CN111807922A - Continuous automatic preparation method of 2, 3-dichloropropene - Google Patents
Continuous automatic preparation method of 2, 3-dichloropropene Download PDFInfo
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- CN111807922A CN111807922A CN202010718883.5A CN202010718883A CN111807922A CN 111807922 A CN111807922 A CN 111807922A CN 202010718883 A CN202010718883 A CN 202010718883A CN 111807922 A CN111807922 A CN 111807922A
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- Prior art keywords
- reaction
- dichloropropene
- catalyst
- continuous
- trichloropropane
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- FALCMQXTWHPRIH-UHFFFAOYSA-N 2,3-dichloroprop-1-ene Chemical compound ClCC(Cl)=C FALCMQXTWHPRIH-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- CFXQEHVMCRXUSD-UHFFFAOYSA-N 1,2,3-Trichloropropane Chemical compound ClCC(Cl)CCl CFXQEHVMCRXUSD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 15
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims abstract description 8
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims abstract description 6
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims abstract description 6
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 4
- 238000009776 industrial production Methods 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 claims description 3
- ZAIDIVBQUMFXEC-UHFFFAOYSA-N 1,1-dichloroprop-1-ene Chemical compound CC=C(Cl)Cl ZAIDIVBQUMFXEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 230000001502 supplementing effect Effects 0.000 claims description 2
- 238000004065 wastewater treatment Methods 0.000 claims description 2
- 238000007259 addition reaction Methods 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- AVGQTJUPLKNPQP-UHFFFAOYSA-N 1,1,1-trichloropropane Chemical compound CCC(Cl)(Cl)Cl AVGQTJUPLKNPQP-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- VRMUIVKEHJSADG-UHFFFAOYSA-N 2-chloro-5-(chloromethyl)-1,3-thiazole Chemical compound ClCC1=CN=C(Cl)S1 VRMUIVKEHJSADG-UHFFFAOYSA-N 0.000 description 1
- 239000005941 Thiamethoxam Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- NWWZPOKUUAIXIW-FLIBITNWSA-N thiamethoxam Chemical compound [O-][N+](=O)\N=C/1N(C)COCN\1CC1=CN=C(Cl)S1 NWWZPOKUUAIXIW-FLIBITNWSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a continuous automatic preparation method of 2, 3-dichloropropene, which comprises the following steps: the reaction mass: 1,2, 3-trichloropropane, a catalyst and liquid caustic soda are respectively and continuously pumped into a reaction mixer by a metering pump according to a preset proportion to continuously react to generate 2, 3-dichloropropene, wherein the catalyst is at least one of triethylbenzylammonium chloride, tetrabutylammonium hydroxide and polyethylene glycol-400. The invention adopts continuous and simultaneous dropwise addition reaction to change the catalyst or adjust the dosage of the catalyst, which has no influence on the yield, compared with the prior art, the product quality, the product yield and the like are greatly improved by more than 15 percent compared with the prior art, the production cost is further reduced, and the production process is safe and controllable, thereby realizing green, environment-friendly and safe industrialized production process.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a continuous automatic preparation method of 2, 3-dichloropropene.
Background
2, 3-dichloropropene is a basic raw material for the medicine ritonafil and the production of the pesticide thiamethoxam. The existing process for producing 2, 3-dichloropropene adopts 1,2, 3-trichloropropane as a starting material and adopts a reaction kettle interval reaction mode for production, the production process has low safety coefficient, the liquid caustic soda addition process is easy to cause severe reaction to cause safety accidents, and the raw material consumption is large, so the cost is high; and the product quality is unstable, the yield is lower, the three wastes treatment and the salt-containing wastewater are difficult, and the like. The method comprises the following specific steps:
(1) the existing production process adopts a gap reaction mode, liquid caustic soda is dropwise added after a catalyst is added, the production process has low safety coefficient, and the product quality and the yield are low. (2) In the prior art, TEBA and the like are adopted as a catalyst for reaction, and the catalyst is easily decomposed under an alkaline condition to cause non-uniform reaction control process, so that the quality and the yield of a product are influenced.
Disclosure of Invention
The invention discloses a continuous synthesis method of 2-chloro-5-chloromethyl thiazoie (2-chloro-5-chloromethyl thiazole), which adopts continuous and simultaneous dropwise addition reaction to change the catalyst or adjust the dosage of the catalyst, thereby having no influence on the yield, greatly improving the product quality, the product yield and the like compared with the prior art, improving the product quality, the product yield and the like by more than 15 percent compared with the prior art, further reducing the production cost, and ensuring the safe and controllable production process, thereby realizing the green, environment-friendly and safe industrialized production process.
The purpose of the invention is realized by the following technical scheme:
a continuous automatic preparation method of 2, 3-dichloropropene comprises the following steps:
the reaction mass: 1,2, 3-trichloropropane, a catalyst and liquid caustic soda are respectively and continuously pumped into a reaction mixer by a metering pump according to a preset proportion to continuously react to generate 2, 3-dichloropropene, wherein the catalyst is at least one of triethylbenzylammonium chloride, tetrabutylammonium hydroxide and polyethylene glycol-400.
In a further improvement, the reaction temperature of the reaction is 65-95 ℃.
The further improvement is that the feeding proportion of the 1,2, 3-trichloropropane, the liquid caustic soda and the catalyst is as follows: in terms of molar ratio, 1,2, 3-trichloropropane: liquid caustic soda is 1.0: 0.95; according to the mass ratio of 1,2, 3-trichloropropane: catalyst 1.0: 0.4 percent.
Further improvement, the amount of reaction raw materials in the reaction process is always controlled to be 10 percent of the total reaction materials, so as to ensure the continuous and stable reaction process.
The further improvement is that after the reaction is finished, the reaction material enters a rectifying tower in a continuous feeding mode after passing through the phase splitting of an automatic phase splitter, dichloropropene is extracted from the rectifying tower, and the material at the bottom of the tower returns to a reaction mixer to be used as a synthetic raw material, so that no distillation waste liquid is generated.
In a further improvement, after the reaction is finished, the reaction materials are subjected to phase splitting through an automatic phase splitter, the wastewater enters a wastewater treatment device in a continuous feeding mode, the treated reclaimed water is used for supplementing process water, and the sodium chloride is used for industrial production recovery.
In a further improvement, the addition rate of the reaction mass is 379.8g added dropwise every 1-1.5 h.
The invention has the following advantages:
1. the invention adopts a continuous production process, propane and liquid are simultaneously added, and the concentration of the catalyst is controlled to be reduced, so that the cost of raw materials is reduced, and the product quality and the yield are obviously improved.
2. The invention adopts catalysts such as polyethylene glycol-400 and the like, and the reaction process does not generate decomposition and is milder than other catalysts.
3. The reaction condition for synthesizing the 2, 3-dichloropropene is simple to operate, is very suitable for automatic production control, is beneficial to safe production, and has the production purpose of environmental protection, equipment has no special requirement, the excessive propane is controlled to ensure that liquid caustic soda is reacted completely, the excessive propane is recycled after product rectification, and the raw material cost of the 2, 3-dichloropropene and the generation of three wastes are reduced.
4. The content of the 2, 3-dichloropropene produced by the method can reach 99 percent, and the yield can reach more than 95 percent.
Drawings
FIG. 1 is a schematic flow chart 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 described in further detail below.
The chemical reaction of the invention is as follows:
CH2Cl-CHCl-CH2Cl+NaOH→CH2＝CCl-CH2Cl+H2O+NaCl
example 1
(1) 100 g of water was added to the reaction flask. Stirring, heating, and heating to 90 deg.C.
(2) 179 g of 30% aqueous base is weighed, mixed with 0.8 g of polyethylene glycol-400 and placed in a dropper. 200 g (99%) of 1,2, 3-trichloropropane were weighed into a dropper.
(3) And (3) simultaneously dropwise adding the prepared liquid caustic soda and trichloropropane material into 100 g of water heated to 90 ℃, controlling the temperature to be 65-95 ℃, completing dropwise addition within 1-1.5 hours, and keeping the temperature for 30 min. Then cooling, standing and layering.
(4) Separating out an oil phase, and carrying out negative pressure rectification to collect 75-85 ℃ fractions to obtain 141 g of 2, 3-dichloropropene, wherein the content is 99%, and the yield is 94.6%.
Example 2:
(1) 100 g of water was added to the reaction flask. Stirring, heating, and heating to 90 deg.C.
(2) 179 g of 30% aqueous base are weighed out, 1.2 g of polyethylene glycol-400 are added, mixed and placed in a dropper. 200 g (99%) of 1,2, 3-trichloropropane were weighed into a dropper.
(3) And (3) simultaneously dropwise adding the prepared liquid caustic soda and trichloropropane material into 100 g of water heated to 90 ℃, controlling the temperature to be 65-95 ℃, completing dropwise addition within 1-1.5 hours, and keeping the temperature for 30 min. Then cooling and standing, layering, separating out an oil phase, carrying out negative pressure rectification, and collecting 75-85 ℃ fractions to obtain 140.5 g of 2, 3-dichloropropene, wherein the content is 99%, and the yield is 94.3%.
Example 3:
(1) 100 g of water was added to the reaction flask. Stirring, heating, and heating to 90 deg.C.
(2) 179 g of 30% strength liquid base are weighed out, 0.8 g of tetrabutylammonium hydroxide are added, mixed and placed in a dropping vessel. 200 g (99%) of 1,2, 3-trichloropropane were weighed into a dropper.
(3) And (3) simultaneously dropwise adding the prepared liquid caustic soda and trichloropropane material into 100 g of water heated to 90 ℃, controlling the temperature to be 65-95 ℃, completing dropwise addition within 1-1.5 hours, and keeping the temperature for 30 min. Then cooling and standing, layering, separating out an oil phase, carrying out negative pressure rectification, and collecting 75-85 ℃ fractions to obtain 2, 3-dichloro
140.9 g of propylene, content 99% and yield 94.6%.
Example 4:
(1) 100 g of water was added to the reaction flask. Stirring, heating, and heating to 90 deg.C.
(2) 179 g of 30% aqueous alkali is weighed, 0.8 g of triethylbenzylammonium chloride is added, mixed and charged into a dropping vessel. 200 g (99%) of 1,2, 3-trichloropropane were weighed into a dropper.
(3) And (3) simultaneously dropwise adding the prepared liquid caustic soda and trichloropropane material into 100 g of water heated to 90 ℃, controlling the temperature to be 65-95 ℃, completing dropwise addition within 1-1.5 hours, and keeping the temperature for 30 min. Then cooling and standing, layering, separating out an oil phase, carrying out negative pressure rectification, and collecting 75-85 ℃ fractions to obtain 140 g of 2, 3-dichloropropene, wherein the content is 99%, and the yield is 94.0%.
As can be seen from the above examples, the method provided by the invention mainly adopts continuous and simultaneous dropwise addition reaction to change the catalyst or adjust the catalyst dosage, which has no influence on the yield, and compared with the existing process, the product quality, the product yield and the like are greatly improved, the product yield is improved by more than 15% compared with the existing process, the production cost is further reduced, and the production process is safe and controllable, so that the green, environment-friendly and safe industrial production process is realized.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (7)
1. A continuous automatic preparation method of 2, 3-dichloropropene is characterized by comprising the following steps:
the reaction mass: 1,2, 3-trichloropropane, a catalyst and liquid caustic soda are respectively and continuously pumped into a reaction mixer by a metering pump according to a preset proportion to continuously react to generate 2, 3-dichloropropene, wherein the catalyst is at least one of triethylbenzylammonium chloride, tetrabutylammonium hydroxide and polyethylene glycol-400.
2. The continuous automatic process for the preparation of 2, 3-dichloropropene according to claim 1, wherein: the reaction temperature of the reaction is 65-95 ℃.
3. The continuous automatic process for the preparation of 2, 3-dichloropropene according to claim 1, wherein: the feeding proportion of the 1,2, 3-trichloropropane, the liquid caustic soda and the catalyst is as follows: in terms of molar ratio, 1,2, 3-trichloropropane: liquid caustic soda is 1.0: 0.95; according to the mass ratio of 1,2, 3-trichloropropane: catalyst 1.0: 0.4 percent.
4. The continuous automatic production method of 2, 3-dichloropropene according to claim 1 or 2, characterized in that: the reaction raw material amount is always controlled to be 10% of the total reaction materials in the reaction process so as to ensure the continuous and stable reaction process.
5. The production process according to claim 1 or 2, characterized in that: after the reaction is finished, the reaction material enters a rectifying tower in a continuous feeding mode after being subjected to phase splitting through an automatic phase splitter, dichloropropene is extracted from the rectifying tower, the material at the bottom of the tower returns to a reaction mixer to be used as a synthetic raw material, and no distillation waste liquid is generated.
6. The continuous automatic production method of 2, 3-dichloropropene according to claim 1 or 2, characterized in that: after the reaction is finished, the reaction materials are subjected to phase splitting through an automatic phase splitter, the wastewater enters a wastewater treatment device in a continuous feeding mode, the treated reclaimed water is used for supplementing process water, and the sodium chloride is used for industrial production recovery.
7. The continuous automated process of claim 16, wherein: the addition rate of the reaction mass was 379.8g added dropwise every 1-1.5 h.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5479208A (en) * | 1977-12-05 | 1979-06-25 | Showa Denko Kk | Preparation of 1,3-dichloropropene |
| US20080015369A1 (en) * | 2004-07-21 | 2008-01-17 | Kruper William J Jr | Batch, semi-continuous or continuous hydrochlorination of glycerin with reduced volatile chlorinated hydrocarbon by-products and chloracetone levels |
| CN102964207A (en) * | 2012-12-22 | 2013-03-13 | 威海新元化工有限公司 | Preparation method of 2-bromo-3,3,3-trifluoropropene |
| CN103864570A (en) * | 2012-12-18 | 2014-06-18 | 中化蓝天集团有限公司 | Preparation method of 1-chloro-3,3,3-trifluoropropene |
| CN105152852A (en) * | 2015-09-16 | 2015-12-16 | 湖南城市学院 | Preparation method of 1-bromo-1-chloro-2,2-difluoroethylene |
| CN110746267A (en) * | 2019-12-03 | 2020-02-04 | 湖南莱万特化工有限公司 | Preparation method and preparation device of 2, 3-dichloropropene compound |
-
2020
- 2020-07-23 CN CN202010718883.5A patent/CN111807922A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5479208A (en) * | 1977-12-05 | 1979-06-25 | Showa Denko Kk | Preparation of 1,3-dichloropropene |
| US20080015369A1 (en) * | 2004-07-21 | 2008-01-17 | Kruper William J Jr | Batch, semi-continuous or continuous hydrochlorination of glycerin with reduced volatile chlorinated hydrocarbon by-products and chloracetone levels |
| CN103864570A (en) * | 2012-12-18 | 2014-06-18 | 中化蓝天集团有限公司 | Preparation method of 1-chloro-3,3,3-trifluoropropene |
| CN102964207A (en) * | 2012-12-22 | 2013-03-13 | 威海新元化工有限公司 | Preparation method of 2-bromo-3,3,3-trifluoropropene |
| CN105152852A (en) * | 2015-09-16 | 2015-12-16 | 湖南城市学院 | Preparation method of 1-bromo-1-chloro-2,2-difluoroethylene |
| CN110746267A (en) * | 2019-12-03 | 2020-02-04 | 湖南莱万特化工有限公司 | Preparation method and preparation device of 2, 3-dichloropropene compound |
Non-Patent Citations (2)
| Title |
|---|
| 李文波等: "微波辐射下多卤代烃的消除反应研究", 《西北师范大学学报(自然科学版)》 * |
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