CN103524291A - Continuous synthetic method of chloralkane - Google Patents
Continuous synthetic method of chloralkane Download PDFInfo
- Publication number
- CN103524291A CN103524291A CN201310428106.7A CN201310428106A CN103524291A CN 103524291 A CN103524291 A CN 103524291A CN 201310428106 A CN201310428106 A CN 201310428106A CN 103524291 A CN103524291 A CN 103524291A
- Authority
- CN
- China
- Prior art keywords
- reactor
- reaction
- chloroparaffin
- continuously
- tetracol phenixin
- 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.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a continuous synthetic method of chloralkane. The method comprises the following steps: (1) adding a mixture of carbon tetrachloride and iron powder into a reactor, wherein the volume of the mixture is 10-30% of the volume of the reactor, and the mass ratio of carbon tetrachloride to the iron powder in the mixture is 1:(0.1-1); (2) continuously adding a mixture of carbon tetrachloride and a catalyst with the molar ratio of (40-50):1 to the reactor from the bottom of the reactor, controlling the reaction temperature at 90-150 DEG C, and meanwhile, continuously introducing olefin to the reactor from the bottom of the reactor to control the reaction pressure at 0.5-1.2MPa to react; (3) collecting a reacting liquid overflowing from the upper part of the reactor and rectifying the reacting liquid to obtain a chloralkane product. The method provided by the invention has the advantages of simplicity in operation, less equipment investment, high production efficiency and recycling of the catalyst without separation.
Description
Technical field
The present invention relates to a kind of method for continuously synthesizing of chloroparaffin.
Background technology
Tetracol phenixin is the byproduct of producing methane chloride, as Ozone Depleting Substances, is prohibited for clean-out system.The most feasible way of outlet that solves a large amount of tetracol phenixin is exactly as industrial chemicals, is converted into non-ODS material.Tetracol phenixin and alkene carry out telomerization, generate chloroparaffin, more further fluoridize as fluoric ether, are widely adopted.This synthetic method must just can be carried out under catalyzer exists, and bibliographical information is more, and catalyzer mainly contains superoxide, metal inorganic salt and nitrile, metal carbonyl, alkyl phosphorous acid ester and metal chloride etc.
Superoxide is as catalyzer, and telomerization is too violent, restive, has explosion hazard, should not carry out industrialization; Metal inorganic salt and nitrile catalyst system need to just can obtain higher product yield under low pressure, do not possess industrialization prospect; Metal carbonyl is expensive, and toxicity is large, is difficult to industrialization; Alkyl phosphorous acid ester and metal chloride catalyst system exist the degree of depth to telomerize, and easily generate a large amount of tarry superpolymer, reduce equipment heat transfer efficiency, waste raw material.After researchist improves alkyl phosphorous acid ester and metal chloride catalyst system, researched and developed with the catalyst system of alkyl phosphorous acid ester and reduced iron powder and prepared chloroparaffin, alleviate the degree that the degree of depth telomerizes, under lower temperature, pressure, also can obtain higher yields.
But in prior art, with the catalyst system of alkyl phosphorous acid ester and reduced iron powder, preparing chloroparaffin is all to take autoclave rhythmic reaction as main, have that facility investment is large, technique is loaded down with trivial details, reaction efficiency is low, the shortcomings such as the difficult recovery of catalyzer, have greatly hindered industrialization process.
As US Patent No. 6313360 discloses the preparation method of 1,1,1,3,3-pentachloropropane (HCC-240fa), in lining tetrafluoroethylene autoclave, take iron powder and tributyl phosphate and prepare 1,1,1,3,3-pentachloropropane as catalyzer, the reaction times reaches 9 hours.Weak point is that this reaction is batch production, complex operation, and long reaction time, production efficiency is low; Lining tetrafluoroethylene autoclave manufacturing expense is high; During dispersed the and catalyst recovery of iron powder in solution, the problem of occluding device and pipeline is difficult for solving.
Summary of the invention
The object of the invention is to overcome the defect of above-mentioned prior art, provide a kind of simple to operate, facility investment is few, the continuous synthesis technique of the chloroparaffin that production efficiency is high, catalyzer does not need separated reusable edible.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: a kind of method for continuously synthesizing of chloroparaffin, comprises the following steps:
(1) in reactor, add the mixture of tetracol phenixin and iron powder, described volume of mixture is reactor volume 10～30%, and in mixture, the mass ratio of tetracol phenixin and iron powder is 1:0.1～1;
(2) from reactor bottom to reactor, adding continuously mol ratio is the tetracol phenixin of 40～50:1 and the mixture of catalyzer, and to control temperature of reaction be 90～150 ℃, by passing into continuously alkene from reactor bottom to reactor, to control reaction pressure be that 0.5～1.2MPa reacts simultaneously;
(3) collect and obtain chloroparaffin product from reaction solution the rectifying of the overflow of reactor top.
Further:
Iron powder order number described in step (1) is 100～500.
Volume of mixture described in step (1) is reactor volume 15～25%.
The mass ratio of the tetracol phenixin described in step (1) and iron powder is 1:0.3～0.5.
Temperature of reaction described in step (2) is 110～120 ℃, and reaction pressure is 0.8～1.0MPa.
The mol ratio of the tetracol phenixin described in step (2) and catalyzer is 45～47:1.
Catalyzer described in step (2) is a kind of in triethyl phosphate, triethyl-phosphite, n-Butyl Amine 99, Isopropylamine.
Alkene described in step (2) is a kind of in ethene, vinylchlorid, vinylidene chloride, vinylbenzene.
In reaction process, in order to allow iron powder in recurrent state, so that the catalyzer adding continuously with bottom fully contacts, preferably in reaction process, the reaction solution in reactor is drawn and turned back to reactor from top from reactor bottom, circulate.
In a preferred embodiment of the invention, in reaction process, the reaction solution that contains iron powder is drawn by reactor bottom, after recycle pump circulates, squeeze into again reactor, add continuously the mixture of tetracol phenixin, catalyzer and alkene simultaneously from reactor bottom to reaction system.Iron powder is slow decreasing under action of gravity, under the catalyzer co-catalysis adding with bottom, tetracol phenixin and olefine reaction, generate chloroparaffin, reaction solution is drawn continuously finally by reactor top overflow port, through rectifying, reclaims unreacted tetracol phenixin recycled, obtain chloroparaffin product, the carrying out continuously of realization response simultaneously.The present invention has simple to operate, and facility investment is few, the advantage that production efficiency is high, catalyzer does not need separated reusable edible.
When reaction starts, first adding volume is 10～30% tetracol phenixin, iron mixture of reactor volume, and make iron powder in recurrent state, and can make iron powder and material and the liquid catalyst that adds continuously from reactor bottom fully contacts, improve the efficiency of reaction.The mass ratio of tetracol phenixin and iron powder is 1:0.1～1, preferably 1:0.3～0.5.It is suitable that iron particle size will be selected, and excessive surface-area is little, and catalyst effect is poor, and too small unsuitable sedimentation, causes catalyzer to run off from overflow port with product, and general order number selects 100～500, and preferably 200～300.
Temperature of reaction is synthesized and is had important impact continuously chloroparaffin.Temperature is too low, and speed of response is too slow, and a large amount of alkene unreacteds, cause the waste of material; Temperature of reaction is too high, aggravates side reaction.Therefore, in the present invention, temperature of reaction is controlled at 90～150 ℃, preferably 110～120 ℃.
In reaction process, catalyzer, in continuous decomposition, need to keep there are enough catalyzer in reaction solution, just can make reaction constantly carry out.Therefore, in the present invention, the mol ratio of tetracol phenixin and catalyzer is 40～50:1, preferably 45～47:1.
Reaction pressure in the present invention is to control by passing into the amount of the alkene of reactor, and when the amount of alkene that passes into reactor is very little time, reaction pressure is too low, and the density loss of alkene in reaction system causes speed of reaction to decline, the efficiency of impact reaction; When passing into the amount of alkene of reactor when too many, reaction pressure is too high, and the concentration of alkene in reaction system rises, and causes speed of reaction too fast, and temperature should not be controlled, and local temperature is too high, and by product increases.Therefore, in the present invention, by controlling the intake of alkene, reaction pressure is controlled be 0.5～1.2MPa, be preferably 0.8～1.0MPa.
Reactor material of the present invention can adopt the materials such as carbon steel, stainless steel, the conventional reactor types in this area such as that reactor types can adopt is tower, autoclave.
Compared with prior art, the present invention has the following advantages:
1, simple to operate, facility investment is few, and production efficiency is high, has realized operate continuously, and catalyzer does not need separated reusable edible, is applicable to large-scale industrial production;
2, reaction yield is high, and selectivity is good, and yield reaches as high as 89.3%, and selectivity reaches as high as 99.7%.
Embodiment
By the following examples the present invention is carried out to more specific description, but the present invention is not limited to described embodiment.
Embodiment 1:
In stainless steel reactor at volume 10L with outer circulation, add 2L tetracol phenixin, 300 order iron mixtures, the mass ratio of tetracol phenixin and iron powder is 1:0.3.Start recycle pump, the reaction solution that contains iron powder is drawn by reactor bottom, after recycle pump pressurization, then squeeze into reactor from reactor head.From reactor bottom to reactor, adding continuously mol ratio is the tetracol phenixin of 47:1 and the mixed solution of triethyl-phosphite, heating up and controlling temperature of reaction is 100 ℃, and by passing into continuously ethene from reactor bottom to reactor, to control reaction pressure be that 1.0MPa reacts simultaneously.Reaction solution is drawn continuously by reactor top overflow port, through rectifying, reclaims unreacted tetracol phenixin, obtains 1,1,1,3-tetrachloro propane product, 1,1,1,3-tetrachloro propane yield 85.3%, selectivity 97.6% simultaneously.
Embodiment 2:
In stainless steel reactor at volume 10L with outer circulation, add 2L tetracol phenixin, 500 order iron mixtures, the mass ratio of tetracol phenixin and iron powder is 1:0.1.Start recycle pump, the reaction solution that contains iron powder is drawn by reactor bottom, after recycle pump pressurization, then squeeze into reactor from reactor head.From reactor bottom to reactor, adding continuously mol ratio is the tetracol phenixin of 40:1 and the mixed solution of triethyl-phosphite, heating up and controlling temperature of reaction is 120 ℃, and by passing into continuously ethene from reactor bottom to reactor, to control reaction pressure be that 1.2MPa reacts simultaneously.Reaction solution is drawn continuously by reactor top overflow port, through rectifying, reclaims unreacted tetracol phenixin, obtains 1,1,1,3-tetrachloro propane product, 1,1,1,3-tetrachloro propane yield 83.7%, selectivity 93.6% simultaneously.
Embodiment 3:
In stainless steel reactor at volume 10L with outer circulation, add 1L tetracol phenixin, 400 order iron mixtures, the mass ratio of tetracol phenixin and iron powder is 1:0.8.Start recycle pump, the reaction solution that contains iron powder is drawn by reactor bottom, after recycle pump pressurization, then squeeze into reactor from reactor head.From reactor bottom to reactor, adding continuously mol ratio is the tetracol phenixin of 50:1 and the mixed solution of triethyl-phosphite.Heating up and controlling temperature of reaction is 150 ℃, and by passing into continuously ethene from reactor bottom to reactor, to control reaction pressure be that 0.5MPa reacts simultaneously.Reaction solution is drawn continuously by reactor top overflow port, through rectifying, reclaims unreacted tetracol phenixin, obtains 1,1,1,3-tetrachloro propane product, 1,1,1,3-tetrachloro propane yield 83.7%, selectivity 90.1% simultaneously.
Embodiment 4:
In stainless steel reactor at volume 10L with outer circulation, add 2L tetracol phenixin, 100 order iron mixtures, the mass ratio of tetracol phenixin and iron powder is 1:1.Start recycle pump, the reaction solution that contains iron powder is drawn by reactor bottom, after recycle pump pressurization, then squeeze into reactor from reactor head.From reactor bottom to reactor, adding continuously mol ratio is the tetracol phenixin of 45:1 and the mixed solution of triethyl-phosphite.Heating up and controlling temperature of reaction is 90 ℃, and by passing into continuously ethene from reactor bottom to reactor, to control reaction pressure be that 0.8MPa reacts simultaneously.Reaction solution is drawn continuously by reactor top overflow port, through rectifying, reclaims unreacted tetracol phenixin, obtains 1,1,1,3-tetrachloro propane product, 1,1,1,3-tetrachloro propane yield 89.3%, selectivity 98.2% simultaneously.
Embodiment 5:
In carbon steel reactor at volume 10L with outer circulation, add 3L tetracol phenixin, 200 order iron mixtures, the mass ratio of tetracol phenixin and iron powder is 1:0.7.Start recycle pump, the reaction solution that contains iron powder is drawn by reactor bottom, after recycle pump pressurization, then squeeze into reactor from reactor head.From reactor bottom to reactor, adding continuously mol ratio is the tetracol phenixin of 45:1 and the mixed solution of triethyl-phosphite, heating up and controlling temperature of reaction is 110 ℃, and by passing into continuously ethene from reactor bottom to reactor, to control reaction pressure be that 1.1MPa reacts simultaneously.Reaction solution is drawn continuously by reactor top overflow port, through rectifying, reclaims unreacted tetracol phenixin, obtains 1,1,1,3-tetrachloro propane product, 1,1,1,3-tetrachloro propane yield 84.3%, selectivity 97.5% simultaneously.
Embodiment 6:
In carbon steel reactor at volume 10L with outer circulation, add 1.5L tetracol phenixin, 200 order iron mixtures, the mass ratio of tetracol phenixin and iron powder is 1:0.3.Start recycle pump, the reaction solution that contains iron powder is drawn by reactor bottom, after recycle pump pressurization, then squeeze into reactor since reactor head.From reactor bottom to reactor, adding continuously mol ratio is the tetracol phenixin of 46:1 and the mixed solution of triethyl phosphate, heating up and controlling temperature of reaction is 120 ℃, and by passing into continuously vinylidene chloride from reactor bottom to reactor, to control reaction pressure be that 0.9MPa reacts simultaneously.Reaction solution is drawn continuously by reactor top overflow port, through rectifying, reclaims unreacted tetracol phenixin, obtains 1,1,1,3,3,3-chlordene propane product, 1,1,1,3,3,3-chlordene propane yield 84.6%, selectivity 99.5% simultaneously.
Embodiment 7:
In carbon steel reactor at volume 10L with outer circulation, add 2L tetracol phenixin, 250 order iron mixtures, the mass ratio of tetracol phenixin and iron powder is 1:0.5.Start recycle pump, the reaction solution that contains iron powder is drawn by reactor bottom, after recycle pump pressurization, then squeeze into reactor from reactor head, heating up and controlling temperature of reaction is 100 ℃.From reactor bottom to reactor, adding continuously mol ratio is the tetracol phenixin of 45:1 and the mixed solution of triethyl phosphate, and by passing into continuously vinylchlorid from reactor bottom to reactor, to control reaction pressure be that 0.8MPa reacts simultaneously.Reaction solution is drawn continuously by reactor top overflow port, through rectifying, reclaims unreacted tetracol phenixin, obtains 1,1,1,3,3-pentachloropropane product, 1,1,1,3,3-pentachloropropane yield 88.5%, selectivity 99.7% simultaneously.
Embodiment 8:
In stainless steel reactor at volume 10L with outer circulation, add 2.5L tetracol phenixin, 300 order iron mixtures, the mass ratio of tetracol phenixin and iron powder is 1:0.4.Start recycle pump, the reaction solution that contains iron powder is drawn by reactor bottom, after recycle pump pressurization, then squeeze into reactor from reactor head, heating up and controlling temperature of reaction is 110 ℃.From reactor bottom to reactor, adding continuously mol ratio is the tetracol phenixin of 47:1 and the mixed solution of triethyl phosphate.By passing into continuously vinylbenzene from reactor bottom to reactor, to control reaction pressure be that 1.0MPa reacts simultaneously.Reaction solution is drawn continuously by reactor top overflow port, through rectifying, reclaims unreacted tetracol phenixin, obtains 1,3,3,3-tetrachloro-3-phenyl-propane product, 1,3,3,3-tetrachloro-3-phenyl-propane yield 85.3%, selectivity 99.4% simultaneously.
Claims (9)
1. a method for continuously synthesizing for chloroparaffin, is characterized in that, comprises the following steps:
(1) in reactor, add the mixture of tetracol phenixin and iron powder, described volume of mixture is reactor volume 10～30%, and in mixture, the mass ratio of tetracol phenixin and iron powder is 1:0.1～1;
(2) from reactor bottom to reactor, adding continuously mol ratio is the tetracol phenixin of 40～50:1 and the mixture of catalyzer, and to control temperature of reaction be 90～150 ℃, by passing into continuously alkene from reactor bottom to reactor, to control reaction pressure be that 0.5～1.2MPa reacts simultaneously;
(3) collect and obtain chloroparaffin product from reaction solution the rectifying of the overflow of reactor top.
2. the method for continuously synthesizing of chloroparaffin according to claim 1, is characterized in that the iron powder order number described in step (1) is 100～500.
3. the method for continuously synthesizing of chloroparaffin according to claim 1, it is characterized in that the volume of mixture described in step (1) is reactor volume 15～25%.
4. the method for continuously synthesizing of chloroparaffin according to claim 1, the mass ratio that it is characterized in that the tetracol phenixin described in step (1) and iron powder is 1:0.3～0.5.
5. the method for continuously synthesizing of chloroparaffin according to claim 1, is characterized in that the temperature of reaction described in step (2) is 110～120 ℃, and reaction pressure is 0.8～1.0MPa.
6. the method for continuously synthesizing of chloroparaffin according to claim 1, the mol ratio that it is characterized in that the tetracol phenixin described in step (2) and catalyzer is 45～47:1.
7. the method for continuously synthesizing of chloroparaffin according to claim 1, is characterized in that the catalyzer described in step (2) is a kind of in triethyl phosphate, triethyl-phosphite, n-Butyl Amine 99, Isopropylamine.
8. the method for continuously synthesizing of chloroparaffin according to claim 1, is characterized in that the alkene described in step (2) is a kind of in ethene, vinylchlorid, vinylidene chloride, vinylbenzene.
9. the method for continuously synthesizing of chloroparaffin according to claim 1, is characterized in that in reaction process, the reaction solution in reactor being drawn and being turned back to reactor from top from reactor bottom, circulates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310428106.7A CN103524291B (en) | 2013-09-18 | 2013-09-18 | A kind of method for continuously synthesizing of chloroparaffin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310428106.7A CN103524291B (en) | 2013-09-18 | 2013-09-18 | A kind of method for continuously synthesizing of chloroparaffin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103524291A true CN103524291A (en) | 2014-01-22 |
| CN103524291B CN103524291B (en) | 2015-09-23 |
Family
ID=49926703
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310428106.7A Active CN103524291B (en) | 2013-09-18 | 2013-09-18 | A kind of method for continuously synthesizing of chloroparaffin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103524291B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105218299A (en) * | 2015-09-30 | 2016-01-06 | 巨化集团技术中心 | A kind of continuous production method for tetracol phenixin and olefin production hydrochloric ether |
| CN105622330A (en) * | 2016-01-26 | 2016-06-01 | 巨化集团技术中心 | Continuous preparation method of chlorohydrocarbons |
| CN114835554A (en) * | 2021-02-02 | 2022-08-02 | 中国科学院宁波材料技术与工程研究所 | Preparation method of 1,1,1, 3-tetrachloropropane |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101362070A (en) * | 2007-08-09 | 2009-02-11 | 宏大化纤技术装备有限公司 | Reaction device with outer circulation device and method for controlling the reaction process |
| CN101535226A (en) * | 2006-10-06 | 2009-09-16 | 索尔维公司 | Process for the preparation of halogenated hydrocarbons with at least 3 carbon atoms in the presence of iron and a phosphite |
| CN101558031A (en) * | 2006-10-11 | 2009-10-14 | 霍尼韦尔国际公司 | Process for the manufacture of 1,1,1,3,3-pentachloropropane |
| CN102177116A (en) * | 2009-06-24 | 2011-09-07 | 株式会社德山 | Method for producing chlorinated hydrocarbon |
-
2013
- 2013-09-18 CN CN201310428106.7A patent/CN103524291B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101535226A (en) * | 2006-10-06 | 2009-09-16 | 索尔维公司 | Process for the preparation of halogenated hydrocarbons with at least 3 carbon atoms in the presence of iron and a phosphite |
| CN101558031A (en) * | 2006-10-11 | 2009-10-14 | 霍尼韦尔国际公司 | Process for the manufacture of 1,1,1,3,3-pentachloropropane |
| CN101362070A (en) * | 2007-08-09 | 2009-02-11 | 宏大化纤技术装备有限公司 | Reaction device with outer circulation device and method for controlling the reaction process |
| CN102177116A (en) * | 2009-06-24 | 2011-09-07 | 株式会社德山 | Method for producing chlorinated hydrocarbon |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105218299A (en) * | 2015-09-30 | 2016-01-06 | 巨化集团技术中心 | A kind of continuous production method for tetracol phenixin and olefin production hydrochloric ether |
| CN105218299B (en) * | 2015-09-30 | 2020-03-31 | 巨化集团技术中心 | Continuous preparation method for producing chlorohydrocarbon from carbon tetrachloride and olefin |
| CN105622330A (en) * | 2016-01-26 | 2016-06-01 | 巨化集团技术中心 | Continuous preparation method of chlorohydrocarbons |
| CN114835554A (en) * | 2021-02-02 | 2022-08-02 | 中国科学院宁波材料技术与工程研究所 | Preparation method of 1,1,1, 3-tetrachloropropane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103524291B (en) | 2015-09-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102675035B (en) | Method for preparing vinyl chloride from acetylene and dichloroethane | |
| CN101255109B (en) | Technique for producing propenoic acid by dehydrating biomass lactic acid | |
| CN104761429A (en) | Dimethyl carbonate and ethylene glycol production process | |
| CN104387236B (en) | A kind of propilolic alcohol, 1,4-butynediols and methenamine three coproduction continuous producing method | |
| CN105732350B (en) | A kind of method that anaerobic dehydrogenation prepares anhydrous formaldehyde | |
| CN103524291B (en) | A kind of method for continuously synthesizing of chloroparaffin | |
| CN106928021A (en) | A kind of method of preparing ethylene glycol by using dimethyl oxalate plus hydrogen | |
| CN103804142A (en) | System and method used for preparing glycol via hydrogenation of oxalic ester | |
| CN102068945B (en) | Reactive distillation device and method for separating and purifying methylal | |
| CN103373894B (en) | Continuous method for preparing C3 saturated halogenated hydrocarbon alkyl | |
| CN102911008B (en) | Trichloro ethylene preparation method | |
| CN105218299B (en) | Continuous preparation method for producing chlorohydrocarbon from carbon tetrachloride and olefin | |
| CN102010321A (en) | Process for continuously producing isobutyric acid | |
| CN101768062B (en) | Industrial method for simultaneously preparing propaldehyde and butyraldehyde by catalytic dry gas concentrating gas | |
| CN102633620B (en) | Method for producing stearoyl chloride and homologs thereof by liquid-phase phosgenation | |
| CN108530254A (en) | A method of mixing carbon four prepares normal butane | |
| CN103709010B (en) | A kind of by tetrahydrobenzene, carboxylic acid and water Reactive Synthesis hexalin method | |
| CN105585468B (en) | A method of cyclopentanone is prepared by raw material of cyclopentene | |
| CN103708999B (en) | Catalysis hydration is produced the method for ethylene glycol | |
| CN103641676A (en) | Method for preparing methyl cyclopentadiene | |
| CN107673974B (en) | Recycling method and device for nitrogen oxides | |
| CN108033872B (en) | Method and equipment for clean and environment-friendly production of 1,1',2, 3-tetrachloropropene | |
| CN114605225A (en) | Method for continuously synthesizing 1,1,1,3, 3-pentachloropropane | |
| CN106478402A (en) | The method that ethanol acid crystal is prepared by methyl glycollate | |
| CN110204514A (en) | A kind of production technology of epoxidized vegetable oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |