CN103351302A - Production method for preparing cyclohexylamine from phenylamine - Google Patents
Production method for preparing cyclohexylamine from phenylamine Download PDFInfo
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- CN103351302A CN103351302A CN2013102459690A CN201310245969A CN103351302A CN 103351302 A CN103351302 A CN 103351302A CN 2013102459690 A CN2013102459690 A CN 2013102459690A CN 201310245969 A CN201310245969 A CN 201310245969A CN 103351302 A CN103351302 A CN 103351302A
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- hexahydroaniline
- aniline
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- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 128
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000000047 product Substances 0.000 claims abstract description 22
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 41
- 239000001257 hydrogen Substances 0.000 claims description 41
- 229910052739 hydrogen Inorganic materials 0.000 claims description 41
- 239000012043 crude product Substances 0.000 claims description 30
- 238000009833 condensation Methods 0.000 claims description 24
- 230000005494 condensation Effects 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 19
- 230000008016 vaporization Effects 0.000 claims description 17
- 239000007791 liquid phase Substances 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000009835 boiling Methods 0.000 claims description 10
- 239000006200 vaporizer Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 238000009834 vaporization Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000000034 method Methods 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000004364 calculation method Methods 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- UDIPTWFVPPPURJ-UHFFFAOYSA-M Cyclamate Chemical compound [Na+].[O-]S(=O)(=O)NC1CCCCC1 UDIPTWFVPPPURJ-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000625 cyclamic acid and its Na and Ca salt Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000003599 food sweetener Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- NJNQUTDUIPVROZ-UHFFFAOYSA-N nitrocyclohexane Chemical compound [O-][N+](=O)C1CCCCC1 NJNQUTDUIPVROZ-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 235000020995 raw meat Nutrition 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229960001462 sodium cyclamate Drugs 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000003765 sweetening agent Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of the production and preparation of cyclohexylamine and particularly relates to a production method for preparing cyclohexylamine from phenylamine. Through controlling parameters, such as time, temperature, pressure and the like, of all steps, the yield of cyclohexylamine products is high and is over 98%, the quality is stable, the yield is high, the production capacity is large, the side reactions are few, a small amount of byproduct dicyclohexylamine produced during reaction can be recovered and purified, and the added value of the products is increased; and through engineering calculation and advanced DCS (Distributed Control System) control, the parameters are stable and are little in fluctuation, and qualified materials in a negative pressure tower are directly transferred to a rectification tower from the negative pressure tower through pressure difference between the negative pressure tower and the rectification tower, so that the working procedure is efficient and energy-saving, the continuous rectification procedure is completed, the continuity of the whole process is strong, the degree of automation is high, the staff ratio is low, the unit consumption is low, and the yield is high.
Description
Technical field
The invention belongs to the technical field of hexahydroaniline manufacture, be specially the production method that aniline prepares hexahydroaniline.
Background technology
Aniline is that a hydrogen atom in the benzene molecular replaces the compound that generates for amino.Molecular formula C
6H
5NH
2It is the simplest one-level aromatic amine.Colourless oil liquid.Fusing point-6.3 ℃, 184 ℃ of boiling points, relative density 1.02 (20/4 ℃), relative molecular weight 93.128 is heated to 370 ℃ of decomposition.Slightly water-soluble, be soluble in the organic solvents such as ethanol, ether.Be exposed in the air or daylight under become brown.Used water steam distillation adds a small amount of zinc powder with anti-oxidation during distillation.Aniline after the purification can add the NaBH4 of 10～15ppm, in case deterioration by oxidation.
Hexahydroaniline: colourless liquid.Fish raw meat amine smell is arranged.Relative density 0.8647 (25/25 ℃).134.5 ℃ of boiling points.Zero pour-17.7 ℃.Specific refractory power 1.4565 (25 ℃).Can be miscible with water and common organic solvents.Can volatilize with water vapour, and form azeotropic mixture with water.Inflammable, poisonous.
Hexahydroaniline is a kind of important fine-chemical intermediate, the main intermediate that is used as metal inhibitor, petroleum products additive, reactor treatment agent, boiler feed-water compound, sterilizing insecticide, static inhibitor and is used as rubber ingredients, dyestuff and tensio-active agent, sweetening agent Sugaron (Sodium Cyclamate) and rubber accelerator N cyclohexyl 2 benzothiazole sulfenamide (accelerator CBS), also can be used as simultaneously the preparation hexalin, pimelinketone, hexanolactam, cellulose acetate and nylon 6 etc.
The preparation method of hexahydroaniline is got by the aniline shortening, can be divided into non-pressure process and pressurization.In addition, by the catalysis ammonia solution of hexanaphthene or hexalin, the nitrocyclohexane reduction, and the methods such as pimelinketone catalysis ammonia solution under the hydrogen existence all can make hexahydroaniline.
Technique before, except the active ingredient of catalyzer, the processing condition of reaction, comprise that the factors such as temperature of reaction, reaction pressure, reaction ratio, reaction velocity all can produce larger impact to the yield of product, and catalyzer is difficult to reclaim, complex operation, the appliance arrangement expense is high, and reaction parameter control is unstable.
Summary of the invention
The object of the invention is to for the problem of above-mentioned existence and provide aniline to prepare the production method of hexahydroaniline.
Technical scheme of the present invention is:
Aniline prepares the production method of hexahydroaniline, aniline is by being pumped to the preheating of aniline interchanger, then enter in the same way vaporizer with hydrogen after the preheating of hydrogen interchanger, aniline enters superheater after vaporizing fully, after heat-conducting oil heating, enter reaction bed, reaction in the presence of catalyzer generates hexahydroaniline again; Reaction bed gas mixture out by hydrogen interchanger and the heat exchange of aniline interchanger cooling after, enter condenser condenses, wherein, the condensation liquid phase of getting off is advanced the crude product tank, non-condensable gas (H
2) deliver to hydrogen recycle by blower fan; Hexahydroaniline crude product in the crude product tank takes off low boiling and water by being pumped to negative pressure tower, and from negative pressure tower reactor punishment in advance to rectifying tower, the hexahydroaniline dry product boils at rectifying tower Nei Tuogao and enters the hexahydroaniline finished pot by condensation qualified dry product hexahydroaniline by vacuum; After the rectifying tower bottoms was collected, by being pumped to the dicyclohexyl amine separation column, overhead fraction reclaimed dicyclohexyl amine after condensation again, and the tar of liquid phase is processed by Tar Column at the bottom of the tower.
Described catalyzer is CuO/NiO/ γ-Al
2O
3Catalyzer.
The temperature of described reaction bed is 160-180 ℃, and pressure is 0.03-0.04MPa, and the reaction times is 3s-4s.
The mol ratio of aniline and hydrogen is 1:15-20.
Described negative pressure tower pressure is-0.065/-0.060MPa that temperature is 110-80 ℃.
Described Rectification column pressure position-0.075/-0.080 MPa, temperature is 125-95 ℃.
Described separation column pressure is-0.089/-0.085 MPa that temperature is 150-110 ℃.
The temperature 140-180 of described vaporizer ℃, pressure 0.03-0.04Mpa.
The temperature of described superheater is 150-180 ℃, and pressure is 0.03-0.04Mpa.
The present invention is controlled by DCS.
Aniline prepares the production method of hexahydroaniline, controlled by DCS, its concrete steps are: aniline is preheating to 160-180 ℃ by being pumped to the aniline interchanger, then enter in the same way vaporizer with the hydrogen that is preheating to 140-170 ℃ through the hydrogen interchanger, the temperature 140-180 of vaporization ℃, pressure 0.03-0.04Mpa, the mol ratio of aniline and hydrogen is 1:15-20, aniline enters superheater after vaporizing fully, and the temperature of superheater is 150-180 ℃, and pressure is 0.03-0.04Mpa; After heat-conducting oil heating, enter again reaction bed, at CuO/NiO/ γ-Al
2O
3There is lower reaction in catalyzer, and temperature of reaction is 160-180 ℃, and pressure is 0.03-0.04MPa, and the reaction times is 3s-4s, generates hexahydroaniline; After reaction bed gas mixture out returns hydrogen interchanger and the heat exchange of aniline interchanger cooling, enter below the condenser condenses to 50 ℃, wherein, the condensation liquid phase of getting off is advanced the crude product tank, and crude product purity is 95-98%, non-condensable gas (H
2) deliver to hydrogen recycle by blower fan; Hexahydroaniline crude product in the crude product tank is by being pumped to negative pressure tower, negative pressure tower pressure is-0.065/-0.060MPa, temperature is 110-80 ℃, take off low boiling and water, qualified dry product hexahydroaniline by vacuum from negative pressure tower reactor punishment in advance to rectifying tower, Rectification column pressure is-0.075/-0.080 MPa, and temperature is 125-95 ℃, and the hexahydroaniline dry product boils at rectifying tower Nei Tuogao and enters the hexahydroaniline finished pot by condensation; After the rectifying tower bottoms was collected, again by being pumped to the dicyclohexyl amine separation column, separation column pressure was-0.089/-0.085 MPa, and temperature is 150-110 ℃, and overhead fraction reclaims dicyclohexyl amine after condensation, and the tar of liquid phase is processed by Tar Column at the bottom of the tower.
The aniline shortening generates the hexahydroaniline reaction
Beneficial effect of the present invention is: the method for production hexahydroaniline of the present invention, in addition, technique of the present invention
Technique of the present invention is by the parameter in each step of control, such as time, temperature, pressure etc., the hexahydroaniline product yield is high, product yield is more than 98%, steady quality, and productive rate is high, throughput is large, side reaction is few, and a small amount of by product dicyclohexyl amine in the reaction can reclaim purification, the increase added value of product.By engineering calculation and advanced DCS control, parameter stability, the fluctuation little, the qualified pressure reduction of material by existing between two towers in the negative pressure tower, directly in the negative pressure tower to the rectifying tower punishment in advance, operation is energy-efficient, thereby finish the continuous rectification operation, whole technique continuity is strong, and level of automation is high, and personnel's proportioning is few, unit consumption is few, and output is high.In a word, the method technique of production hexahydroaniline of the present invention is simple, easy to operate, safe, and facility investment is few, and technique is simple.
Description of drawings
Fig. 1 is process flow sheet of the present invention.
Embodiment
Below by specific embodiment technical scheme of the present invention is described in detail.
Embodiment 1
Aniline prepares the production method of hexahydroaniline, its concrete steps are: aniline is preheating to 160 ℃ by being pumped to the aniline interchanger, then enter in the same way vaporizer with the hydrogen that is preheating to 140 ℃ through the hydrogen interchanger, 150 ℃ of the temperature of vaporization, pressure 0.03Mpa, the mol ratio of aniline and hydrogen is 1:15, aniline enters superheater after vaporizing fully, the temperature of superheater is 150 ℃, and pressure is 0.03Mpa; After heat-conducting oil heating, enter again reaction bed, at CuO/NiO/ γ-Al
2O
3There is lower reaction in catalyzer, and temperature of reaction is 160 ℃, and pressure is 0.03MPa, and the reaction times is 3s-4s, generates hexahydroaniline; After reaction bed gas mixture out returns hydrogen interchanger and the heat exchange of aniline interchanger cooling, enter below the condenser condenses to 50 ℃, wherein, the condensation liquid phase of getting off is advanced the crude product tank, and crude product purity is 96%, non-condensable gas (H
2) deliver to hydrogen recycle by blower fan; Hexahydroaniline crude product in the crude product tank is by being pumped to negative pressure tower, negative pressure tower pressure is-0.065MPa, temperature is 110 ℃, take off low boiling and water, qualified dry product hexahydroaniline by vacuum from negative pressure tower reactor punishment in advance to rectifying tower, Rectification column pressure is-0.075 MPa, and temperature is 125 ℃, and the hexahydroaniline dry product boils at rectifying tower Nei Tuogao and enters the hexahydroaniline finished pot by condensation; After the rectifying tower bottoms was collected, by being pumped to the dicyclohexyl amine separation column, separation column pressure was-0.089 MPa again, and temperature is 150 ℃, and overhead fraction reclaims dicyclohexyl amine after condensation, and the tar of liquid phase is processed by Tar Column at the bottom of the tower.
Embodiment 2
Aniline prepares the production method of hexahydroaniline, controlled by DCS, its concrete steps are: aniline is preheating to 180 ℃ by being pumped to the aniline interchanger, then enter in the same way vaporizer with the hydrogen that is preheating to 170 ℃ through the hydrogen interchanger, 180 ℃ of the temperature of vaporization, pressure 0.04Mpa, the effect of vaporization is that material is become gas from liquid, purpose is to allow fully contact with catalyzer, increases and the contact area of catalyzer makes that reaction is more abundant, transformation efficiency is higher.
The mol ratio of aniline and hydrogen is 1:20, and aniline enters superheater after vaporizing fully, and the temperature of superheater is 180 ℃, and pressure is 0.04Mpa; The effect of superheater is to allow liquid fully gasify.
After heat-conducting oil heating, enter again reaction bed, at CuO/NiO/ γ-Al
2O
3There is lower reaction in catalyzer, and temperature of reaction is 180 ℃, and pressure is 0.04MPa, and the reaction times is 3s-4s, generates hexahydroaniline; After reaction bed gas mixture out returns hydrogen interchanger and the heat exchange of aniline interchanger cooling, enter below the condenser condenses to 50 ℃, wherein, the condensation liquid phase of getting off is advanced the crude product tank, and crude product purity is 98%, non-condensable gas (H
2) deliver to hydrogen recycle by blower fan; Hexahydroaniline crude product in the crude product tank is by being pumped to negative pressure tower, negative pressure tower pressure is-0.060MPa, temperature is 80 ℃, take off low boiling and water, qualified dry product hexahydroaniline by vacuum from negative pressure tower reactor punishment in advance to rectifying tower, Rectification column pressure is-0.080 MPa, and temperature is 100 ℃, and the hexahydroaniline dry product boils at rectifying tower Nei Tuogao and enters the hexahydroaniline finished pot by condensation; After the rectifying tower bottoms was collected, by being pumped to the dicyclohexyl amine separation column, separation column pressure was-0.085 MPa again, and temperature is 110 ℃, and overhead fraction reclaims dicyclohexyl amine after condensation, and the tar of liquid phase is processed by Tar Column at the bottom of the tower.
Embodiment 3
Aniline prepares the production method of hexahydroaniline, controlled by DCS, its concrete steps are: aniline is preheating to 170 ℃ by being pumped to the aniline interchanger, then enter in the same way vaporizer with the hydrogen that is preheating to 160 ℃ through the hydrogen interchanger, 170 ℃ of the temperature of vaporization, pressure 0.04Mpa, the effect of vaporization is that material is become gas from liquid, purpose is to allow fully contact with catalyzer, increases and the contact area of catalyzer makes that reaction is more abundant, transformation efficiency is higher.
The mol ratio of aniline and hydrogen is 1:18, and aniline enters superheater after vaporizing fully, and the temperature of superheater is 170 ℃, and pressure is 0.035Mpa; The effect of superheater is to allow liquid fully gasify.
After heat-conducting oil heating, enter again reaction bed, at CuO/NiO/ γ-Al
2O
3There is lower reaction in catalyzer, and temperature of reaction is 180 ℃, and pressure is 0.035MPa, and the reaction times is 3s-4s, generates hexahydroaniline; After reaction bed gas mixture out returns hydrogen interchanger and the heat exchange of aniline interchanger cooling, enter below the condenser condenses to 50 ℃, wherein, the condensation liquid phase of getting off is advanced the crude product tank, and crude product purity is 97%, non-condensable gas (H
2) deliver to hydrogen recycle by blower fan; Hexahydroaniline crude product in the crude product tank is by being pumped to negative pressure tower, negative pressure tower pressure is-0.060MPa, temperature is 100 ℃, take off low boiling and water, qualified dry product hexahydroaniline by vacuum from negative pressure tower reactor punishment in advance to rectifying tower, Rectification column pressure is-0.078 MPa, and temperature is 120 ℃, and the hexahydroaniline dry product boils at rectifying tower Nei Tuogao and enters the hexahydroaniline finished pot by condensation; After the rectifying tower bottoms was collected, by being pumped to the dicyclohexyl amine separation column, separation column pressure was-0.087 MPa again, and temperature is 130 ℃, and overhead fraction reclaims dicyclohexyl amine after condensation, and the tar of liquid phase is processed by Tar Column at the bottom of the tower.
Embodiment 4
Aniline prepares the production method of hexahydroaniline, controlled by DCS, its concrete steps are: aniline is preheating to 150 ℃ by being pumped to the aniline interchanger, then enter in the same way vaporizer with the hydrogen that is preheating to 150 ℃ through the hydrogen interchanger, 160 ℃ of the temperature of vaporization, pressure 0.035Mpa, the effect of vaporization is that material is become gas from liquid, purpose is to allow fully contact with catalyzer, increases and the contact area of catalyzer makes that reaction is more abundant, transformation efficiency is higher.
The mol ratio of aniline and hydrogen is 1:16, and aniline enters superheater after vaporizing fully, and the temperature of superheater is 160 ℃, and pressure is 0.03Mpa; The effect of superheater is to allow liquid fully gasify.
After heat-conducting oil heating, enter again reaction bed, at CuO/NiO/ γ-Al
2O
3There is lower reaction in catalyzer, and temperature of reaction is 170 ℃, and pressure is 0.04MPa, and the reaction times is 3s-4s, generates hexahydroaniline; After reaction bed gas mixture out returns hydrogen interchanger and the heat exchange of aniline interchanger cooling, enter below the condenser condenses to 50 ℃, wherein, the condensation liquid phase of getting off is advanced the crude product tank, and crude product purity is 97%, non-condensable gas (H
2) deliver to hydrogen recycle by blower fan; Hexahydroaniline crude product in the crude product tank is by being pumped to negative pressure tower, negative pressure tower pressure is-0.063MPa, temperature is 90 ℃, take off low boiling and water, qualified dry product hexahydroaniline by vacuum from negative pressure tower reactor punishment in advance to rectifying tower, Rectification column pressure is-0.079 MPa, and temperature is 110 ℃, and the hexahydroaniline dry product boils at rectifying tower Nei Tuogao and enters the hexahydroaniline finished pot by condensation; After the rectifying tower bottoms was collected, by being pumped to the dicyclohexyl amine separation column, separation column pressure was-0.088 MPa again, and temperature is 120 ℃, and overhead fraction reclaims dicyclohexyl amine after condensation, and the tar of liquid phase is processed by Tar Column at the bottom of the tower.
Claims (10)
1. aniline prepares the production method of hexahydroaniline, aniline is by being pumped to the preheating of aniline interchanger, then enter in the same way vaporizer with hydrogen after the preheating of hydrogen interchanger, aniline enters superheater after vaporizing fully, after heat-conducting oil heating, enter reaction bed, reaction in the presence of catalyzer generates hexahydroaniline again; Reaction bed gas mixture out by hydrogen interchanger and the heat exchange of aniline interchanger cooling after, enter condenser condenses, wherein, the condensation liquid phase of getting off is advanced the crude product tank, non-condensable gas (H
2) deliver to hydrogen recycle by blower fan; Hexahydroaniline crude product in the crude product tank takes off low boiling and water by being pumped to negative pressure tower, and from negative pressure tower reactor punishment in advance to rectifying tower, the hexahydroaniline dry product boils at rectifying tower Nei Tuogao and enters the hexahydroaniline finished pot by condensation qualified dry product hexahydroaniline by vacuum; After the rectifying tower bottoms was collected, by being pumped to the dicyclohexyl amine separation column, overhead fraction reclaimed dicyclohexyl amine after condensation again, and the tar of liquid phase is processed by Tar Column at the bottom of the tower.
2. aniline according to claim 1 prepares the production method of hexahydroaniline, it is characterized in that, described catalyzer is CuO/NiO/ γ-Al
2O
3Catalyzer.
3. aniline according to claim 1 prepares the production method of hexahydroaniline, it is characterized in that, the mol ratio of aniline and hydrogen is 1:15-20.
4. aniline according to claim 1 prepares the production method of hexahydroaniline, it is characterized in that, described negative pressure tower pressure is-0.065/-0.060MPa that temperature is 110-80 ℃.
5. aniline according to claim 1 prepares the production method of hexahydroaniline, it is characterized in that, described Rectification column pressure position-0.075/-0.080 MPa, and temperature is 125-95 ℃.
6. aniline according to claim 1 prepares the production method of hexahydroaniline, it is characterized in that, described separation column pressure is-0.089/-0.085 MPa that temperature is 150-110 ℃.
7. aniline according to claim 1 prepares the production method of hexahydroaniline, it is characterized in that, and the temperature 140-180 of described vaporizer ℃, pressure 0.03-0.04Mpa.
8. aniline according to claim 1 prepares the production method of hexahydroaniline, it is characterized in that, the temperature of described superheater is 150-180 ℃, and pressure is 0.03-0.04Mpa.
9. aniline according to claim 1 prepares the production method of hexahydroaniline, it is characterized in that, the temperature of described reaction bed is 160-180 ℃, and pressure is 0.03-0.04MPa, and the reaction times is 3s-4s.
10. aniline prepares the production method of hexahydroaniline, controlled by DCS, its concrete steps are: aniline is preheating to 160-180 ℃ by being pumped to the aniline interchanger, then enter in the same way vaporizer with the hydrogen that is preheating to 140-170 ℃ through the hydrogen interchanger, the temperature 140-180 of vaporization ℃, pressure 0.03-0.04Mpa, the mol ratio of aniline and hydrogen is 1: 15-20, aniline enters superheater after vaporizing fully, and the temperature of superheater is 150-180 ℃, and pressure is 0.03-0.04Mpa; After heat-conducting oil heating, enter again reaction bed, at CuO/NiO/ γ-Al
2O
3There is lower reaction in catalyzer, and temperature of reaction is 160-180 ℃, and pressure is 0.03-0.04MPa, and the reaction times is 3s-4s, generates hexahydroaniline; After reaction bed gas mixture out returns hydrogen interchanger and the heat exchange of aniline interchanger cooling, enter below the condenser condenses to 50 ℃, wherein, the condensation liquid phase of getting off is advanced the crude product tank, and crude product purity is 95-98%, non-condensable gas (H
2) deliver to hydrogen recycle by blower fan; Hexahydroaniline crude product in the crude product tank is by being pumped to negative pressure tower, negative pressure tower pressure is-0.065/-0.060MPa, temperature is 110-80 ℃, take off low boiling and water, qualified dry product hexahydroaniline by vacuum from negative pressure tower reactor punishment in advance to rectifying tower, Rectification column pressure is-0.075/-0.080 MPa, and temperature is 125-95 ℃, and the hexahydroaniline dry product boils at rectifying tower Nei Tuogao and enters the hexahydroaniline finished pot by condensation; After the rectifying tower bottoms was collected, again by being pumped to the dicyclohexyl amine separation column, separation column pressure was-0.089/-0.085 MPa, and temperature is 150-110 ℃, and overhead fraction reclaims dicyclohexyl amine after condensation, and the tar of liquid phase is processed by Tar Column at the bottom of the tower.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237434A (en) * | 2015-10-29 | 2016-01-13 | 中石化南京工程有限公司 | Method for producing cyclohexanone oxime |
| CN110665244A (en) * | 2019-10-09 | 2020-01-10 | 万华化学集团股份有限公司 | Gas phase reaction device and method for preparing dicyclohexylamine |
| CN113200864A (en) * | 2021-05-31 | 2021-08-03 | 金城化学(江苏)有限公司 | Continuous production process and device of cyclohexylamine and dicyclohexylamine |
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| CN102516087A (en) * | 2011-10-25 | 2012-06-27 | 江苏诺盟化工有限公司 | Resource utilization preparation method for high-purity dicyclohexyl amine |
| CN102633649A (en) * | 2012-03-29 | 2012-08-15 | 山东潍焦集团有限公司 | Method for synthesizing cyclohexylamine with aniline by means of gas-phase catalytic hydrogenation |
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| CN102516087A (en) * | 2011-10-25 | 2012-06-27 | 江苏诺盟化工有限公司 | Resource utilization preparation method for high-purity dicyclohexyl amine |
| CN102633649A (en) * | 2012-03-29 | 2012-08-15 | 山东潍焦集团有限公司 | Method for synthesizing cyclohexylamine with aniline by means of gas-phase catalytic hydrogenation |
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| 任世彪等: "CuO-NiO／γ-Al2O3表面分散状态、还原行为与催化加氢性能", 《第十三届全国催化学术会议论文集》, 1 September 2006 (2006-09-01), pages 601 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237434A (en) * | 2015-10-29 | 2016-01-13 | 中石化南京工程有限公司 | Method for producing cyclohexanone oxime |
| CN110665244A (en) * | 2019-10-09 | 2020-01-10 | 万华化学集团股份有限公司 | Gas phase reaction device and method for preparing dicyclohexylamine |
| CN110665244B (en) * | 2019-10-09 | 2021-10-22 | 万华化学集团股份有限公司 | Gas phase reaction device and method for preparing dicyclohexylamine |
| CN113200864A (en) * | 2021-05-31 | 2021-08-03 | 金城化学(江苏)有限公司 | Continuous production process and device of cyclohexylamine and dicyclohexylamine |
| CN113200864B (en) * | 2021-05-31 | 2023-10-24 | 金城化学(江苏)有限公司 | Continuous production process and device for cyclohexylamine and dicyclohexylamine |
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