CN1027889C - Process for preparing chloroacetic acid - Google Patents
Process for preparing chloroacetic acid Download PDFInfo
- Publication number
- CN1027889C CN1027889C CN 91100434 CN91100434A CN1027889C CN 1027889 C CN1027889 C CN 1027889C CN 91100434 CN91100434 CN 91100434 CN 91100434 A CN91100434 A CN 91100434A CN 1027889 C CN1027889 C CN 1027889C
- Authority
- CN
- China
- Prior art keywords
- reaction
- temperature
- acetic acid
- chlorine
- reaction solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229940106681 chloroacetic acid Drugs 0.000 title 1
- 238000004519 manufacturing process Methods 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000460 chlorine Substances 0.000 claims abstract description 30
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 21
- 229960000583 acetic acid Drugs 0.000 claims abstract description 19
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 19
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005864 Sulphur Substances 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 230000011218 segmentation Effects 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 239000012452 mother liquor Substances 0.000 abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 230000006872 improvement Effects 0.000 abstract description 2
- 239000013543 active substance Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 230000008569 process Effects 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 3
- 239000012346 acetyl chloride Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000002587 enol group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of monochloroacetic acid, which is an improvement of a method for preparing monochloroacetic acid by introducing chlorine into glacial acetic acid under the action of sulfur (or red phosphorus) for reaction and then crystallizing and separating, and mainly comprises the steps of reacting at 50-100 ℃ in a chlorination reaction stage, dividing the reaction temperature into a plurality of sections, and introducing the chlorine, thereby avoiding the escape of intermediate active substances in the reaction process, improving the conversion rate of the glacial acetic acid, and reducing the generation and the discharge of mother liquor.
Description
The present invention relates to a kind of method of producing Monochloro Acetic Acid, is exactly to react feeding chlorine with Glacial acetic acid under sulphur (or red phosphorus) effect particularly, and Crystallization Separation is produced the improvement of Monochloro Acetic Acid method then.
Mono Chloro Acetic Acid is widely used in industries such as agricultural chemicals, dyestuff, chemical industry, medicine and daily necessities, along with widening of Application Areas, it will bring into play more and more big effect in development and national economy, the method of producing Monochloro Acetic Acid that industrial production adopted, using maximum is the Glacial acetic acid chlorination process, this method is to feed chlorine with Glacial acetic acid under the katalysis of sulphur (or red phosphorus) to react, Crystallization Separation and making then, and the total equation of its reaction is:
Speed of response controlled step in its reaction mechanism is
, the enol form (CH of chlorine and Acetyl Chloride 98Min. just
2=C
OH Cl) reaction, the Acetyl Chloride 98Min. that generates in the generative process of Monochloro Acetic Acid recycles, it together plays katalysis together with the active intermediate that generates in chlorination reaction process.
The method close with the present invention, its chlorination stage temperature of reaction is generally got 100 ± 5 ℃, under this temperature, the steam of composition that the reaction system mid-boiling point is lower such as Acetyl Chloride 98Min. (51 ℃ of boiling points) etc. is overflowed with hydrogen chloride gas, though through cooling, still some is pulled away, when particularly temperature was high, the active intermediate with katalysis can not participate in reaction well, in addition because temperature of reaction is too high, increased the weight of degree of depth chlorination, cause the dichloroacetic acid content in the mother liquor to increase, the Glacial acetic acid reaction conversion ratio generally about 80%, has also influenced the performance of capacity of equipment simultaneously, facts have proved, the key of problem is not caught in only effort on the slave unit, and the someone proposes to make the chlorination reaction still into tubular, gas-liquid two-phase is fully contacted, produce little effect.
Purpose of the present invention just provides a kind of improved method of producing Monochloro Acetic Acid, reduces chlorination reaction temperature, improves the transformation efficiency of Glacial acetic acid, reduces the mother liquor discharging.
The object of the present invention is achieved like this.
Substantially do not changing under the situation of proportioning raw materials and conversion unit, the chlorination stage temperature of reaction is controlled between 50-100 ℃, when segmentation feeds chlorine, the speed that controlled temperature rises, and be that standard improves temperature of reaction with the proportion of reaction solution, help the generation of active intermediate and participate in reaction, reducing degree of depth chlorating takes place, make the active intermediate that produces in the middle of the process of sowing distrust among one's enemies as often as possible participate in chlorination reaction, make the unreacted Glacial acetic acid of gas phase return former reaction again, reduce the loss of chlorine, improve the transformation efficiency of Glacial acetic acid, reduce the generation of mother liquor.
Chlorination stage is divided into plurality of sections with temperature range, and the segmentation method of recommendation is:
Fs: temperature 50-75 ℃, feed small amounts of chlorine, to 0.9-1.15/80 ℃ of reaction solution proportion.
Subordinate phase: temperature 75-85 ℃, to reaction solution proportion be 1.20/80 ℃.
Phase III: temperature of reaction 85-90 ℃ to 1.30/80 ℃ of reaction solution proportion.
Quadravalence section: temperature of reaction 90-95 ℃, to 1.33/80 ℃ of reaction solution proportion.
Five-stage: temperature of reaction is raised to 95-100 ℃, to 1.35-1.36/80 ℃ of reaction solution proportion.
Should point out that above-mentioned segmentation method is not unique, chlorine is to feed continuously in the reaction process, in the present invention, chlorination reaction stage temperature control is at 70-100 ℃, better effects if, the temperature control interval is basically with reference to above-mentioned each stage, and temperature is at 70 ℃-75 ℃ when being initial feeding chlorine.
In the method for the invention, reducing Glacial acetic acid and active intermediate and brought into absorption unit by HCI, also is effective measure that improve the Glacial acetic acid transformation efficiency.
Method proportion of raw materials of the present invention is calculated with common proportioning basically, Glacial acetic acid: chlorine: sulphur=1000: 1240-1270: the 30-33(weight ratio), chlorine and sulphur can be in above-mentioned scope adjustment, and to react better, conservation is a principle.
The present invention compares with conventional art has following advantage: avoided original high-temp chlorination polychloride to produce, make more active intermediate participate in reaction, improved the transformation efficiency of Glacial acetic acid, easy control of process conditions, the generation and the discharging of mother liquor have been reduced, need not increase more equipment, solve pollution problem substantially.
The following examples can further specify the present invention.
Embodiment 1
In the glass chlorinator, be equipped with to the chlorine bubbler, thermometer, reflux exchanger, refrigerated brine, pack into 200 the gram Glacial acetic acid, 6 gram SULPHUR POWDER, chlorinator is heated to 50 ℃, begin logical a spot of chlorine, change temperature of reaction to 75-85 ℃ to 1.0/80 ℃ of reaction solution proportion, strengthen logical chlorine dose to 1.20/80 ℃ of reaction solution proportion, continue to heat up and be controlled at 85-90 ℃, weigh 1.30/80 ℃ to the reaction solution ratio, raise reacting liquid temperature 90-95 ℃ again, when reaction solution proportion to 1.33/80 ℃, reduce logical chlorine dose, keep reacting liquid temperature 95-98 ℃ and be reaction end when reaction solution proportion to 1.36/80 ℃, whole process chlorination continues 15 hours, chlorine feeding amount 250 grams.
Chlorinated exhaust is through behind the reflux exchanger, and by being cooled to-the coiled pipe trap of 10--15 ℃, with the condensation volatile products, then water absorbs HCI, and alkaline solution absorbs unreacted chlorine, and the material in the trap returned chlorinator once in per 2 hours.
The chlorizate that obtains gets Monochloro Acetic Acid product 280 grams through crystallization, separation, and the Glacial acetic acid transformation efficiency 86% as calculated.Product Monochloro Acetic Acid content 96.5%, analytical procedure adopts the total chlorine measurement method of sodium hydroxide.
Embodiment 2
In the enamel reaction still of 500 liters that have stirring, add 400 kilograms in Glacial acetic acid, 12 kilograms of SULPHUR POWDER, be heated to 70 ℃ earlier and begin to feed a small amount of chlorine, to 1.10/80 ℃ of reaction solution proportion, change temperature of reaction to 75-85 ℃, strengthening the chlorine feeding measures to 1.20/80 ℃ of reaction solution proportion, continue to heat up, at 85-90 ℃, be warming up to 90-95 ℃ again until 1.30/80 ℃ of reaction solution proportion, reduce logical chlorine dose when 1.34/80 ℃ of reaction solution proportion, holding temperature is at 95-100 ℃, when the reaction solution ratio weighs 1.36/80 ℃, promptly arrive reaction end, total time of chlorinating 19 hours, 500 kilograms of chlorine feeding amounts.
By being cooled to-trapper of 15-20 ℃, the condensation of volatility intermediate, then water absorbs HCI and absorbs unreacted chlorine with alkaline solution chlorinated exhaust behind reflux exchanger, whenever through 2 hours the material in the trapper is returned chlorinator.
Chlorated liquid is poured in the crystallization kettle, after separating, got 560 kilograms of Monochloro Acetic Acid products, content 97%, the Glacial acetic acid transformation efficiency 85.6% as calculated, (weight).
Make catalyzer with phosphorus trichloride, can obtain satisfied result equally.
In industrial application, the chlorination reaction still is that a positive pair is used, only when main still leads to chlorine, secondary still temperature will be lower than the main reaction still, it works the effect that absorbs unreacted chlorine and other intermediate, treats that the reaction of main reaction still finishes, and secondary reacting kettle then becomes the main reaction still again.
Claims (2)
1, a kind of method of producing Monochloro Acetic Acid, Glacial acetic acid is under the katalysis of sulphur, and logical chlorine reacts, and Crystallization Separation and making is characterized in that chlorination reaction stage temperature control 50-100 ℃ then, and with alternating temperature mode segmentation controlled temperature, feeds chlorine.Method proportioning raw materials of the present invention is: Glacial acetic acid: chlorine: sulphur=1000: 1240-1270: 30-30 (weight ratio).
2, by the described method of claim 1, it is characterized in that the chlorination reaction stage is a standard with reaction solution proportion, temperature section controlled:
Fs: temperature 50-75 ℃, to 0.9-1.15/80 ℃ of reaction solution proportion
Subordinate phase: temperature 75-85 ℃, to 1.20/80 ℃ of reaction solution proportion.
Phase III: temperature of reaction 85-95 ℃, to 1.30/80 ℃ of reaction solution proportion.
Quadravalence section: temperature of reaction 90-95 ℃, to 1.33/80 ℃ of reaction solution proportion.
Five-stage: temperature of reaction 95-100 ℃, to 1.35-1.36/80 ℃ of reaction solution proportion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91100434 CN1027889C (en) | 1991-01-31 | 1991-01-31 | Process for preparing chloroacetic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91100434 CN1027889C (en) | 1991-01-31 | 1991-01-31 | Process for preparing chloroacetic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1063677A CN1063677A (en) | 1992-08-19 |
| CN1027889C true CN1027889C (en) | 1995-03-15 |
Family
ID=4904629
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91100434 Expired - Fee Related CN1027889C (en) | 1991-01-31 | 1991-01-31 | Process for preparing chloroacetic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1027889C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066431C (en) * | 1994-12-05 | 2001-05-30 | 萨尔斯吉特设备有限公司 | Preparation of monochloro acetic acid |
| CN1059662C (en) * | 1996-10-03 | 2000-12-20 | 北京清华紫光英力化工技术有限责任公司 | Chloroacetic acid producing process |
| CN1105702C (en) * | 2000-01-14 | 2003-04-16 | 重庆嘉陵化学制品有限公司 | Process for preparing monochloroacetic acid |
| CN102863325B (en) * | 2012-09-26 | 2015-10-28 | 河北东华冀衡化工有限公司 | Prepare chloroacetic Periodic automatic control method |
| CN103922916B (en) * | 2014-04-30 | 2015-10-28 | 中国天辰工程有限公司 | A kind of Mono Chloro Acetic Acid chlorination mother solution treatment process |
| CN105152908A (en) * | 2015-08-14 | 2015-12-16 | 河南红东方化工股份有限公司 | Method for recovering acetic acid from tail gas produced during preparation of chloroacetic acid |
| CN111548266A (en) * | 2020-05-11 | 2020-08-18 | 无锡贝塔医药科技有限公司 | Stable isotope13Method for synthesizing C-marked dichloroacetic acid |
-
1991
- 1991-01-31 CN CN 91100434 patent/CN1027889C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1063677A (en) | 1992-08-19 |
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