CN110724068A - Process for producing high-purity acrylonitrile - Google Patents
Process for producing high-purity acrylonitrile Download PDFInfo
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- CN110724068A CN110724068A CN201810778736.XA CN201810778736A CN110724068A CN 110724068 A CN110724068 A CN 110724068A CN 201810778736 A CN201810778736 A CN 201810778736A CN 110724068 A CN110724068 A CN 110724068A
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- acrylonitrile
- defoaming agent
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- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 64
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 50
- -1 polyoxypropylene Polymers 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 24
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000032050 esterification Effects 0.000 claims abstract description 10
- 238000005886 esterification reaction Methods 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 7
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 6
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 238000010791 quenching Methods 0.000 claims description 27
- 230000000171 quenching effect Effects 0.000 claims description 26
- 238000011084 recovery Methods 0.000 claims description 18
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 238000007255 decyanation reaction Methods 0.000 claims description 3
- 239000013530 defoamer Substances 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 abstract description 19
- 238000006703 hydration reaction Methods 0.000 abstract description 8
- 230000036571 hydration Effects 0.000 abstract description 7
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 23
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 22
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 14
- 238000009826 distribution Methods 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 230000000813 microbial effect Effects 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000013048 microbiological method Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 3
- 241001052560 Thallis Species 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 108010024026 Nitrile hydratase Proteins 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical group N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000004391 petroleum recovery Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
- C07C253/34—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
- C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of high-purity acrylonitrile, belonging to the technical field of acrylonitrile preparation. The preparation method of the high-purity acrylonitrile adopts a Sohio method, propylene, ammonia and air are fed into a fluidized bed catalytic reactor for catalytic reaction, polyoxypropylene ether containing polyoxyethylene and modified by terminal group esterification is added in the reaction and serves as a defoaming agent, the addition amount of the defoaming agent is 10-20ppm, and the hourly yield of the acrylonitrile is taken as a reference. The invention has scientific and reasonable design, reduces the influence of trace components and residual defoaming agent in acrylonitrile on acrylonitrile hydration and acrylamide polymerization, and is beneficial to industrial production.
Description
Technical Field
The invention relates to a preparation method of high-purity acrylonitrile, belonging to the technical field of acrylonitrile preparation.
Background
Acrylonitrile (AN) is AN important monomer for synthetic fibers, synthetic rubbers and synthetic resins. In recent years, with the development of acrylonitrile downstream products such as polyacrylonitrile fiber, acrylonitrile-butadiene-styrene plastic, nitrile rubber, nitrile latex, acrylamide, hexamethylene diamine and the like, particularly the continuous development and application of new downstream fine chemical products, the demand of acrylonitrile in the world is continuously increased.
Nowadays, more than 95% of acrylonitrile is produced globally by the Sohio process. According to the process, chemical-grade propylene (the mass fraction of the propylene is not less than 93 percent), fertilizer-grade ammonia and air are fed into a fluidized bed catalytic reactor according to the mass ratio of 1.0 to (1.15-1.25) to (9.3-10), a catalyst adopts silicon dioxide-loaded bismuth phosphomolybdate, the reaction temperature is 430-445 ℃, the pressure is 0.03-0.10 MPa, and the contact time is 5-10 s. The reaction is rapidly released, the reaction heat is removed through a U-shaped pipe heat exchanger, steam is generated, and the steam is used as the driving force of an air compressor and an ice machine steam turbine. While generating acrylonitrile, byproducts such as hydrocyanic acid, acetonitrile, propionitrile, acetone, acetaldehyde, acetic acid and the like are also generated.
The acrylonitrile device mainly comprises three main systems of reaction, recovery and refining. The core of the reaction system is a fluidized bed catalytic reactor, and propylene reacts under the action of a catalyst to generate acrylonitrile, acetonitrile, hydrocyanic acid and the like; the recovery system is used for recovering acrylonitrile and other organic matters, and simultaneously neutralizing unreacted ammonia to generate ammonium sulfate; the refining system is used for refining the acrylonitrile product to prepare the final acrylonitrile finished product.
Along with the improvement of the requirement of environmental protection in China, the dosage of acrylamide and polyacrylamide is gradually increased, wherein the dosage of the acrylamide accounts for 50 percent of that of acrylonitrile, the acrylamide is a main raw material for preparing the polyacrylamide, and the polyacrylamide can be used as a water treatment flocculant, a petroleum recovery agent, a reinforcing agent in the paper industry and the like.
There are two main methods for preparing acrylamide by hydrating acrylonitrile, one is a copper catalyst method in which acrylonitrile is hydrated to obtain an aqueous acrylamide solution under the catalysis of a copper catalyst (metallic copper, reduced copper, or skeletal copper); the other is a microbiological method in which hydration is carried out using a microbial cell containing nitrile hydratase, a treated product of the cell, or the like as a catalyst; among the above methods, the microbiological method is higher in conversion rate and selectivity of acrylonitrile than the copper catalytic method, and therefore, most industrial apparatuses now use the microbiological method to prepare an aqueous acrylamide solution.
When acrylamide is prepared by a microbiological method, operations such as washing of microbial thalli after reaction are needed to recycle the microbial thalli, and acrylonitrile residue in an acrylamide aqueous solution prepared in each batch is required to be lower than 0.1 wt% in order to ensure reaction efficiency of acrylonitrile hydration reaction of each batch because acrylonitrile has a toxic effect on the microbial thalli; in general industrial production, the microbial thallus can be reused for 3-5 times.
Because the acrylonitrile products of different manufacturers have different types and contents of trace impurities, when the acrylonitrile products of different manufacturers are subjected to hydration tests on the same microbial thallus, the reaction batches and the acrylonitrile residues of each batch are different, and different acrylonitrile manufacturers require that the same batch and the same acrylonitrile residues are achieved as far as possible when the hydration tests are carried out.
However, when part of the existing acrylonitrile is used for synthesis by the existing biological acrylamide manufacturers, the problems that the activity of the hydratase is reduced, the reaction batch is shortened and even the reaction cannot be carried out easily occur; the prepared acrylamide cannot be used for synthesizing high molecular weight (molecular weight is more than 2500 ten thousand) polyacrylamide, so that the development of acrylonitrile suitable for the production requirement of high-end acrylamide is required.
CN103804226B mainly reduces the content of oxazole in acrylonitrile by changing the position of acrylonitrile plant material at the outlet of the product tower and adding the material into a condensation recovery device, and patent 102199104B mainly controls the parameters of the acrylonitrile plant such as process control temperature, pressure, number of tower plates, reflux ratio, etc. to reduce the content of impurities in acrylonitrile; the above patent only adjusts the process partially, only reduces the impurity content in acrylonitrile, and does not consider the influence of the residual defoaming agent on acrylamide hydration and polymerization.
Disclosure of Invention
The invention aims to provide a preparation method of high-purity acrylonitrile, which has scientific and reasonable design, reduces the influence of trace components and residual defoaming agent in acrylonitrile on acrylonitrile hydration and acrylamide polymerization, and is beneficial to industrial production.
The preparation method of the high-purity acrylonitrile adopts a Sohio method, propylene, ammonia and air are fed into a fluidized bed catalytic reactor for catalytic reaction, polyoxypropylene ether containing polyoxyethylene and modified by terminal group esterification is added in the reaction and serves as a defoaming agent, the addition amount of the defoaming agent is 10-20ppm, and the hourly yield of the acrylonitrile is taken as a reference.
The ammonia-nitrogen ratio is controlled to be 1.0-1.2. The mass ratio of the propylene, the ammonia and the air disclosed in the prior art is 1.0: 1.0-1.2: 9.3-10, and the invention greatly improves the ammonia-nitrogen ratio to reduce impurities in the reaction.
The total aldehyde content in the reaction product is 10-15 ppm.
The pH value of the upper section of the quenching tower used in the reaction is controlled to be 3-5, and the pH value of the lower section of the quenching tower is controlled to be 7-9.
And controlling the pH value of a large circulation system used in the reaction to be 6.5-7.5.
And controlling the pH value of the decyanation tower bottom liquid used in the reaction to be 4.0-4.3.
And controlling the pH value of the finished product tower acrylonitrile used in the reaction to be 6.3-7.0, and controlling the average value to be about 6.7.
The temperature of the sensitive point of the recovery tower is controlled between 75 and 85 ℃.
The modification process of the defoaming agent comprises the following steps:
(1) taking dihydric alcohol or trihydric alcohol as a modified end group, and grafting the dihydric alcohol or trihydric alcohol onto polyoxypropylene ether;
(2) and (2) carrying out esterification modification on the alcohol end group of the grafted polyoxypropylene ether obtained in the step (1) to obtain an ester group, thus obtaining the esterified polyoxypropylene ether containing polyoxyethylene. The polyoxyethylene is produced by grafting with the addition of ethylene oxide. The small amount of polyoxyethylene is beneficial to improving the hydrophilicity of the esterification modified polyoxypropylene ether.
The mass content of polyoxyethylene in the esterification modified polyoxypropylene ether is 1-5%.
In order to further improve the dispersibility and low-temperature solubility of the esterification modified polyether defoamer in acrylonitrile, a performance-improving low-molecular-weight amine substance such as dimethylamine and the like is added into the modified defoamer.
The molecular weight of the esterification modified polyoxypropylene ether is 3500-4000, and the molecular weight distribution is 1.0-1.2.
The residual quantity of the defoaming agent in the acrylonitrile is controlled to be 5-10 ppm.
The process aims to reduce system impurities, reduce the addition of the defoaming agent and improve the defoaming property.
The invention has the following beneficial effects:
according to the invention, analysis shows that the acrylonitrile raw material contains various trace impurities such as acetaldehyde, hydrocyanic acid, acetone, acrolein, methacrylonitrile, oxazole, propionitrile, butenenitrile, a polymerization inhibitor, peroxide, iron ions and the like, which can affect nitrile hydratase, so that the reaction batch and the product quality of acrylamide are affected; meanwhile, researches find that excessive residues of polyoxypropylene ether defoaming agents added into the existing acrylonitrile for preventing a recovery system from generating foams in the acrylonitrile can influence the polymerization of acrylamide, so that the product quality is influenced, and products with the molecular weight of more than or equal to 2500 ten thousand cannot be prepared.
According to the invention, by adjusting conditions such as ammonia-nitrogen ratio, pH value of a quench tower, pH value of a large circulation and pH value of a decyanation tower of devices such as a recovery tower and the like, and the type and the addition amount of the defoaming agent, trace components such as oxazole, total aldehyde, total cyanide and defoaming agent residue in acrylonitrile are controlled within a certain range, the influence of the trace components in the acrylonitrile on acrylonitrile hydration is reduced, and meanwhile, the consumption of the defoaming agent is reduced on the basis of not influencing the existing defoaming efficiency of the device, so that the acrylonitrile suitable for high-end acrylamide requirement is prepared.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.
Example 1
The ammonia-nitrogen ratio is 1.0, the pH value of the upper section of the quenching tower is 3, the pH value of the lower end of the quenching tower is 8, the pH value of a large circulation is 6.5, the control temperature of a recovery tower is 75 ℃, the pH value of acrylonitrile of a finished product tower is 6.3, the type of the defoaming agent is polyoxypropylene ether containing 1% of polyoxyethylene, the molecular weight of the defoaming agent is 3500, the molecular weight distribution is 1.0, the addition amount of the defoaming agent is 10ppm, the acrolein content in finally obtained acrylonitrile is 12ppm, the oxazole content is 4ppm, the total cyanogen content is 1ppm, and the residual amount of the defoaming agent is 7 ppm.
Example 2
The ammonia-nitrogen ratio is 1.2, the pH value of the upper section of the quenching tower is 4, the pH value of the lower end of the quenching tower is 9, the pH value of a large circulation is 7.5, the control temperature of a recovery tower is 85 ℃, the pH value of acrylonitrile of a finished product tower is 7, the type of the defoaming agent is polyoxypropylene ether containing 5% of polyoxyethylene, the molecular weight of the defoaming agent is 4000, the molecular weight distribution is 1.2, the addition amount of the defoaming agent is 20ppm, the acrolein content in finally obtained acrylonitrile is 14ppm, the oxazole content is 7ppm, the total cyanogen content is 5ppm, and the residual amount of the defoaming agent is 9 ppm.
Example 3
The ammonia-nitrogen ratio is 1.1, the pH value of the upper section of the quenching tower is 5, the pH value of the lower end of the quenching tower is 8, the pH value of a large circulation is 7, the control temperature of a recovery tower is 80 ℃, the pH value of acrylonitrile of a finished product tower is 6.6, the type of the defoaming agent is polyoxypropylene ether containing 2% of polyoxyethylene, the molecular weight of the defoaming agent is 3700, the molecular weight distribution is 1.1, the addition amount of the defoaming agent is 6ppm, the acrolein content in finally obtained acrylonitrile is 10ppm, the oxazole content is 6ppm, the total cyanogen content is 3ppm, and the residual amount of the defoaming agent is 8 ppm.
Example 4
The ammonia-nitrogen ratio is 1.15, the pH value of the upper section of the quenching tower is 3, the pH value of the lower end of the quenching tower is 7.5, the pH value of a large circulation is 7.2, the temperature of a recovery tower is controlled to be 81 ℃, the pH value of acrylonitrile of a finished product tower is controlled to be 6.7, the type of the defoaming agent is polyoxypropylene ether containing 3 percent of polyoxyethylene, the molecular weight of the defoaming agent is 3800, the molecular weight distribution is 1.0, the addition amount of the defoaming agent is controlled to be 9ppm, the acrolein content in the finally obtained acrylonitrile is 9ppm, the oxazole content is 7ppm, the total cyanogen content is 4ppm, and the residual amount of the defoaming agent is.
Example 5
The ammonia-nitrogen ratio is 1.0, the pH value of the upper section of the quenching tower is 3, the pH value of the lower end of the quenching tower is 8.5, the pH value of a large circulation is 6.9, the control temperature of a recovery tower is 80 ℃, the pH value of acrylonitrile of a finished product tower is 7, the type of the defoaming agent is polyoxypropylene ether containing 2% of polyoxyethylene, the molecular weight of the defoaming agent is 4000, the molecular weight distribution is 1.1, the addition amount of the defoaming agent is 10ppm, the acrolein content in finally obtained acrylonitrile is 14ppm, the oxazole content is 9ppm, the total cyanogen content is 3ppm, and the residual amount of the defoaming agent is 10 ppm.
Example 6
The ammonia-nitrogen ratio is 1.2, the pH value of the upper section of the quenching tower is 4, the pH value of the lower end of the quenching tower is 8, the pH value of a large circulation is 7.4, the control temperature of a recovery tower is 85 ℃, the pH value of acrylonitrile of a finished product tower is 6.3, the type of the defoaming agent is polyoxypropylene ether containing 5% of polyoxyethylene, the molecular weight of the defoaming agent is 3900, the molecular weight distribution is 1.0, the addition amount of the defoaming agent is 10ppm, the acrolein content in finally obtained acrylonitrile is 15ppm, the oxazole content is 9ppm, the total cyanogen content is 4ppm, and the residual amount of the defoaming agent is 5 ppm.
Example 7
The ammonia-nitrogen ratio is 1.2, the pH value of the upper section of a quenching tower is 4, the pH value of the lower end of the quenching tower is 8, the pH value of a large circulation is 7.4, the control temperature of a recovery tower is 85 ℃, the pH value of acrylonitrile of a finished product tower is 6.3, the end group of a defoaming agent is glycerol, a modification additive is methylamine, the modification defoaming agent is esterified and modified polyoxypropylene ether containing 2% polyoxyethylene, the molecular weight of the modification defoaming agent is 3900, the molecular weight distribution is 1.0, the addition amount of the defoaming agent is 10ppm, the acrolein content in finally obtained acrylonitrile is 15ppm, the oxazole content is 9ppm, the total cyanogen content is 4ppm, and the residual amount of the defoaming agent is 3 ppm.
Example 8
The ammonia-nitrogen ratio is 1.2, the pH value of the upper section of a quenching tower is 4, the pH value of the lower end of the quenching tower is 8, the pH value of a large circulation is 7.4, the control temperature of a recovery tower is 85 ℃, the pH value of acrylonitrile of a finished product tower is 6.3, the end group of a defoaming agent is glycol, a modifying additive is dimethylamine, the modifying defoaming agent is esterified and modified polyoxypropylene ether containing 3% of polyoxyethylene, the molecular weight of the modifying defoaming agent is 3900, the molecular weight distribution is 1.0, the addition amount of the defoaming agent is 10ppm, the acrolein content in finally obtained acrylonitrile is 15ppm, the oxazole content is 9ppm, the total cyanogen content is 4ppm, and the residual amount of the defoaming agent is 2 ppm.
Comparative example 1
The ammonia-nitrogen ratio is 1.2, the pH value of the upper section of the quenching tower is 4, the pH value of the lower end of the quenching tower is 6.5, the pH value of a large circulation is 7.4, the temperature of the recovery tower is controlled to be 85 ℃, the pH value of acrylonitrile of a finished product tower is controlled to be 6.3, the type of the defoaming agent is polyoxypropylene ether, the molecular weight of the defoaming agent is 3900, the molecular weight distribution is 1.0, the addition amount of the defoaming agent is controlled to be 50ppm, the acrolein content in finally obtained acrylonitrile is 15ppm, the oxazole content is 9ppm, the total cyanogen content is 4ppm, and the residual amount of the defoaming agent is.
Comparative example 2
The ammonia-nitrogen ratio is 1.6, the pH value of the upper section of the quenching tower is 4, the pH value of the lower end of the quenching tower is 6.5, the pH value of a large circulation is 7.4, the temperature of the recovery tower is controlled to be 85 ℃, the pH value of acrylonitrile of a finished product tower is controlled to be 6.3, the type of the defoaming agent is polyoxypropylene ether, the molecular weight of the defoaming agent is 3900, the molecular weight distribution is 1.0, the addition amount of the defoaming agent is controlled to be 50ppm, the acrolein content in finally obtained acrylonitrile is 30ppm, the oxazole content is 20ppm, the total cyanogen content is 10ppm, and the residual amount of the defoaming agent is.
Comparative example 3
The ammonia-nitrogen ratio is 1.6, the pH value of the upper section of the quenching tower is 4, the pH value of the lower end of the quenching tower is 6.5, the pH value of a large circulation is 9, the control temperature of a recovery tower is 85 ℃, the pH value of acrylonitrile of a finished product tower is 6.3, the type of the defoaming agent is polyoxypropylene ether, the molecular weight of the defoaming agent is 3900, the molecular weight distribution is 1.0, the addition amount of the defoaming agent is controlled to 50ppm, the acrolein content in finally obtained acrylonitrile is 35ppm, the oxazole content is 25ppm, the total cyanogen content is 15ppm, and the residual amount of the defoaming agent is 30 ppm.
The acrylonitrile sample is used for synthesizing acrylamide by a biological method, and the synthesis process conditions are as follows:
20g of hydratase and 350g of deionized water are added into a 500mL four-neck flask, the pH of the mixed solution is adjusted to 5.5, stirring is started, the stirring speed is 200rpm, when the temperature of the mixed solution rises to 16 ℃, 100g of acrylonitrile is added into the mixed solution in a dropwise manner, the adding speed of the acrylonitrile is 1mL/min, and the reaction control temperature of the mixed solution is 21 ℃.
TABLE 1 dispersing effect of defoaming agent in acrylonitrile in examples and comparative examples
TABLE 2 Acrylonitrile residue and hydratase use batches for each of the examples and comparative examples
Claims (10)
1. A preparation method of high-purity acrylonitrile is characterized by comprising the following steps: sending propylene, ammonia and air into a fluidized bed catalytic reactor for catalytic reaction by adopting a Sohio method, adding polyoxyethylene polyoxypropylene ether modified by terminal esterification as a defoaming agent in the reaction, wherein the addition amount of the defoaming agent is 10-20ppm based on the hourly output of acrylonitrile.
2. The process for producing high-purity acrylonitrile according to claim 1, wherein: the ammonia-nitrogen ratio is controlled to be 1.0-1.2.
3. The process for producing high-purity acrylonitrile according to claim 1, wherein: the pH value of the upper section of the quenching tower used in the reaction is controlled to be 3-5, and the pH value of the lower section of the quenching tower is controlled to be 7-9.
4. The process for producing high-purity acrylonitrile according to claim 1, wherein: and controlling the pH value of a large circulation system used in the reaction to be 6.5-7.5.
5. The process for producing high-purity acrylonitrile according to claim 1, wherein: and controlling the pH value of the decyanation tower bottom liquid used in the reaction to be 4.0-4.3.
6. The process for producing high-purity acrylonitrile according to claim 1, wherein: and controlling the pH value of the finished product tower acrylonitrile used in the reaction to be 6.3-7.0.
7. The process for producing high-purity acrylonitrile according to claim 1, wherein: the temperature of the sensitive point of the recovery tower is controlled between 75 and 85 ℃.
8. The process for producing high-purity acrylonitrile according to claim 1, wherein: the modification process of the defoaming agent comprises the following steps:
(1) taking dihydric alcohol or trihydric alcohol as a modified end group, and grafting the dihydric alcohol or trihydric alcohol onto polyoxypropylene ether;
(2) and (2) carrying out esterification modification on the alcohol end group of the grafted polyoxypropylene ether obtained in the step (1) to obtain an ester group, thus obtaining the esterified polyoxypropylene ether containing polyoxyethylene.
9. The process for producing high-purity acrylonitrile according to claim 8, wherein: the mass content of polyoxyethylene in the esterification modified polyoxypropylene ether is 1-5%.
10. The process for producing high-purity acrylonitrile according to claim 1, wherein: adding a low molecular weight amine to the defoamer.
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