CN1260344A - Preparation method for trichlor-acetyl chloride - Google Patents
Preparation method for trichlor-acetyl chloride Download PDFInfo
- Publication number
- CN1260344A CN1260344A CN 99113977 CN99113977A CN1260344A CN 1260344 A CN1260344 A CN 1260344A CN 99113977 CN99113977 CN 99113977 CN 99113977 A CN99113977 A CN 99113977A CN 1260344 A CN1260344 A CN 1260344A
- Authority
- CN
- China
- Prior art keywords
- oxygen
- preparation
- reaction
- zellon
- logical
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The preparation method of trichlorotriacylchloride includes the following steps: 1. adding tetrachloroethylene, oxygen gas and catalyst in reator, heating to 180-260 deg.C, retaining temp. in reactor and stabilizing pressure, then introducing oxygen to 1.0-6.5 MPa, promptly removing reaction heat, and introducing oxygen until the reaction is completed; 2. after reaction, transferring the feed liquid into chlorination still, and converting the residual tetrachloroethylene in the system into hexachloroethane; 3. after chlorination transferring the feed liquid into rectifying still to separate and collect the trichlorotriacylchloride. It is applicable to industrial production.
Description
The invention belongs to the method for preparing the organic intermediate trichoroacetic chloride.
Trichoroacetic chloride is an intermediate of making agricultural chemicals " Chlorpyrifos 94 ", can obtain trichoroacetic chloride with oxygen and zellon oxidizing reaction.U.S. Pat 3959367 (1976) has disclosed without catalyzer and initiator carries out oxygen and the zellon reaction makes trichoroacetic chloride, for obtaining high transformation efficiency, oxidizing reaction needs to carry out in two placed in-line containers, so both increased facility investment and production site, and also made operation sequence become complicated.German patent DE 3933559 (1991) has been introduced to cause with UV-light and has been carried out the experimental technique that trichoroacetic chloride is produced in oxygen and zellon reaction, is reflected in the small-sized Glass Containers and carries out, and as if carrying out large-scale production, its condition is still immature.
The object of the present invention is to provide a kind of preparation method who is suitable for the trichoroacetic chloride of large-scale production, present method oxidizing reaction is to carry out in a reactor, its transformation efficiency height, yield height, constant product quality.
The preparation method of trichoroacetic chloride of the present invention is achieved through the following technical solutions:
Add zellon, oxygen, catalyzer in reaction vessel, heating increases oxygen and presses, and carries out reaction product isolated after the zellon oxidizing reaction, and its special character is to carry out as follows:
(1) zellon, oxygen, catalyzer are added reactor together, stop heating behind heat temperature raising to 165～260 ℃, after question response temperature in the kettle, the pressure-stabilisation, stop logical oxygen after opening the logical oxygen to 1.0 of logical oxygen valve～6.5MPa, in time remove reaction heat to described temperature range, logical then oxygen to reaction ends;
(2) will react back feed liquid input chlorination tank, make that remaining zellon is converted into hexachloroethane in the system;
(3) with feed liquid input rectifying still after the chlorination, separate and the collection trichoroacetic chloride.
In order to improve yield, can in step (1) reactor, add promotor, promotor can be organic oxygen-containing compound, as paraldehyde, methylethylketone;
Can also add initiator again in step (1) reactor, to improve speed of response, reduce by product, initiator can be hydrogen peroxide Trimethylmethane or 2,2'-Azobis(2,4-dimethylvaleronitrile).
Below the invention will be further described.
Oxidizing reaction of the present invention is carried out in a container, and the reaction times can be in 12 hours.
Oxygen can adopt the empty pure oxygen that divides, and also can be through rare gas element such as Ar, N
2Dilution, but it must be an exsiccant; Zellon must be anhydrous.
Oxidizing reaction is carried out in stainless steel cauldron, and above-mentioned steps (1) heat temperature raising to 220 is ℃ proper, so far stops heating after the temperature, treat that temperature no longer rises and stable after, open the logical oxygen of logical oxygen valve.Logical first oxygen is proper to 2.5Mpa, so far closes logical oxygen valve behind the pressure.Reacting phenomenon is that temperature rises, and pressure is toward descending, and should in time remove reaction heat this moment.Thereafter continue logical oxygen, along with the carrying out of reaction, the pressure of logical oxygen also improves thereupon, up to 6.5Mpa.Follow the tracks of the transformation efficiency of zellon with gas-chromatography.
Because the boiling point of zellon and trichoroacetic chloride only differs 2 ℃, be difficult to separate with ordinary method.So generally be to zellon content when 1.5% left and right sides, the synthetic liquid of oxidation is carried out chlorination in the presence of catalyzer (Diisopropyl azodicarboxylate class), remaining zellon in the system all is converted into hexachloroethane.Chlorination is after treating that system temperature is reduced to 110 ℃, opens tail gas absorption condensation system earlier, slowly opens blow-off valve, and exhaust pressure relief is closed exhaust-valve to 0.5Mpa, open the feed valve of chlorination tank, utilizes pressure reduction that the mixed liquor in the stills for air blowing is pressed into chlorination tank.The chlorating optimum temps is 120～140 ℃, pressure 0.2MPa～1.5Mpa.After the chlorination feed liquid being imported rectifying still separates.
Normal pressure or slightly negative pressure rectifying are adopted in rectifying, with trichoroacetic chloride from the rectifying tower top part from coming out.Collect the by product hexachloroethane with crystallization mode then.
Consider that hexachloroethane is solid at normal temperatures, being discharged to crystallization kettle in the rectifying still acquires a certain degree of difficulty, suitable way is, mol ratio to trichoroacetic chloride and hexachloroethane to be separated is 1: 1～1.5 o'clock, stop rectifying, open the rectifying still bottom valve while hot mixed liquor is put into the crystallization kettle that fills a certain amount of zellon through precooling, continue refrigeration, feed liquid is cooled to below-4 ℃, make hexachloroethane in zellon, separate out crystal, utilize suction filtration to separate, mother liquor is used as raw material and is added during following batch of stills for air blowing feed intake.
The present invention is because in the reaction of carrying out zellon and oxygen in the presence of the catalyzer in an oxidizing reactor, temperature of reaction is at 180～260 ℃, and pressure is 2.5～6.0Mpa, and the reaction times can be in 12 hours, the present invention with oxidizing reaction after remaining zellon be converted into hexachloroethane so that separate through chlorination, so it is short that the present invention has technical process, the three wastes are few, easy industrialized characteristics, trial production shows, conversion rate of products height of the present invention, yield height, constant product quality.
The following describes the specific embodiment of the present invention, wherein per-cent refers to molar percentage.
Embodiment 1 adds the 1600ml zellon in the 2L stainless steel autoclave, 15.0g initiator, 15.0g composite catalyst, 5.0g promotor, close all valves and carry out heat temperature raising, when temperature rises to 220 ℃, stop to heat up, at this moment the gauge pressure in the reactor is 0.8Mpa, after treating temperature, pressure-stabilisation, open logical oxygen valve, with the oxygen voltage rise behind 2.5Mpa, close logical oxygen valve, the temperature on the visualizer dial plate and the variation of pressure, reacting phenomenon are that temperature rises, and pressure is toward descending, in time reaction heat is removed, in order to avoid temperature surpasses the specified temperature upper limit in the reaction system.By the time temperature returns in the scope of specified temperature, carries out the logical oxygen second time.Temperature and pressure when noting each logical oxygen with cooling.Along with the oxygen that carries out of reaction is pressed raising thereupon, every sampling in 2 hours once, the detection reaction degree.Oxidation time listed by table 1 and corresponding converted product is formed.
Table 1
| Time | Converted product is formed (%) | |||
| ??CCl 2CCl 2 | ?HCCl 2COCl | ?CCl 3COCl | ??C 2Cl 6 | |
| ????2 | ????80.5 | ????0.1 | ????18.8 | ????0.6 |
| ????4 | ????65.4 | ????0.3 | ????32.2 | ????2.1 |
| ????6 | ????50.2 | ????0.4 | ????46.4 | ????3.0 |
| ????8 | ????10.5 | ????0.7 | ????84.5 | ????4.2 |
| ????10 | ????4.8 | ????0.8 | ????89.5 | ????4.9 |
| ????12 | ????1.5 | ????0.8 | ????92.5 | ????5.2 |
| ????14 | ????0.1 | ????0.9 | ????93.5 | ????5.5 |
In the last table data last 2 hours, in chlorination tank, finish, question response is complete, send rectifying still to separate, trichoroacetic chloride 2501.7g, content 99.3%, yield 86.77%.
Embodiment 2 testing installations and logical oxygen mode are with example 1, and temperature of reaction is made as 180 ℃, and oxygen is pressed also with example 1, and the result is as shown in table 2.
Table 2
| Time | Converted product is formed (%) | |||
| ??CCl 2CCl 2 | ?HCCl 2COCl | ?CCl 3COCl | ??C 2Cl 6 | |
| ????2 | ????86.2 | ????0.1 | ????13.2 | ????0.5 |
| ????4 | ????78.1 | ????0.1 | ????21.0 | ????0.8 |
| ????6 | ????65.8 | ????0.3 | ????32.5 | ????1.4 |
| ????10 | ????50.4 | ????0.4 | ????47.4 | ????1.8 |
| ????12 | ????40.5 | ????0.6 | ????55.4 | ????3.5 |
| ????14 | ????31.8 | ????0.6 | ????63.5 | ????4.1 |
| ????16 | ????20.2 | ????0.7 | ????74.3 | ????4.8 |
| ????18 | ????10.3 | ????0.7 | ????83.5 | ????5.5 |
| ????20 | ????1.4 | ????0.8 | ????92.9 | ????5.9 |
From last table data as can be seen, temperature of reaction reduces, and the reaction times prolongs, and at last rectifying after the feed liquid chlorination is got trichoroacetic chloride 2485.1g, and content 99.1%, yield are 86.02%.
Embodiment 3 testing installations and charge ratio are with example 1, and temperature of reaction system is set at 260 ℃, and other operational conditions are with example 1.Its result is as shown in table 3.
Table 3
| Time | Converted product is formed (%) | |||
| ??CCl 2CCl 2 | ?HCCl 2COCl | ?CCl 3COCl | ????C 2Cl 6 | |
| ????2 | ????70.4 | ????0.1 | ????25.3 | ????4.2 |
| ????4 | ????55.6 | ????0.3 | ????37.7 | ????7.4 |
| ????6 | ????29.5 | ????0.5 | ????50.7 | ????10.3 |
| ????8 | ????8.1 | ????0.7 | ????76.4 | ????14.8 |
| ????10 | ????1.0 | ????0.8 | ????82.7 | ????16.5 |
| ????12 | ????0.03 | ????0.8 | ????82.3 | ????16.9 |
By last table data as can be seen, along with the raising of temperature of reaction, speed of response also improves thereupon, but by product obviously increases, and finishes in chlorination tank in last 2 hours of reaction.Rectifying gets trichoroacetic chloride 2350.5g, content 99.8%, yield 81.94%.
Embodiment 4 testing installations and logical oxygen mode do not add catalyzer with example 1, and other conditions are with example 1, and its result is as shown in table 4.
Table 4
| Time | Converted product is formed (%) | |||
| ??CCl 2CCl 2 | ?HCCl 2COCl | ?CCl 3COCl | ??C 2Cl 6 | |
| ????2 | ????85.3 | ????0.1 | ????13.6 | ????1.0 |
| ????4 | ????80.1 | ????0.1 | ????17.3 | ????2.5 |
| ????6 | ????71.8 | ????0.2 | ????24.0 | ????4.0 |
| ????8 | ????60.3 | ????0.3 | ????34.3 | ????5.1 |
| ????10 | ????49.5 | ????0.5 | ????42.2 | ????7.8 |
| ????12 | ????30.6 | ????0.6 | ????60.8 | ????9.0 |
| ????14 | ????25.4 | ????0.6 | ????63.9 | ????10.1 |
| ????16 | ????20.8 | ????0.7 | ????67.6 | ????10.9 |
| ????18 | ????11.3 | ????0.7 | ????76.7 | ????11.3 |
| ????20 | ????2.1 | ????0.8 | ????85.0 | ????12.1 |
| ????22 | ????0.1 | ????0.8 | ????85.1 | ????14.0 |
Learn do not having under the condition of catalyzer from last table data, the reaction times prolongs greatly, and by product has also increased; From reacting phenomenon, temperature of reaction ratio 1 difficulty is controlled in the optimum temps zone.Last rectifying gets trichoroacetic chloride 2365.1g, content 99.4%, yield 82.12%.
Embodiment 5 does not add initiator according to example 1 test conditions in the system, its reaction result is as shown in table 5.
Table 5
| Time | Converted product is formed (%) | |||
| ??CCl 2CCl 2 | ?HCCl 2COCl | ?CCl 3COCl | ??C 2Cl 6 | |
| ????2 | ????90.1 | ????0.0 | ????8.5 | ????1.4 |
| ????4 | ????85.8 | ????0.1 | ????11.5 | ????2.6 |
| ????6 | ????76.3 | ????0.4 | ????19.0 | ????4.3 |
| ????8 | ????59.8 | ????0.5 | ????34.7 | ????5.0 |
| ????10 | ????30.3 | ????0.6 | ????63.6 | ????5.8 |
| ????12 | ????21.3 | ????0.6 | ????71.9 | ????6.2 |
| ????14 | ????9.5 | ????0.8 | ????83.2 | ????6.5 |
| ????16 | ????1.7 | ????0.8 | ????90.6 | ????6.9 |
| ????18 | ????0.1 | ????0.9 | ????90.7 | ????8.3 |
From last table data as can be known, when lacking initiator, initial reaction stage has a tangible inductive phase, and speed of response is slow, and the reaction times prolongs, and by product slightly increases.Get trichoroacetic chloride 2430.5g through rectifying, content 99.0%, yield 84.05%.
Embodiment 6 is amplified to 500L according to example 1 condition with reactor, and its charge ratio is as follows: zellon 400L, initiator 3.75kg, composite catalyst 1.25kg, promotor 0.4kg.The gas chromatograph track data is as shown in table 6.
Table 6
| Time | Converted product is formed (%) | |||
| ??CCl 2CCl 2 | ?HCCl 2COCl | ?CCl 3COCl | ??C 2Cl 6 | |
| ????2 | ????71.3 | ????0.1 | ????28.3 | ????0.3 |
| ????4 | ????50.2 | ????0.3 | ????48.6 | ????0.9 |
| ????6 | ????32.5 | ????0.4 | ????64.6 | ????2.5 |
| ????8 | ????10.7 | ????0.5 | ????84.0 | ????4.8 |
| ????10 | ????1.1 | ????0.7 | ????92.9 | ????5.3 |
| ????12 | ????0.2 | ????0.7 | ????93.0 | ????6.1 |
From last table data as can be seen, the pilot scale data match with lab scale basically, reach re-set target, get trichoroacetic chloride 630.5kg through rectifying, content 99.5%, yield 87.65%.
Embodiment 7 is amplified to 1200L according to example 1 condition again with reaction vessel, and corresponding charge ratio is as follows: zellon 960L, and composite catalyst 3.0kg, initiator 9.0kg, it is as shown in table 7 that promotor 0.96kg, gas chromatograph follow the tracks of the detection data.
Table 7
| Time | Converted product is formed (%) | |||
| ??CCl 2CCl 2 | ?HCCl 2COCl | ?CCl 3COCl | ??C 2Cl 6 | |
| ????2 | ????68.3 | ????0.2 | ????30.7 | ????0.8 |
| ????4 | ????41.2 | ????0.3 | ????57.6 | ????0.9 |
| ????6 | ????20.8 | ????0.5 | ????76.3 | ????2.4 |
| ????8 | ????5.4 | ????0.6 | ????90.1 | ????3.9 |
| ????10 | ????1.0 | ????0.7 | ????93.8 | ????4.5 |
| ????12 | ????0.1 | ????0.7 | ????94.3 | ????4.9 |
From last table data as can be seen, scale-up is behind the reaction vessel of 1200L, and is still consistent with lab scale, gets trichoroacetic chloride 1496.0kg through rectifying, content 99.3%, yield 86.48%.
Claims (9)
1, the preparation method of trichoroacetic chloride adds zellon, oxygen, catalyzer in reaction vessel, heating increases oxygen and presses, and carries out reaction product isolated after the zellon oxidizing reaction, it is characterized in that carrying out as follows:
(1) zellon, oxygen, catalyzer are added reactor together, stop heating behind heat temperature raising to 165～260 ℃, after question response temperature in the kettle, the pressure-stabilisation, stop logical oxygen after opening the logical oxygen to 1.0 of logical oxygen valve～6.5MPa, in time remove reaction heat to described temperature range, logical then oxygen to reaction ends;
(2) will react back feed liquid input chlorination tank, make that remaining zellon is converted into hexachloroethane in the system;
(3) with feed liquid input rectifying still after the chlorination, separate and the collection trichoroacetic chloride.
2, the preparation method of trichoroacetic chloride as claimed in claim 1 is characterized in that step (1) adds the promotor that also has of reactor.
3, the preparation method of trichoroacetic chloride as claimed in claim 2 is characterized in that step (1) adds the initiator that also has of reactor.
4, as the preparation method of claim 1,2 or 3 described trichoroacetic chlorides, it is characterized in that mol ratio that step (3) is separated to trichoroacetic chloride and hexachloroethane in rectifying still is to stop rectifying at 1: 1～1: 5 o'clock, open bottom valve mixed liquor is put into the crystallization kettle that fills zellon through precooling, continue refrigeration to below-4 ℃, the hexachloroethane crystallization is separated out, and separate, mother liquor is used as raw material and is added during following batch of stills for air blowing feed intake.
5, as the preparation method of claim 1,2 or 3 described trichoroacetic chlorides, it is characterized in that step (1) heat temperature raising to 220 ℃, logical first oxygen is to 2.5Mpa; Logical one by one then oxygen is until 6.5Mpa.
6, the preparation method of trichoroacetic chloride as claimed in claim 4 is characterized in that step (1) heat temperature raising to 220 ℃, and logical first oxygen is to 2.5Mpa; Logical one by one then oxygen is until 6.5Mpa.
7,, it is characterized in that the described reaction end of a period of step (1) is meant that zellon content (mole) is in the reactor at＜1.5% o'clock as the preparation method of claim 1,2 or 3 described trichoroacetic chlorides.
8, the preparation method of trichoroacetic chloride as claimed in claim 4 is characterized in that the described reaction end of a period of step (1) is meant that zellon content (mole) is in the reactor at＜1.5% o'clock.
9, as the preparation method of claim 1,2 or 3 described trichoroacetic chlorides, it is characterized in that described catalyzer is heterocyclic nitrogen base and derivative thereof, initiator is hydrogen peroxide Trimethylmethane or 2,2'-Azobis(2,4-dimethylvaleronitrile), and promotor is the organic oxygen-containing thing, as paraldehyde, methylethylketone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99113977 CN1260344A (en) | 1999-08-13 | 1999-08-13 | Preparation method for trichlor-acetyl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99113977 CN1260344A (en) | 1999-08-13 | 1999-08-13 | Preparation method for trichlor-acetyl chloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1260344A true CN1260344A (en) | 2000-07-19 |
Family
ID=5277109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99113977 Pending CN1260344A (en) | 1999-08-13 | 1999-08-13 | Preparation method for trichlor-acetyl chloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1260344A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9221853B2 (en) | 2009-12-09 | 2015-12-29 | Zhejiang Wynca Chemical Industry Group Co., Ltd. | Glyphosate dimethylamine salt crystal, preparation method and use thereof |
-
1999
- 1999-08-13 CN CN 99113977 patent/CN1260344A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9221853B2 (en) | 2009-12-09 | 2015-12-29 | Zhejiang Wynca Chemical Industry Group Co., Ltd. | Glyphosate dimethylamine salt crystal, preparation method and use thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hanika et al. | Butylacetate via reactive distillation—modelling and experiment | |
| CN1993473B (en) | A process for the production of polylactic acid (PLA) from renewable feedstocks | |
| US6569989B2 (en) | Process for producing lactide and process for producing polylactic acid from fermented lactic acid employed as starting material | |
| JP6549582B2 (en) | Improved process for producing polylactic acid | |
| KR920003924B1 (en) | Process for the preparation of formic acid | |
| EP0662943A1 (en) | A recycling process for the production of adipic acid and other aliphatic dibasic acids | |
| CN109503827B (en) | Catalyst for preparing polypeptide by ring-opening polymerization of amino acid cyclic anhydride and method for preparing polypeptide by using catalyst | |
| WO2016007865A1 (en) | Novel lactic acid recovery process | |
| CN1260344A (en) | Preparation method for trichlor-acetyl chloride | |
| CN111269151B (en) | Method for preparing taurine from sodium isethionate | |
| CN110479234B (en) | Catalyst for synthesizing dimethylaminoethyl methacrylate, preparation method and application thereof | |
| CN101337923B (en) | Process for purifying crude pyridine | |
| CN115806536B (en) | Method for preparing 5-hydroxymethylfurfural by solvent-free system | |
| CN113549026B (en) | Synthesis process of N-vinyl oxazolidone compound | |
| EP0705813A1 (en) | Phenol tar waste reduction process | |
| CN105315155A (en) | Method used for preparing polyglycolic acid oligomer | |
| CN114478606A (en) | Synthetic method of tributyl borate | |
| CN1093528C (en) | Preparation method of high-purity endocyclic type cyclopentadiene | |
| CN218795842U (en) | Continuous production device of propionyl chloride | |
| KR101183982B1 (en) | Process for preparing lactide and polylactide from Lactic acid fermentation | |
| CN112341341B (en) | Preparation method of N-ethylaniline | |
| JPH01242547A (en) | Method for absorbing methacrolein | |
| CN1951933A (en) | Preparation process of lactide | |
| EP3041816B1 (en) | Lactate production process | |
| CN113563160B (en) | Preparation method of pyrogallic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |