CN115677531A - Production process of ethyl 2, 3-dicyanopropionate - Google Patents
Production process of ethyl 2, 3-dicyanopropionate Download PDFInfo
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- CN115677531A CN115677531A CN202211379324.1A CN202211379324A CN115677531A CN 115677531 A CN115677531 A CN 115677531A CN 202211379324 A CN202211379324 A CN 202211379324A CN 115677531 A CN115677531 A CN 115677531A
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- dicyanopropionate
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- IATZLNCRIIUXJM-UHFFFAOYSA-N methyl hept-2-ynoate Chemical compound CCCCC#CC(=O)OC IATZLNCRIIUXJM-UHFFFAOYSA-N 0.000 title claims description 87
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- NPZOLWMDTPEVEI-UHFFFAOYSA-N ethyl 2,3-dicyanopropanoate Chemical compound CCOC(=O)C(C#N)CC#N NPZOLWMDTPEVEI-UHFFFAOYSA-N 0.000 claims abstract description 17
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- -1 polypropylene Polymers 0.000 claims abstract description 15
- 229920001155 polypropylene Polymers 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 78
- 239000000047 product Substances 0.000 claims description 47
- 239000002904 solvent Substances 0.000 claims description 35
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 33
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 30
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 16
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- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 239000012043 crude product Substances 0.000 claims description 12
- 230000018044 dehydration Effects 0.000 claims description 12
- 238000006297 dehydration reaction Methods 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 10
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 229920002866 paraformaldehyde Polymers 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims description 6
- 238000004817 gas chromatography Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 5
- 238000004807 desolvation Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
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- 238000012544 monitoring process Methods 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 1
- 238000001471 micro-filtration Methods 0.000 claims 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 abstract description 18
- 239000002699 waste material Substances 0.000 abstract description 9
- 238000012824 chemical production Methods 0.000 abstract description 2
- SAVROPQJUYSBDD-UHFFFAOYSA-N formyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)=CO SAVROPQJUYSBDD-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 32
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 17
- 239000007789 gas Substances 0.000 description 10
- 230000020477 pH reduction Effects 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 9
- 239000011780 sodium chloride Substances 0.000 description 9
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 8
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- 238000011084 recovery Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
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- 150000003839 salts Chemical class 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
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- 235000019253 formic acid Nutrition 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- ZOCSXAVNDGMNBV-UHFFFAOYSA-N 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile Chemical compound NC1=C(S(=O)C(F)(F)F)C(C#N)=NN1C1=C(Cl)C=C(C(F)(F)F)C=C1Cl ZOCSXAVNDGMNBV-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005899 Fipronil Substances 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
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- 239000004280 Sodium formate Substances 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
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- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012864 cross contamination Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940013764 fipronil Drugs 0.000 description 1
- LTYRAPJYLUPLCI-UHFFFAOYSA-N glycolonitrile Chemical compound OCC#N LTYRAPJYLUPLCI-UHFFFAOYSA-N 0.000 description 1
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 description 1
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Abstract
The invention relates to the technical field of chemical production, and particularly discloses a production process of 2, 3-dicyano ethyl propionate, which comprises the following steps: adding hydrogen chloride N, N-dimethylformamide solution (water content is less than or equal to 100 ppm) into the synthetic solution of 2, 3-dicyanopropionic acid ethyl ester, and adjusting pH to 1.5-2.0 to obtain an acidizing solution; cooling the acidizing fluid to 0-10 ℃, and decyanating through a polypropylene hollow fiber microporous hydrophobic membrane to obtain decyanation fluid; adding alkaline substances into the decyanation solution, adjusting the pH value to 6.0-7.5, dehydrating, filtering, desolventizing and rectifying to obtain the 2, 3-dicyanopropionic acid ethyl ester product. The purity of the 2, 3-dicyano ethyl propionate product prepared by the invention can reach more than 99.5 percent, the yield can reach more than 95 percent, the product is colorless and transparent in appearance, the product quality is greatly improved, the three wastes are generated in the whole process, and the method is a green and clean production process of the 2, 3-dicyano ethyl propionate.
Description
Technical Field
The invention relates to the technical field of chemical production, in particular to a production process of 2, 3-dicyanopropionic acid ethyl ester.
Background
Ethyl 2, 3-dicyanopropionate is an important intermediate for the synthesis of fipronil. At present, the synthesis method of 2, 3-dicyanopropionic acid ethyl ester reported in literature is mainly divided into a one-step method and a two-step method, wherein the two-step method is basically not adopted due to low product yield and large generation amount of three wastes. A process for producing 2, 3-dicyano ethyl propionate by one-step method comprises the steps of taking ethyl cyanoacetate, sodium cyanide and paraformaldehyde as raw materials, reacting in a solvent, and then carrying out acidification, water washing, extraction, desolventizing and rectification treatment to obtain a finished product of 2, 3-dicyano ethyl propionate. The process has the disadvantages of complicated steps, relatively large waste water production amount, and cross contamination of two solvents in the reaction and extraction processes, so that the recovery of the high-purity solvent is relatively difficult.
In the reaction and extraction processes, dichloromethane is adopted as a solvent, but dichloromethane is inevitably carried in the tail gas produced in the desolventizing and rectifying links, and even trace dichloromethane is decomposed to generate hydrogen chloride in high-temperature incineration treatment, so that a production system is greatly influenced by corrosion. Recently, a production process is reported in which diethyl malonate and hydroxyacetonitrile are used as raw materials and reacted in a methanol solution of sodium methoxide to obtain an intermediate 1 α -cyanomethyl-diethyl malonate, the intermediate I is reacted with ammonia gas in a toluene solvent to obtain an intermediate II 2-amido-3-ethyl cyanopropionate reaction solution, and finally the intermediate II reaction solution is reacted with phosgene under the action of a catalyst 1, 4-diazabicyclo [2.2.2] octane (abbreviated as DABCO) to obtain a product ethyl 2, 3-dicyanopropionate. Although the solvent can be recycled, the process has the advantages of more related raw materials, difficult raw material acquisition, higher raw material storage requirement, high risk and high industrial implementation difficulty, and in addition, the prepared product has higher impurity content and the purity needs to be further improved. Therefore, it is necessary to provide a production process of ethyl 2, 3-dicyanopropionate, which has the advantages of simple operation, small three-waste generation amount, and higher product yield and purity.
Disclosure of Invention
The invention provides a production process of ethyl 2, 3-dicyanopropionate, aiming at the problems of complex operation, large generation amount of three wastes, high difficulty in solvent recycling and the problem that the yield and purity of the prepared ethyl 2, 3-dicyanopropionate need to be further improved in the existing production process of ethyl 2, 3-dicyanopropionate.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a production process of ethyl 2, 3-dicyanopropionate comprises the following steps:
a, using ethyl cyanoacetate, paraformaldehyde and solid sodium cyanide as raw materials to react in N, N-dimethylformamide to obtain a synthetic solution of 2, 3-dicyanopropionic acid ethyl ester;
b, adding hydrogen chloride organic solution into the synthetic liquid of the ethyl 2, 3-dicyanopropionate, and adjusting the pH value to 1.5-2.0 to obtain acidizing liquid; the hydrogen chloride organic solution is N, N-dimethylformamide solution of hydrogen chloride, and the moisture content of the hydrogen chloride organic solution is less than or equal to 100ppm;
step c, cooling the acidizing fluid to 0-10 ℃, and then decyanating through a polypropylene hollow fiber microporous hydrophobic membrane to obtain decyanation fluid;
d, adding an alkaline substance into the decyanation solution, adjusting the pH value to 6.0-7.5, dehydrating, filtering, and performing desolventization on the obtained filtrate to obtain a crude product of the 2, 3-dicyano ethyl propionate and a recovered solvent;
and e, rectifying the crude product of the ethyl 2, 3-dicyanopropionate to obtain an ethyl 2, 3-dicyanopropionate product.
The inventor finds in the experimental process that the ethyl 2, 3-dicyanopropionate product prepared by the conventional process is pink and turns black and red after being placed for a period of time, so that the appearance of the product is poor. The inventor finds out the reason in many ways, and finds that excessive sodium cyanide added in the synthesis process generates hydrocyanic acid through subsequent acidification, and the hydrocyanic acid generates polymerization reaction in the process of desolventizing or rectification, so that hydrocyanic acid included in the prepared 2, 3-dicyanopropionic acid ethyl ester product is a polymer, and the 2, 3-dicyanopropionic acid ethyl ester product presents pink.
Compared with the prior art, the production process of the ethyl 2, 3-dicyanopropionate provided by the invention adopts the N, N-dimethylformamide solution of the hydrogen chloride with the water content of less than or equal to 100ppm for acidification, so that on the premise of ensuring the acidification effect, the production of three wastes can be reduced, the difficulty in recovering a high-purity solvent is reduced, more importantly, the hydrolysis problem of the ethyl 2, 3-dicyanopropionate product can be avoided, and the product quality is improved; the decyanation process is introduced into the synthesis process, so that the product color problem caused by the polymerization of a cyanogen-containing compound can be avoided, the prepared 2, 3-dicyanopropionic acid ethyl ester product is colorless and transparent, and the market competitiveness of the product is improved; the decyanation liquid is neutralized after decyanation, so that the problem of decomposition of the intermediate material of the ethyl 2, 3-dicyanopropionate caused by high-temperature treatment under the strong acid condition can be avoided, and the stability of the ethyl 2, 3-dicyanopropionate product is improved; in addition, the whole process only relates to one solvent, can avoid the problem that the solvent in the traditional process is cross-polluted and can not realize the recovery of the high-purity solvent, does not relate to a chlorine-containing solvent, and can avoid the corrosion problem of hydrochloric acid gas generated when tail gas in production is treated at high temperature to equipment.
The production process of the ethyl 2, 3-dicyanopropionate provided by the invention has simple process steps, saves the operations of washing, extraction and the like in the traditional process, greatly reduces the generation of three wastes, greatly reduces the operation difficulty of recovering high-purity solvents, and has the advantages that the prepared ethyl 2, 3-dicyanopropionate product is colorless and transparent, the product purity can reach more than 99.5 percent, the yield can reach more than 95 percent, the product quality is greatly improved, the economic benefit and the environmental protection benefit are higher, and the market prospect is wide.
Preferably, step a specifically comprises: adding ethyl cyanoacetate into N, N-dimethylformamide, uniformly mixing, cooling to 15-20 ℃, adding paraformaldehyde, uniformly mixing, adding solid sodium cyanide in a flowing manner at 15-20 ℃, carrying out heat preservation reaction after the feeding is finished, and monitoring by gas chromatography until the reaction is finished to obtain the ethyl 2, 3-dicyanopropionate synthetic liquid.
Further, the feeding time of the solid sodium cyanide is 4.5-5.5h.
Preferably, in step b, the concentration of the hydrogen chloride organic solution is 16wt% to 18wt%.
Further, in the step b, the temperature of the fed-in hydrogen chloride organic solution is controlled to be 5-10 ℃.
The concentration of the preferred hydrogen chloride organic solution reduces the introduction amount of the organic solvent (N, N-dimethylformamide) on the premise of ensuring the acidification effect, reduces the energy consumption of the subsequent solvent recovery, and improves the solvent recovery efficiency. Meanwhile, the concentration and the temperature of the preferred hydrogen chloride organic solution can ensure the stability of the hydrogen chloride in the organic solvent and reduce the hydrolysis of the ethyl 2, 3-dicyanopropionate on the premise of ensuring that the concentration of the hydrogen chloride is as high as possible.
Further, in the step b, the adding amount of the hydrogen chloride organic solution is 0.08-0.085 time of the mass of the ethyl cyanoacetate in terms of hydrogen chloride per hour.
The N, N-dimethylformamide solution of hydrogen chloride with the water content of less than or equal to 100ppm is adopted for acidification, the problem of hydrolysis of the 2, 3-dicyanopropionic acid ethyl ester product can be remarkably reduced, and in order to ensure smooth proceeding of an acidification procedure and guarantee an acidification effect, an acidification substance needs to be fed into a system at a specific speed.
Preferably, in step c, the polypropylene hollow fiber microporous hydrophobic membrane has a membrane thickness of 30-100 μm and a membrane pore size of 1-3nm.
Further, in step c, the polypropylene hollow fiber microporous hydrophobic membrane is E3-8827 produced by Jiehai Ruijuan membrane technology (Tianjin) Co.
The invention adopts a polypropylene hollow fiber microporous hydrophobic membrane as a barrier for acidizing fluid and alkali absorption fluid, one side of the membrane is acidizing fluid, the other side of the membrane is alkali absorption fluid, cyanide in the acidizing fluid diffuses to the surface of the hydrophobic micropores through a concentration boundary, and then diffuses into the alkali absorption fluid through the membrane, so that the purpose of removing hydrogen radical ions is achieved.
The preferable polypropylene hollow fiber micropore is of a hollow structure, and the micropores are filled with air, so that the acidizing fluid has a high mass transfer coefficient without blowing a large amount of air to contact with the acidizing fluid, cyanide ions in the acidizing fluid quickly enter an alkali absorption side, the removal efficiency of the cyanide ions is improved, and the HCN content in the acidizing fluid is controlled within 1 ppm; and the decyanation process can be carried out in a closed system, so that no toxic component in the acidizing fluid is blown into the air, and secondary pollution is avoided.
It should be noted that, the temperature of the acidizing fluid is reduced to 0-10 ℃ and then decyanation is carried out, so that the stability of the polypropylene hollow fiber microporous hydrophobic membrane can be ensured on the premise of ensuring the decyanation effect and the decyanation efficiency, and the problem that the decyanation system cannot efficiently and stably operate due to the fact that the polypropylene hollow fiber microporous hydrophobic membrane is corroded by the N, N-dimethylformamide solvent is avoided. In addition, the polymerization reaction of hydrocyanic acid in the decyanation process can be avoided, and the problem of product color reversion can be effectively avoided.
It should be noted that the flow rate of the acidizing fluid for the gaseous membrane decyanation is determined according to the content of cyanide ions in the acidizing fluid and the area of the gaseous membrane. Preferably, the flow rate of the acidizing fluid is 2.5-3.0kg/m 2 /h。
Preferably, in step d, the basic substance is flake alkali, sodium carbonate or triethylamine.
The preferable alkaline substance is added into the decyanated acidizing fluid to neutralize excessive acidic substance, so that the decomposition of the ethyl 2, 3-dicyanopropionate product in the subsequent purification process can be reduced, and the yield and the purity of the ethyl 2, 3-dicyanopropionate product are improved.
Preferably, in the step d, a negative pressure dehydration mode is adopted, the vacuum degree of dehydration is less than or equal to 100Pa, the temperature of dehydration is less than or equal to 50 ℃, and dehydration is carried out until the moisture content of the material is less than or equal to 0.1%.
The dehydration temperature is controlled within 50 ℃, and the hydrolysis rate of the 2, 3-dicyano ethyl propionate in the dehydration process can be greatly reduced by adopting negative pressure dehydration.
Furthermore, as the N, N-Dimethylformamide (DMF) and water are relatively difficult to separate, the water content of the intermediate material is controlled within 0.1 percent, and the dehydration efficiency is not influenced on the premise of ensuring the minimum production amount of the aqueous solvent DMF; meanwhile, the high-purity DMF solvent with lower water content can be obtained in the desolventizing procedure on the premise of ensuring that the hydrolysis degree of the 2, 3-dicyano ethyl propionate product is smaller.
Preferably, in the step d, the vacuum degree of the desolventizing is less than or equal to 100Pa, and the end point temperature of the desolventizing is 120-125 ℃.
The desolvation end point temperature is controlled to be 120-125 ℃, so that less solvent DMF can be entrained in the crude product of the 2, 3-dicyanopropionic acid ethyl ester, and meanwhile, the problem of lower product yield caused by excessive 2, 3-dicyanopropionic acid ethyl ester entrained in the solvent DMF obtained by desolvation is avoided.
Preferably, in step d, a two-stage filtration mode is adopted, the dehydrated material is firstly centrifuged, and then the obtained centrifugate is filtered by a microporous membrane with the aperture of 0.25-0.35 μm.
Further, in the step d, the desolventized material is cooled to 10-20 ℃ before filtration, and then filtration is carried out.
In the desolventizing process, the amount of DMF in the production system is gradually reduced along with continuous desorption of DMF, sodium chloride solid generated in the acidification process is gradually separated out, the desolventized material is cooled to 10-20 ℃, the sodium chloride solid in the production system can be ensured to be completely separated out, then a 0.25-0.35 mu m filter membrane is utilized for filtration, the sodium chloride solid in the system is fully removed, and therefore the sodium chloride is prevented from influencing a subsequent rectification and purification system, and the stable operation of the rectification and purification system is ensured.
Preferably, in the step e, the vacuum degree of the rectification is less than or equal to 100Pa, and the end point temperature of the rectification is less than or equal to 140 ℃.
The optimized rectification condition can quickly separate the crude product of the 2, 3-dicyano ethyl propionate from a DMF solvent, thereby improving the production efficiency; rectifying the crude product of the ethyl 2, 3-dicyanopropionate under the vacuum condition of less than 100Pa, and controlling the temperature of the end point of rectification within 140 ℃, so as to prevent impurities from entering the ethyl 2, 3-dicyanopropionate product, reduce the decomposition rate of the ethyl 2, 3-dicyanopropionate at high temperature, reduce the retention time of the ethyl 2, 3-dicyanopropionate in a high-temperature system, further ensure the purity of the product, and stabilize the purity of the ethyl 2, 3-dicyanopropionate product to be more than 99.5 percent.
Preferably, step e further comprises: and (c) adding a sodium hydroxide solution into the recovered solvent, dehydrating until the water content of the system is less than or equal to 1%, filtering, and returning the filtrate to the step (a) to be used as a reaction solvent.
Further, in combination with the above aspect, the mass concentration of the sodium hydroxide solution is 30% to 50%.
The recovered solvent is washed by sodium hydroxide solution, and formic acid generated by the high-temperature decomposition of the ethyl 2, 3-dicyanopropionate can be converted into sodium formate to be removed, so that the recovered solvent is purified, and the influence on the synthesis reaction of the ethyl 2, 3-dicyanopropionate caused by the change of the pH value of a reaction system due to the formic acid contained in the recovered solvent is avoided.
The production process of the ethyl 2, 3-dicyanopropionate provided by the invention has simple operation steps, can realize full recovery of reaction solvent, and the obtained ethyl 2, 3-dicyanopropionate product has high yield and purity, the prepared ethyl 2, 3-dicyanopropionate is a transparent colorless product, the product quality is obviously improved, and meanwhile, the three wastes in the whole system are generated in a small amount, so that the production process of the green and recycled ethyl 2, 3-dicyanopropionate has high popularization and application values.
Drawings
FIG. 1 is a scheme showing a production process of ethyl 2, 3-dicyanopropionate in the example of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The polypropylene hollow fiber microporous hydrophobic membranes used in the following examples and comparative examples were E3-8827 manufactured by Jiehai Rui spring Membrane technology (Tianjin) Co., ltd; the hydrogen chloride solution used had a water content of 80ppm in N, N-dimethylformamide.
Example 1
A production process of ethyl 2, 3-dicyanopropionate comprises the following steps:
step a, 4000kg of N, N-dimethylformamide and 1500kg of ethyl cyanoacetate are added into a reactor, the mixture is uniformly stirred, the temperature is reduced to 15-20 ℃, 435kg of paraformaldehyde is added, the mixture is stirred for 30min, the temperature of the reactor is controlled to be 15-20 ℃, 720kg of solid sodium cyanide is fed in a flowing mode, the feeding time is 5h, after the solid sodium cyanide is fed in, the heat preservation and stirring reaction is carried out at 15-20 ℃, the gas chromatography detection is carried out until the gas phase content of the ethyl cyanoacetate is less than 0.5%, and the reaction is finished, so that 6655kg of ethyl 2, 3-dicyanopropionate synthetic liquid is obtained;
step b, cooling the synthetic liquid of the ethyl 2, 3-dicyanopropionate to 10 ℃, adding 3937.3kg of N, N-dimethylformamide solution of hydrogen chloride with the mass concentration of 18% into the synthetic liquid at the rate of 666kg/h (calculated by hydrogen chloride), and adjusting the pH value to 1.5 to obtain an acidizing liquid;
step c, cooling the acidizing fluid to 0 ℃, and enabling the acidizing fluid to pass through a polypropylene hollow fiber microporous hydrophobic membrane (the membrane area is 266.7 m) at a feeding speed of 800kg/h 2 ) Decyanation is carried out to obtain decyanation liquid with the cyanogen concentration of 0.8 ppm;
d, adding caustic soda flakes into the decyanation solution, adjusting the pH to 6.0, and dehydrating at the vacuum degree of 80Pa and the temperature of 45 ℃ to obtain 318kg of DMF 25.0% aqueous solution and 10274kg of intermediate material with the water content of 0.05%;
step e, cooling the intermediate material to 10 ℃, centrifuging, and filtering the centrifugate through a filter membrane with the aperture of 0.25 mu m to obtain 1170kg of sodium chloride byproduct salt and 9100kg of filtrate;
step f, carrying out negative pressure desolventizing on the filtrate, controlling the vacuum degree of a desolventizing system to be 90Pa, finishing the desolventizing when the desolventizing temperature reaches 120 ℃, obtaining 2170kg of crude 2, 3-dicyanopropionic acid ethyl ester, and recovering 6910kg of DMF solvent;
step g, rectifying and purifying the crude product of the ethyl 2, 3-dicyanopropionate, controlling the vacuum degree of a rectifying system to be 60Pa, and finishing rectification when the temperature of a rectifying kettle reaches 138 ℃ to obtain 1940kg of the ethyl 2, 3-dicyanopropionate product, wherein the gas phase purity is 99.635%, the yield is 96.156% in terms of the weight of the ethyl 2, 3-dicyanopropionate product, and the ethyl 2, 3-dicyanopropionate product is colorless and transparent;
and h, adding a sodium hydroxide solution with the mass concentration of 32% into the recovered DMF solvent obtained in the step f, adjusting the pH to 7, filtering, dehydrating until the water content of the system is less than or equal to 1%, and obtaining 6868kg of the recovered DMF solvent which can be used as a reaction solvent in the step a.
Example 2
A production process of ethyl 2, 3-dicyanopropionate comprises the following steps:
step a, 4000kg of N, N-dimethylformamide and 1500kg of ethyl cyanoacetate are added into a reactor, the mixture is uniformly stirred, the temperature is reduced to 15-20 ℃, 435kg of paraformaldehyde is added, the mixture is stirred for 30min, the temperature of the reactor is controlled to be 15-20 ℃, 720kg of solid sodium cyanide is fed in a flowing mode, the feeding time is 5h, after the solid sodium cyanide is fed in, the heat preservation and stirring reaction is carried out at 15-20 ℃, the gas chromatography detection is carried out until the gas phase content of the ethyl cyanoacetate is less than 0.5%, and the reaction is finished, so that 6655kg of ethyl 2, 3-dicyanopropionate synthetic liquid is obtained;
step b, cooling the synthetic liquid of the ethyl 2, 3-dicyanopropionate to 8 ℃, adding 3925kg of N, N-dimethylformamide solution of hydrogen chloride with the mass concentration of 18% into the synthetic liquid at the speed of 708.3kg/h (calculated by hydrogen chloride), and adjusting the pH value to 1.8 to obtain an acidizing liquid;
step c, cooling the acidizing fluid to 10 ℃, and enabling the acidizing fluid to pass through a polypropylene hollow fiber microporous hydrophobic membrane (the membrane area is 266.7 m) at a feeding speed of 800kg/h 2 ) Decyanation is carried out to obtain decyanation liquid with the cyanogen concentration of 0.8 ppm;
step d, adding triethylamine into the decyanation solution, adjusting the pH value to 6.5, and dehydrating at the vacuum degree of 70Pa and the temperature of 49 ℃ to obtain 327kg of a water solution containing 26.8 percent of DMF and 10250kg of an intermediate material with the water content of 0.03 percent;
step e, cooling the intermediate material to 20 ℃, centrifuging, and filtering the centrifugate through a filter membrane with the aperture of 0.35 mu m to obtain 1172kg of sodium chloride byproduct salt and 9075kg of filtrate;
step f, carrying out negative pressure desolventizing on the filtrate, controlling the vacuum degree of a desolventizing system to be 80Pa, finishing the desolventizing when the desolventizing temperature reaches 125 ℃, obtaining 2169.4kg of crude 2, 3-dicyanopropionic acid ethyl ester, and recovering 6900kg of DMF solvent;
step g, rectifying and purifying the crude product of the ethyl 2, 3-dicyanopropionate, controlling the vacuum degree of a rectifying system to be 70Pa, and finishing the rectification when the temperature of a rectifying still reaches 139 ℃ to obtain 1955kg of the ethyl 2, 3-dicyanopropionate product, wherein the gas phase purity is 99.710%, the weight yield of the ethyl 2, 3-dicyanopropionate product is 96.891%, and the ethyl 2, 3-dicyanopropionate product is colorless and transparent;
and h, adding a sodium hydroxide solution with the mass concentration of 32% into the recovered DMF solvent obtained in the step f, adjusting the pH to 7, filtering, dehydrating until the water content of the system is less than or equal to 1%, and obtaining 6890kg of the recovered DMF solvent which can be used as a reaction solvent in the step a.
Example 3
A production process of ethyl 2, 3-dicyanopropionate comprises the following steps:
step a, adding 4000kg of N, N-dimethylformamide and 1500kg of ethyl cyanoacetate into a reactor, uniformly stirring, cooling to 15-20 ℃, adding 435kg of paraformaldehyde, stirring for 30min, controlling the temperature of the reactor to be 15-20 ℃, feeding 720kg of solid sodium cyanide for 5h, keeping the temperature at 15-20 ℃ after the solid sodium cyanide is added, stirring for reaction, and detecting by using a gas chromatography until the gas phase content of the ethyl cyanoacetate is less than 0.5% after the reaction is finished to obtain 6655kg of ethyl 2, 3-dicyanopropionate synthetic liquid;
step b, cooling the synthetic liquid of the ethyl 2, 3-dicyanopropionate to 5 ℃, adding 3912.2kg of N, N-dimethylformamide solution of hydrogen chloride with the mass concentration of 18% into the synthetic liquid at the speed of 686.74kg/h (calculated by hydrogen chloride), and adjusting the pH value to 2.0 to obtain an acidizing liquid;
step c, cooling the acidizing fluid to 5 ℃, and enabling the acidizing fluid to pass through a polypropylene hollow fiber microporous hydrophobic membrane (the membrane area is 266.7 m) at a feeding speed of 800kg/h 2 ) Decyanation is carried out to obtain decyanation liquid with the cyanogen concentration of 0.8 ppm;
d, adding sodium carbonate into the decyanation solution, adjusting the pH value to 7.0, and dehydrating at the vacuum degree of 80Pa and the temperature of 45 ℃ to obtain 316kg of DMF24.6% aqueous solution and 10247kg of intermediate material with the water content of 0.06%;
step e, cooling the intermediate material to 15 ℃, centrifuging, and filtering the centrifugate through a filter membrane with the aperture of 0.30 mu m to obtain 1175kg of sodium chloride byproduct salt and 9068kg of filtrate;
step f, carrying out negative pressure desolventizing on the filtrate, controlling the vacuum degree of a desolventizing system to be 70Pa, finishing the desolventizing when the desolventizing temperature reaches 123 ℃, obtaining 2150kg of crude 2, 3-dicyanopropionic acid ethyl ester, and recovering 6900kg of DMF solvent;
step g, rectifying and purifying the crude product of the ethyl 2, 3-dicyanopropionate, controlling the vacuum degree of a rectifying system to be 50Pa, finishing rectification when the temperature of a rectifying kettle reaches 137 ℃, and obtaining 1936kg of the ethyl 2, 3-dicyanopropionate product, the gas phase purity of which is 99.702 percent, the weight yield of the ethyl 2, 3-dicyanopropionate product which is converted into 95.958 percent, and the ethyl 2, 3-dicyanopropionate product which is colorless and transparent;
and h, adding a sodium hydroxide solution with the mass concentration of 32% into the recovered DMF solvent obtained in the step f, adjusting the pH to 7, filtering, dehydrating until the water content of the system is less than or equal to 1%, and obtaining 6885kg of recovered DMF solvent which can be used as a reaction solvent in the step a.
Comparative example 1
This comparative example provides a process for the production of ethyl 2, 3-dicyanopropionate:
step a, 4000kg of N, N-dimethylformamide and 1500kg of ethyl cyanoacetate are added into a reactor, the mixture is uniformly stirred, the temperature is reduced to 15-20 ℃, 435kg of paraformaldehyde is added, the mixture is stirred for 30min, the temperature of the reactor is controlled to be 15-20 ℃, 720kg of solid sodium cyanide is fed in a flowing mode, the feeding time is 5h, after the solid sodium cyanide is fed in, the heat preservation and stirring reaction is carried out at 15-20 ℃, the gas chromatography detection is carried out until the gas phase content of the ethyl cyanoacetate is less than 0.5%, and the reaction is finished, so that 6655kg of ethyl 2, 3-dicyanopropionate synthetic liquid is obtained;
step b, cooling the synthetic liquid of the ethyl 2, 3-dicyanopropionate to 10 ℃, adding 2362.3kg of hydrochloric acid solution with the mass concentration of 30%, and adjusting the pH value to 1.5 to obtain an acidizing liquid;
step c, adding 1500kg of water and 3100kg of dichloroethane into the acidizing fluid, stirring, standing, and carrying out phase separation to obtain a saline water phase and a 2, 3-dicyanopropionic acid ethyl ester oil phase;
step d, 1900kg of dichloroethane is used for extracting the brine phase, continuous extraction is carried out for 3 times, the content of the ethyl 2, 3-dicyanopropionate in the brine phase is reduced to be within 0.5 percent, and 4080kg of sodium chloride brine and extract liquor are obtained;
washing the ethyl 2, 3-dicyanopropionate oil phase by 1500L of water, continuously washing for 3 times, removing DMF in the crude oil phase of the ethyl 2, 3-dicyanopropionate, and obtaining crude ethyl 2, 3-dicyanopropionate after washing when the content of DMF in the crude oil phase of the ethyl 2, 3-dicyanopropionate is less than 0.5%;
step e, combining the extract liquor obtained in the step d with the crude ester of the ethyl 2, 3-dicyanopropionate for desolventizing, controlling the vacuum degree of a desolventizing system to be 90Pa, and finishing the desolventizing when the temperature of a desolventizing end point is 120 ℃ to obtain 2080kg of crude product of the ethyl 2, 3-dicyanopropionate;
and f, rectifying and purifying the crude product of the ethyl 2, 3-dicyanopropionate under the condition of vacuum degree of 60Pa, and finishing rectification when the temperature of a rectifying still reaches 138 ℃ to obtain 1840kg of the ethyl 2, 3-dicyanopropionate product, wherein the gas phase purity is 99.462 percent, the yield is 91.200 percent by weight in terms of the ethyl 2, 3-dicyanopropionate product, and the ethyl 2, 3-dicyanopropionate product is pink.
In conclusion, the production method of the ethyl 2, 3-dicyanopropionate provided by the invention has the advantages of simple process, no need of special equipment and low energy consumption, the purity of the prepared ethyl 2, 3-dicyanopropionate product can reach more than 99.5%, the yield can reach more than 95%, the product appearance is colorless and transparent, the product quality is greatly improved, the generation amount of three wastes in the whole process is small, the three-waste treatment cost and the energy consumption are reduced, and the production method is a green and clean production process of the ethyl 2, 3-dicyanopropionate and has high popularization and application values.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A production process of ethyl 2, 3-dicyanopropionate is characterized by comprising the following steps:
a, using ethyl cyanoacetate, paraformaldehyde and solid sodium cyanide as raw materials to react in N, N-dimethylformamide to obtain a synthetic solution of 2, 3-dicyanopropionic acid ethyl ester;
b, adding a hydrogen chloride organic solution into the synthetic liquid of the ethyl 2, 3-dicyanopropionate, and adjusting the pH value to 1.5-2.0 to obtain an acidizing liquid; the hydrogen chloride organic solution is an N, N-dimethylformamide solution of hydrogen chloride, and the water content of the hydrogen chloride organic solution is less than or equal to 100ppm;
step c, cooling the acidizing fluid to 0-10 ℃, and then decyanating through a polypropylene hollow fiber microporous hydrophobic membrane to obtain decyanation fluid;
d, adding an alkaline substance into the decyanation solution, adjusting the pH value to 6.0-7.5, dehydrating, filtering, and performing desolventizing on the obtained filtrate to obtain a crude product of the 2, 3-dicyanopropionic acid ethyl ester and a recovered solvent;
and e, rectifying the crude product of the ethyl 2, 3-dicyanopropionate to obtain an ethyl 2, 3-dicyanopropionate product.
2. The process for producing ethyl 2, 3-dicyanopropionate according to claim 1, wherein step a is specifically: adding ethyl cyanoacetate into N, N-dimethylformamide, uniformly mixing, cooling to 15-20 ℃, adding paraformaldehyde, uniformly mixing, adding solid sodium cyanide in a flowing manner at 15-20 ℃, carrying out heat preservation reaction after the feeding is finished, and monitoring by gas chromatography until the reaction is finished to obtain the ethyl 2, 3-dicyanopropionate synthetic liquid.
3. The process for the production of ethyl 2, 3-dicyanopropionate according to claim 1, wherein in step b, the concentration of the organic solution of hydrogen chloride is from 16% to 18% by weight; and/or
In the step b, the temperature of the hydrogen chloride organic solution is 5-10 ℃.
4. The process for producing ethyl 2, 3-dicyanopropionate according to claim 1 or 3, wherein in the step b, the amount of the organic solution of hydrogen chloride fed per hour is 0.08 to 0.085 times the mass of ethyl cyanoacetate, in terms of hydrogen chloride.
5. The process for producing ethyl 2, 3-dicyanopropionate according to claim 1, wherein in step c, the polypropylene hollow fiber microporous hydrophobic membrane has a membrane thickness of 30 to 100 μm and a membrane pore diameter of 1 to 3nm; and/or
In step c, the acidified solution is added at a concentration of 2.5kg/m 2 /h-3.0kg/m 2 Introducing the microporous hydrophobic membrane of the polypropylene hollow fiber at a flow rate of/h for decyanation.
6. The process for producing ethyl 2, 3-dicyanopropionate according to claim 1, wherein in step d, the basic substance is flake base, sodium carbonate or triethylamine; and/or
In the step d, a negative pressure dehydration mode is adopted, the vacuum degree of dehydration is less than or equal to 100Pa, the dehydration temperature is less than or equal to 50 ℃, and the dehydration is carried out until the moisture content of the material is less than or equal to 0.1 percent.
7. The process for producing ethyl 2, 3-dicyanopropionate according to claim 1, wherein in step d, the dewatered material is first centrifuged by a two-stage filtration method, and the resulting centrifugate is then filtered through a microfiltration membrane having a pore size of 0.25 to 0.35 μm.
8. The process for producing ethyl 2, 3-dicyanopropionate according to claim 1, wherein in step d, the vacuum degree of the desolvation is less than or equal to 100Pa and the end point temperature of the desolvation is 120-125 ℃.
9. The process for producing ethyl 2, 3-dicyanopropionate according to claim 1, wherein in step e, the vacuum degree of rectification is less than or equal to 100Pa, and the end point temperature of rectification is less than or equal to 140 ℃.
10. The process for producing ethyl 2, 3-dicyanopropionate according to claim 1 or 8, wherein in step e, further comprising: and (b) adding a sodium hydroxide solution into the recovered solvent, dehydrating until the water content of the system is less than or equal to 1%, filtering, and returning the filtrate to the step (a) to serve as a reaction solvent.
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| CN1785966A (en) * | 2005-11-07 | 2006-06-14 | 栾忠岳 | Technology of synthesizing 2,3-dicyano ethyl propionate |
| CN111517988A (en) * | 2020-06-02 | 2020-08-11 | 湖北仙盛科技股份有限公司 | Synthesis process of ethyl 2, 3-dicyanopropionate |
| CN111675630A (en) * | 2020-07-21 | 2020-09-18 | 湖北金玉兰医药科技有限公司 | Production process of ethyl 2, 3-dicyanopropionate |
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| CN1785966A (en) * | 2005-11-07 | 2006-06-14 | 栾忠岳 | Technology of synthesizing 2,3-dicyano ethyl propionate |
| CN111517988A (en) * | 2020-06-02 | 2020-08-11 | 湖北仙盛科技股份有限公司 | Synthesis process of ethyl 2, 3-dicyanopropionate |
| CN111675630A (en) * | 2020-07-21 | 2020-09-18 | 湖北金玉兰医药科技有限公司 | Production process of ethyl 2, 3-dicyanopropionate |
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