocapronitrile is 0.01-0.05: 1, the mass ratio of the cocatalyst to the adiponitrile and/or 6-aminocapronitrile is 0.001-0.1, and the molar ratio of hydrogen to the adiponitrile and/or 6-aminocapronitrile is 2-100;
s3: and separating unreacted hydrogen from liquid in the gas-liquid separator, introducing the hydrogen into a hydrogen washing tower to wash out the entrained solvent, pressurizing and circulating the hydrogen to a first channel of a mixing system by a hydrogen circulating compressor, and returning the washed solvent to the hydrogenation reactor. After the gas-liquid separator separates hydrogen, part of the reaction liquid containing the catalyst is circulated back to the hydrogenation reactor, and part of the reaction liquid overflows to the liquid-solid separator; the weight ratio of the reaction liquid which is circulated back to the hydrogenation reaction to the reaction liquid which overflows to the liquid-solid separator is 5 (1 to 10).
The gas-liquid separator is connected with the liquid-solid separator, and the gas-liquid separator is provided with an overflow channel connected with the liquid-solid separator. The top of the liquid-solid separator is provided with a waste catalyst discharge outlet. In order to maintain the concentration and activity of the catalyst in the reactor, a certain amount of catalyst is discharged from the catalyst circulation system to a discharged catalyst washing tank, the catalyst is washed in the tank by water, the washed catalyst is discharged from the bottom, a part of the washed catalyst is returned to a catalyst feeder for recycling, and a part of the washed catalyst is discharged into a catalyst deactivator for passivation treatment and then discharged.
Separating the hydrogenation reaction liquid overflowing from the gas-liquid separator to the liquid-solid separator in the liquid-solid separator, discharging a part of the hydrogenation reaction liquid from a hydrogenation reaction liquid outlet to a post-treatment process, and refining to obtain a hexamethylene diamine product; a part of the liquid phase is returned to the second channel of the mixing system through a liquid phase outlet arranged on the liquid-solid separator. The weight ratio of the reaction liquid returned to the second channel to the reactant discharged to the post-treatment process is 10 (1 to 5).
The utility model discloses a characteristics and effect:
the utility model discloses a hydrogenation unit of preparation hexamethylene diamine because hydrogen and reactant, solvent carry out mesoscopic state's mixture at the hybrid system, form the gas-liquid mixed fluid who contains micro-nano bubble, improved hydrogen mass transfer speed in the reaction liquid, reduced hydrogenation reaction pressure, hydrogenation reaction pressure can be followed prior art's 2.0 to 3.0MPa (G) and dropped to 0.4 ~ 1.0MPa (G). Meanwhile, the using amount of the catalyst is reduced by 50 percent compared with the using amount of the catalyst in the prior art, and the method has the characteristics of low reaction pressure, less using amount of the catalyst, less by-products and high product quality.
Drawings
FIG. 1 is a schematic diagram of a hydrogenation apparatus for preparing hexamethylenediamine according to the present invention;
FIG. 2 is a schematic diagram of the hybrid system of the present invention;
wherein: 1-mixing system; 2-a hydrogenation reactor; 3-a gas-liquid separator; 4-liquid-solid separator; 5-a catalyst washing tank; 6-hydrogen washing tower; 7-a hydrogen recycle compressor; 11-a member; 12-a housing; 13-a hydrogen inlet; 14-a liquid inlet; 15-a liquid outlet; a-fresh hydrogen; b-raw material/solvent; c-recycle of hydrogen; d-recycling material 1; e-recycling the solvent; f-circulating catalyst G-circulating feed 2; h-desalted water; i-crude hexamethylenediamine; j-spent catalyst.
Detailed Description
The following examples will further illustrate the present invention, but the present invention is not limited to these examples.
According to the graph 1, the utility model discloses preparation hexamethylene diamine's hydrogenation device mainly comprises hybrid system 1, hydrogenation ware 2, and the hybrid system is connected with the hydrogenation ware, and hydrogenation ware connection vapour and liquid separator 3, vapour and liquid separator connect hydrogen washing tower 6, and hydrogen washing tower hydrogen export is connected with hydrogen circulating compressor 7, hydrogen circulating compressor and the access connection of the first passageway of hybrid system. The mixing system comprises at least one second channel for containing the raw material mixed liquor and at least one first channel for containing hydrogen, wherein the second channel and the first channel are adjoined through a member, the member comprises a porous area with nanometer-scale pores, and the porous area is one or a combination of more than two of a porous membrane, a porous plate and a porous pipeline, and the average pore diameter of the nanometer-scale pores is 1-1000 nm, preferably 30-800 nm, and further preferably 50-500 nm. The porous region extends in the longitudinal direction of the member, and hydrogen gas is injected into the raw material mixture through the porous region. A porous tube is a tube whose wall is porous. The inner surface and/or the outer surface of the porous pipeline can be attached with a porous membrane, and the pore diameter of the pores on the pipeline can be adjusted by moving the porous membrane. For example: the pores on the wall of the pipe may be micropores, and the pores of the pipe of the porous film attached on the inner surface and/or the outer surface of the pipe are also regarded as nano-scale fine pores; the porous tube may be a membrane tube; the number of the passages in the porous pipe is not particularly limited, and generally, the number of the passages in the porous pipe may be 10 to 50.
In practice, the mixing system may also be formed by using the component 11 (e.g. the component in fig. 2 is a porous pipe) in combination with the housing 12. In particular, at least one component 11 is placed in the housing 12, with a space between the outer wall of the component 11 and the inner wall of the housing 12. A channel surrounded by the member 11 is used as a second channel for containing raw material mixed liquid, and a space formed by the outer wall of the member 11 and the inner wall of the shell 12 is used as a first channel for containing hydrogen; alternatively, the channel surrounded by the member 11 serves as a first channel for accommodating hydrogen gas, and the space formed by the outer wall of the member 11 and the inner wall of the housing 12 serves as a second channel for accommodating the raw material mixed liquid. Preferably, the enclosed channel of the member 11 serves as a second channel for accommodating the raw material mixed liquid, and the space formed by the outer wall of the member 11 and the inner wall of the housing 12 serves as a first channel for accommodating the hydrogen gas reagent.
When the channel surrounded by the members serves as a second channel for accommodating the raw material mixed liquid, and the space formed by the outer wall of the members and the inner wall of the housing serves as a first channel for accommodating hydrogen, as shown in fig. 1, a hydrogen inlet 13, a liquid inlet 14, and a liquid outlet 15 may be provided on the housing 12, and both ends of the second channel are respectively communicated with the liquid inlet 14 and the liquid outlet 15, and the first channel is communicated with the hydrogen inlet 13. Hydrogen is fed into the housing 12 through the inlet 13, the raw material mixture is fed into the passage of the member 11, and the hydrogen is fed into the raw material mixture through the holes in the tube wall by the pressure difference, thereby obtaining a gas-liquid mixture fluid.
The material forming the member may be an inorganic material (such as an inorganic ceramic) or an organic material as long as the material forming the member does not chemically interact with the hydrogen gas and the raw material mixed liquid.
The hydrogenation reactor is a fluidized bed reactor, a stirred reactor, a fixed bed reactor or a magnetically stabilized bed reactor. Preferably a fluidized bed reactor.
The fluidized bed reactor is a gas-liquid-solid three-phase boiling type fluidized bed reactor and consists of two or more similar reaction pipes, a gas-liquid separator and a liquid-solid separator, wherein the reaction pipes are lifted to the gas-liquid separator which is connected with the liquid-solid separator; the gas-phase outlet of the gas-liquid separator is connected with a hydrogen washing tower, the gas-phase outlet of the hydrogen washing tower is connected with a hydrogen circulating compressor, and the liquid-phase outlet of the hydrogen washing tower is connected with the liquid-solid separator; the liquid-solid separator is provided with a waste catalyst discharge port; the bottom of the reaction tube is connected with a material feeding tube. The top tip of the liquid-solid separator is provided with a waste catalyst discharge port. In order to maintain the concentration and activity of the catalyst in the reactor, a certain amount of catalyst is discharged from the catalyst circulation system to a discharged catalyst washing tank, the catalyst is washed in the tank by water, the washed catalyst is discharged from the bottom, a part of the washed catalyst is returned to a catalyst feeder for recycling, and a part of the washed catalyst is discharged into a catalyst deactivator for passivation treatment and then discharged.
The stirring reaction is a horizontal stirring reactor or a vertical continuous stirring reactor.
In the utility model, the connection between each device is through the pipeline, and the related affiliated facilities such as pump, jar can be established.
The following is an example of the production of hexamethylenediamine by means of the hydrogenation apparatus for producing hexamethylenediamine according to the invention.
Example 1: preparation of hexanediamine by hydrogenation of adiponitrile
S1: hydrogen and circulating hydrogen are mixed according to a molar ratio of the hydrogen to the adiponitrile of 50-60. The adiponitrile and the ethanol enter the first channel through the inlet of the first channel of the mixing system, and the adiponitrile and the ethanol enter the second channel through the inlet of the second channel; hydrogen of the first channel enters the second channel through the nanometer-scale pores of the pore region of the adjacent component between the first channel and the second channel to be mixed with adiponitrile and ethanol; the component used for adjoining the first channel and the second channel in the mixing system is a membrane tube with 30 channels (the channels are uniformly distributed on the pipeline, the inner diameter of each channel is 3.3 mm, the average pore diameter of the pores on the substrate is 100 mu m, the average pore diameter of the pores on the porous membrane is 30 nm), hydrogen is dispersed into nanoscale gas through the pores with nanoscale, the nanoscale gas enters the second channel and is mixed with adiponitrile and ethanol to form gas-liquid mixed fluid, and the average diameter of the bubbles is 100 nm-50 mu m.
S2: mixing a catalyst Raney nickel and a cocatalyst NaOH in an auxiliary agent feeding tank, and then conveying the mixture to a hydrogenation reactor, wherein the second channel material mixed in the step S1 enters the hydrogenation reactor and reacts at the temperature of 30-120 ℃ and the pressure of 0.4-1.0 MPaG; wherein the mass ratio of the catalyst to the adiponitrile is 0.01-0.05, and the mass ratio of the cocatalyst to the adiponitrile and/or 6-aminocapronitrile is 0.001-0.1.
The hydrogenation reactor is a fluidized bed reactor, catalyst and NaOH are mixed in an auxiliary agent feeding tank and then are sent to a gas-liquid-solid three-phase boiling type fluidized bed reactor consisting of three similar reaction pipes, gas-liquid mixed fluid mixed by a second channel of a mixing system is supplied from the bottom of the reaction pipes and reacts at the temperature of 60-80 ℃ and under the pressure of 0.8MPaG, hydrogen and reaction liquid rise together from the reaction pipes to a gas-liquid separator, and the reaction is basically finished. This reaction is exothermic and the heat of reaction is removed by external reactor cooling water coolers.
S3: and separating unreacted hydrogen from liquid in the gas-liquid separator, feeding the hydrogen into a hydrogen washing tower to wash off the entrained solvent, then pressurizing and circulating the hydrogen to a first channel of the mixing system by a hydrogen circulating compressor, and returning the washed solvent to the hydrogenation reactor. After the gas-liquid separator separates hydrogen, part of the reaction liquid containing the catalyst is circulated back to the hydrogenation reactor, and part of the reaction liquid overflows to the liquid-solid separator; the weight ratio of the reaction liquid which is circulated back to the hydrogenation reaction to the reaction liquid which overflows to the liquid-solid separator is 5 (1 to 10).
Separating the hydrogenation reaction product overflowing from the gas-liquid separator to the liquid-solid separator in the liquid-solid separator, discharging a part of the hydrogenation reaction product from a hydrogenation reaction product outlet to a post-treatment process, and refining to obtain a hexamethylene diamine product; a part of the liquid phase is returned to the second channel of the mixing system through a liquid phase outlet arranged on the liquid-solid separator. The weight ratio of the reactant returned to the second channel to the reactant discharged to the post-treatment process is 10 (1-5).
The top tip of the liquid-solid separator is provided with a waste catalyst discharge port. In order to maintain the concentration and activity of the catalyst in the reactor, certain amount of catalyst is discharged from the catalyst circulating system to a discharged catalyst washing tank, the catalyst is washed with water in the tank, the washed catalyst is discharged from the bottom, part of the catalyst is returned to the catalyst feeder for recycling, and part of the catalyst is discharged to a catalyst deactivator for deactivation and then discharged.
The adiponitrile conversion rate is 98-99%, and the hexamethylene diamine yield is 95-96%.
EXAMPLE 2 hydrogenation of aminocapronitrile to hexamethylene diamine
The procedure is otherwise as in example 1, except that the starting material, adiponitrile, is changed to 6-aminocapronitrile.
The conversion rate of 6-aminocapronitrile is 99-100%, and the yield of hexamethylene diamine reaches 96-97%.
EXAMPLE 3 hydrogenation of adiponitrile and 6-aminocapronitrile mixtures to produce hexamethylenediamine
Otherwise, the procedure is the same as in example 1 except that the starting material is changed to a mixture of adiponitrile and 6-aminocapronitrile in a mass ratio of adiponitrile to 6-aminocapronitrile of 1 (0.5-2).
The conversion rate of 6-aminocapronitrile is 99-100%, the conversion rate of adiponitrile is 97-98%, and the yield of hexamethylene diamine reaches 98-99%.
Example 4
Otherwise, the same as example 1, except that the hydrogenation product overflowing from the gas-liquid separator to the liquid-solid separator in the step S3 is separated in the liquid-solid separator, and the liquid phase is discharged from the hydrogenation product outlet to the post-treatment step, and is refined to obtain the hexamethylenediamine product, and no part of the hexamethylenediamine product returns to the second channel of the mixing system.
The adiponitrile conversion rate is 92-94%, and the yield of the hexamethylene diamine reaches 95-96%.
Example 5
The other steps are the same as the example 2 except that the hydrogenation reaction product overflowing from the gas-liquid separator to the liquid-solid separator in the step S3 is separated in the liquid-solid separator, the liquid phase is discharged from the hydrogenation reaction product outlet to the post-treatment process, and the hexamethylene diamine product is obtained after refining, and part of the hexamethylene diamine product is not returned to the second channel of the mixing system.
The conversion rate of 6-aminocapronitrile is 93-94%, and the yield of hexamethylene diamine reaches 96-97%.
Example 6
The other steps are the same as example 3, except that the hydrogenation product overflowing from the gas-liquid separator to the liquid-solid separator in the step S3 is separated in the liquid-solid separator, the liquid phase is discharged from the hydrogenation product outlet to the post-treatment process, and the hexamethylene diamine product is obtained through refining, and no part of the product returns to the second channel of the mixing system.
The conversion rate of 6-aminocapronitrile is 92-94%, the conversion rate of adiponitrile is 93-94%, and the yield of hexamethylene diamine reaches 96-98%.
Comparative example 1
Mixing a catalyst, adiponitrile, ethanol and NaOH in a hydrogenation reaction feeding tank, and then feeding the mixture to a gas-liquid-solid three-phase boiling fluidized bed reactor consisting of three similar reaction tubes, wherein the reaction materials and hydrogen from a hydrogen boosting compressor and a hydrogen circulating compressor are respectively supplied from the bottom of the reaction tubes and react at the temperature of 30-120 ℃ and the pressure of 0.4-1.0 MPaG; wherein the mass ratio of the catalyst to the adiponitrile is 0.01-0.05.
The hydrogen gas and the reaction solution rise together from the reaction tube to the gas-liquid separator, and the reaction is almost completed. This reaction is exothermic and the heat of reaction is removed by external reactor cooling water coolers.
Separating unreacted hydrogen from liquid in the gas-liquid separator, introducing the hydrogen into a hydrogen washing tower to wash off the entrained solvent, then pressurizing and recycling the hydrogen by a hydrogen circulating compressor, and returning the washed solvent to the hydrogenation reactor. The lower part of the gas-liquid separator is provided with a liquid-solid separator, and the top tip part of the liquid-solid separator is provided with a waste catalyst discharge outlet. In order to maintain the concentration and activity of the catalyst in the reactor, certain amount of catalyst is discharged from the catalyst circulating system to a discharged catalyst washing tank, the catalyst is washed with water in the tank, the washed catalyst is discharged from the bottom, part of the catalyst is returned to the catalyst feeder for recycling, and part of the catalyst is discharged to a catalyst deactivator for deactivation and then discharged.
The adiponitrile conversion rate is 80-83%, and the hexamethylene diamine yield reaches 90-92%.
Comparative example 2
Mixing a catalyst, aminocapronitrile, ethanol and NaOH in a hydrogenation reaction feeding tank, and then feeding the mixture to a gas-liquid-solid three-phase boiling type fluidized bed reactor consisting of three similar reaction tubes, wherein the reaction materials and hydrogen from a hydrogen boosting compressor and a hydrogen circulating compressor are respectively supplied from the bottom of the reaction tubes and react at the temperature of 30-120 ℃ and the pressure of 0.4-1.0 MPaG; wherein the mass ratio of the catalyst to the adiponitrile is 0.01-0.05, and the mass ratio of the cocatalyst to the aminocapronitrile is 0.001-0.1.
The hydrogen gas and the reaction solution rise together from the reaction tube to the gas-liquid separator, and the reaction is almost completed. This reaction is exothermic and the heat of reaction is removed by external reactor cooling water coolers.
Separating unreacted hydrogen from liquid in a gas-liquid separator, introducing the hydrogen into a hydrogen washing tower to wash out entrained solvent, pressurizing and recycling the hydrogen by a hydrogen circulating compressor, and returning the washed solvent to the hydrogenation reactor. The lower part of the gas-liquid separator is provided with a liquid-solid separator, and the top tip part of the liquid-solid separator is provided with a waste catalyst discharge outlet. In order to maintain the concentration and activity of the catalyst in the reactor, certain amount of catalyst is discharged from the catalyst circulating system to a discharged catalyst washing tank, the catalyst is washed with water in the tank, the washed catalyst is discharged from the bottom, part of the catalyst is returned to the catalyst feeder for recycling, and part of the catalyst is discharged to a catalyst deactivator for deactivation and then discharged.
The conversion rate of aminocapronitrile is 85-86%, and the yield of hexamethylene diamine reaches 88-89%.
Claims (10)
1. The utility model provides a hydrogenation unit of preparation hexane diamine mainly comprises hybrid system, hydrogenation ware, and the hybrid system is connected with hydrogenation ware, its characterized in that: the mixing system comprises at least one second channel, at least one first channel and a component adjacent to the second channel and the first channel, wherein the second channel refers to a space capable of containing raw material mixed liquid, and the first channel refers to a space capable of containing hydrogen; the member includes a porous region extending in a length direction of the member and covering the entire member, through which hydrogen gas is injected into the raw material mixture, the porous region having fine pores of a nanometer scale.
2. The hydrogenation apparatus for preparing hexanediamine according to claim 1, wherein the member is one or a combination of two or more of a porous membrane, a porous plate and a porous pipe, wherein the porous pipe is a pipe whose pipe wall is porous; the inner surface and/or the outer surface of the porous pipeline can be attached with a porous membrane, and the pore diameter of the pores on the pipeline can be adjusted by moving the porous membrane.
3. The hydrogenation apparatus for producing hexamethylenediamine according to claim 1, wherein the mixing system is formed by combining the components with a housing; at least one member is provided inside the housing, the member dividing an inner space of the housing into a second passage and a first passage; the shell is provided with a hydrogen inlet, a liquid inlet and a liquid outlet, two ends of the second channel are respectively communicated with the liquid inlet and the liquid outlet, and the first channel is communicated with the hydrogen inlet.
4. The hydrogenation apparatus for producing hexamethylenediamine according to claim 1, wherein the average pore diameter of the nano-scale fine pores is 1 to 1000 nm.
5. The hydrogenation apparatus for producing hexamethylenediamine according to claim 4, wherein the average pore diameter of the nano-scale fine pores is in the range of 30 to 800 nm.
6. The hydrogenation apparatus according to claim 1, wherein the hydrogenation reactor is a fluidized bed reactor, a stirred reactor, a fixed bed reactor or a magnetically stabilized bed reactor.
7. The hydrogenation device for preparing hexamethylene diamine according to claim 1, wherein the hydrogenation reactor is connected with a gas-liquid separator, the gas-liquid separator is connected with a hydrogen washing tower, a hydrogen outlet of the hydrogen washing tower is connected with a hydrogen circulation compressor, and the hydrogen circulation compressor is connected with an inlet of the first channel of the mixing system.
8. The hydrogenation device for preparing hexamethylene diamine according to claim 7, wherein the gas-liquid separator is connected with the liquid-solid separator, and the gas-liquid separator is provided with an overflow channel connected with the liquid-solid separator; the liquid-solid separator is provided with a liquid phase outlet connected with an inlet of a second channel of the mixing system, and the liquid-solid separator is also provided with a hydrogenation reaction liquid outlet connected with a subsequent hydrogenation reaction liquid treatment process.
9. The hydrogenation device for preparing hexanediamine according to claim 6, characterized in that the fluidized bed reactor is a gas, liquid and solid three-phase boiling fluidized bed reactor, which is composed of two or more similar reaction tubes, a gas-liquid separator and a liquid-solid separator, wherein the reaction tubes are lifted to the gas-liquid separator, and the gas-liquid separator is connected with the liquid-solid separator; the gas-phase outlet of the gas-liquid separator is connected with a hydrogen washing tower, the gas-phase outlet of the hydrogen washing tower is connected with a hydrogen circulating compressor, and the liquid-phase outlet of the hydrogen washing tower is connected with the liquid-solid separator; the liquid-solid separator is provided with a waste catalyst discharge port; the bottom of the reaction tube is connected with a material feeding tube.
10. The hydrogenation apparatus for preparing hexanediamine according to claim 9, wherein the hydrogen recycle compressor is connected with the inlet of the first channel of the mixing system; the liquid-solid separator is provided with a liquid phase outlet connected with an inlet of a second channel of the mixing system, and the liquid-solid separator is also provided with a hydrogenation reaction liquid outlet connected with a subsequent hydrogenation reaction liquid treatment process.
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