CN111018665A - Method for recycling trichloropropane in epichlorohydrin heavy component - Google Patents
Method for recycling trichloropropane in epichlorohydrin heavy component Download PDFInfo
- Publication number
- CN111018665A CN111018665A CN201911303386.2A CN201911303386A CN111018665A CN 111018665 A CN111018665 A CN 111018665A CN 201911303386 A CN201911303386 A CN 201911303386A CN 111018665 A CN111018665 A CN 111018665A
- Authority
- CN
- China
- Prior art keywords
- epichlorohydrin
- trichloropropane
- recycling
- heavy component
- dichloropropanol
- 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
- C07C29/124—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids of halides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention belongs to the technical field of chemical industry, and particularly relates to a method for recycling trichloropropane in an epichlorohydrin heavy component. Adding mixed hydrolysate into the heavy component of the epoxy chloropropane for hydrolysis reaction, distilling at normal pressure, adding analytic salt solution for resolution and layering, rectifying the upper oil phase to obtain a refined dichloropropanol product, and performing saponification reaction on the refined dichloropropanol product to obtain the epoxy chloropropane; the mixed hydrolysate consists of alcohol, water, sodium hydroxide and hydrolysis assistant. The invention can convert trichloropropane in the epoxychloropropane heavy component into the raw material dichloropropanol, and the recovery conversion rate is more than 80 percent, thereby not only improving the utilization rate of the raw material, reducing the environmental pollution and the harm to human bodies, but also reducing the production cost of the product.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a method for recycling trichloropropane in an epichlorohydrin heavy component.
Background
The production process of the epichlorohydrin mainly comprises a propylene chlorination method, an acetic acid propylene ester method and a glycerol chlorination method, but the price of propylene in the current market is gradually increased, the yield of the byproduct glycerol of the biodiesel is increased year by year, and simultaneously, with the continuous promotion of chemical industry and environmental sustainable development concept in China, the two production processes of the propylene chlorination method and the acetic acid propylene ester method are easy to generate a large amount of waste water and waste residue and are gradually eliminated, and the pollution treatment difficulty is extremely high. The glycerol method is a main production process of epichlorohydrin, and a large amount of epichlorohydrin heavy components which mainly comprise trichloropropane are generated in the preparation process through glycerol chlorination reaction and dichloropropanol saponification reaction; heavy components are difficult to treat, the environment is easy to be polluted, the utilization rate of raw materials is reduced, and the cost is increased.
Chinese patent CN 103819304A discloses a process for decolorizing an epoxy high-boiling mixture and extracting trichloropropane therein, wherein the epoxy high-boiling mixture enters a decolorizing tank for decolorizing, the effluent of the decolorizing tank enters an intermediate storage tank, at the same time, at least one azeotropic agent selected from methanol, water, carbon tetrachloride and propanol is injected into the intermediate storage tank, the effluent of the intermediate storage tank enters an azeotropic distillation tower, the obtained product containing trichloropropane and the obtained azeotropic agent flow out of the azeotropic distillation tower and enter a separation tank, the azeotropic agent is removed from the separation tank to obtain the product containing trichloropropane, and the azeotropic agent recovered from the separation tank is returned to the intermediate storage tank for recycling.
Chinese patent CN 108752292A discloses a method for recovering epichlorohydrin based on an epichlorohydrin light component, which comprises the steps of adding a pretreatment agent into the epichlorohydrin light component for reaction, and then carrying out atmospheric distillation and reduced pressure distillation to obtain the epichlorohydrin, wherein the pretreatment agent is triethanolamine or triethylamine.
The above patents do not solve the problem of processing heavy components of epichlorohydrin, so how to get rid of the current situation that heavy components of epichlorohydrin are difficult to process becomes a problem to be solved urgently at present.
Disclosure of Invention
The invention aims to provide a method for recycling trichloropropane in epichlorohydrin heavy components, which solves the problem that the epichlorohydrin heavy components are difficult to treat, improves the utilization rate of raw materials, reduces environmental pollution and harm to human bodies, and reduces the production cost of products.
Adding mixed hydrolysate into the heavy component of the epoxy chloropropane for hydrolysis reaction, distilling at normal pressure, adding analytic salt solution for resolution and layering, rectifying an upper oil phase to obtain a refined dichloropropanol product, and performing saponification reaction on the refined dichloropropanol product to obtain the epoxy chloropropane; the mixed hydrolysate consists of alcohol, water, sodium hydroxide and hydrolysis assistant.
The alcohol is methanol or ethanol.
The hydrolysis auxiliary agent is MnCl2、ZnCl2Or FeCl3One kind of (1).
The mass ratio of the alcohol, the water, the sodium hydroxide and the hydrolysis auxiliary agent in the mixed hydrolysate is 5-10: 15-20: 5-10: 1-5.
The mass ratio of the epichlorohydrin heavy component to the mixed hydrolysate is 100: 25-40.
The hydrolysis reaction temperature is 70-120 deg.C, and the hydrolysis reaction time is 30-60 min.
The resolving salt solution is a sodium chloride solution.
The mass concentration of the resolving salt solution is 35 to 45%, preferably 40%.
The mass ratio of the heavy components of the epichlorohydrin to the resolving salt solution is 100: 20-50.
The resolving temperature is 80-200 deg.C, and resolving time is 30-60 min.
The method for recycling trichloropropane in the heavy component of epoxy chloropropane specifically comprises the steps of adding mixed hydrolysate of alcohol/water/sodium hydroxide/hydrolysis aid into the heavy component generated in the distillation process of epoxy chloropropane, heating, stirring for reaction, distilling at normal pressure, controlling the temperature at the top of a tower to be 85-90 ℃ until no liquid is distilled off, recycling alcohol and a small amount of water, adding 35-45 wt.% of sodium chloride solution for resolution and layering, recycling the lower layer of saline water, obtaining crude dichloropropanol in the upper oil phase, rectifying to obtain refined dichloropropanol, and then the raw material is subjected to saponification reaction with 10-20 wt.% of calcium hydroxide aqueous solution to obtain a crude epoxy chloropropane product, wherein the saponification reaction temperature is 75-85 ℃, and the crude epoxy chloropropane product is rectified at a vacuum degree of-45 to-55 Kpa and a tower top temperature of 70-80 ℃ to obtain a fine epoxy chloropropane product.
The main components contained in the heavy component of the epichlorohydrin comprise a large amount of trichloropropane, and a small amount of epichlorohydrin, dichloropropanol and monochloropropanediol. The content of each component in the epichlorohydrin heavy component is that epichlorohydrin is less than or equal to 1 wt.%; dichloropropanol ≤ 10 wt.%; less than or equal to 8 wt.% monochloropropanediol; trichloropropane ≥ 80 wt.%; the balance of impurities.
The treatment method of the invention is to hydrolyze trichloropropane by adopting an alkaline hydrolysis method to prepare dichloropropanol, analyze and recover oil-phase dichloropropanol, and carry out saponification reaction to generate epichlorohydrin.
The invention has the following beneficial effects:
the invention can convert trichloropropane in the epoxychloropropane heavy component into the raw material dichloropropanol, and the recovery conversion rate is more than 80 percent, thereby not only improving the utilization rate of the raw material, reducing the environmental pollution and the harm to human bodies, but also reducing the production cost of the product. The production cost can be saved by about 1700 more than ten thousand yuan per year according to the design capacity of 10 ten thousand tons.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention is further described below with reference to examples.
The content of each component in the heavy component of the epichlorohydrin used in the examples is epichlorohydrin: 0.5 wt.%; dichloropropanol: 9.1 wt.%; monochloropropanediol: 6.6 wt.%; trichloropropane: 82.1 wt.%; impurities: 1.7 wt.%.
Example 1
100g of heavy component of epichlorohydrin is taken and added into a 250ml three-neck flask, and mixed hydrolysate (methanol: water: sodium hydroxide: MnCl) is added2In a mass ratio of 10:20:10:5) of 40g, heating to 120 ℃ under stirring, reacting for 30min, and distilling under normal pressure to recover the methanol aqueous solution. Then adding 50g of 40 wt.% sodium chloride solution into a three-necked bottle, stirring and reacting for 60min at 80 ℃, standing and layering, taking 93.2g of crude dichloropropanol in the upper oil phase, carrying out reduced pressure distillation, controlling the vacuum degree to be-0.097 MPa, and recovering 82.5g of refined dichloropropanol at the top temperature of about 100 ℃, wherein the recovery conversion rate is 82.5%, and the purity is 99.0%; fine dichloropropanol with 15 wt.% Ca (OH)2The solution is saponified at 80 ℃, and then rectified to obtain 57.1g of fine epichlorohydrin product with the purity of 99.6%; and recycling the lower sodium chloride solution and the recovered methanol aqueous solution.
Example 2
Taking 100g of epichlorohydrin heavy component, adding into a 250ml three-neck flask, adding into the mixed hydrolysate (methanol: water: sodium hydroxide: ZnCl)2In a mass ratio of 5:15:5:5) of 25g, heating to 70 ℃ under stirring, reacting for 30min, and distilling under normal pressure to recover the methanol aqueous solution. Then adding 20g of 40 wt.% sodium chloride solution into a three-necked bottle, stirring and reacting at 120 ℃ for 30min, standing and layering, taking 95.1g of crude dichloropropanol in the upper oil phase, carrying out reduced pressure distillation, controlling the vacuum degree to be-0.097 MPa, and recovering 81.7g of refined dichloropropanol at the top temperature of about 100 ℃, wherein the recovery conversion rate is 81.7% and the purity is 99.2%; fine dichloropropanol with 15 wt.% Ca (OH)2The solution is saponified at 85 ℃, and then rectified to obtain 57.5g of fine epichlorohydrin product with the purity of 99.2%; and recycling the lower sodium chloride solution and the recovered methanol aqueous solution.
Example 3
100g of heavy component of epoxy chloropropane is added into a 250ml three-neck flask, and mixed hydrolysate (ethanol, water, sodium hydroxide and FeCl) is added3In a mass ratio of 5:15:5:5)40g, heating to 80 ℃ under stirring, reacting for 35min, and distilling under normal pressure to recover the ethanol aqueous solution. Adding 25g of 45 wt.% sodium chloride solution into a three-necked bottle, stirring and reacting at 120 ℃ for 60min, standing and layering, taking 95.8g of crude dichloropropanol in the upper oil phase, carrying out reduced pressure distillation, controlling the vacuum degree to be-0.097 MPa, and recovering 82.0g of refined dichloropropanol at the top temperature of about 100 ℃, wherein the recovery conversion rate is 82.0% and the purity is 99.1%; fine dichloropropanol with 15 wt.% Ca (OH)2The solution is saponified at 80 ℃, and then rectified to obtain 58.0g of fine epichlorohydrin product with the purity of 99.5%; and recycling the lower sodium chloride solution and the recovered ethanol water solution.
Example 4
100g of heavy component of epoxy chloropropane is added into a 250ml three-neck flask, and mixed hydrolysate (methanol, water, sodium hydroxide and FeCl) is added3In a mass ratio of 5:15:10:3) to 30g, heating to 95 ℃ under stirring, reacting for 40min, and distilling under normal pressure to recover the methanol aqueous solution. Adding 28g of 35 wt.% sodium chloride solution into a three-necked bottle, stirring and reacting at 120 ℃ for 60min, standing and layering, taking 97.0g of crude dichloropropanol in the upper oil phase, carrying out reduced pressure distillation, controlling the vacuum degree to be-0.097 MPa, and recovering 83.1g of refined dichloropropanol at the top temperature of about 100 ℃, wherein the recovery conversion rate is 83.1% and the purity is 98.9%; fine dichloropropanol with 15 wt.% Ca (OH)2The solution is saponified at 75 ℃, and then rectified to obtain 58.5g of fine epichlorohydrin product with the purity of 99.4%; and recycling the lower sodium chloride solution and the recovered methanol aqueous solution.
Example 5
100g of heavy component of epichlorohydrin is taken and added into a 250ml three-neck flask, and mixed hydrolysate (methanol: water: sodium hydroxide: MnCl) is added2In a mass ratio of 5:16:5:1) of 40g, heating to 80 ℃ under stirring, reacting for 35min, and distilling under normal pressure to recover the methanol aqueous solution. Adding 31g of 40 wt.% sodium chloride solution into a three-necked bottle, stirring at 120 ℃ for reacting for 50min, standing for layering, and taking an upper oil phase II95.8g of chloropropanol crude product is distilled under reduced pressure, 82.2g of dichloropropanol fine product is recovered under the conditions that the vacuum degree is controlled to be-0.097 Mpa and the top temperature is about 100 ℃, the recovery conversion rate is 82.2 percent, and the purity is 99.1 percent; fine dichloropropanol with 15 wt.% Ca (OH)2The solution is saponified at 80 ℃, and then rectified to obtain 58.1g of fine epichlorohydrin product with the purity of 99.5%; and recycling the lower sodium chloride solution and the recovered methanol aqueous solution.
Comparative example 1
The heating to 120 ℃ in example 1 was changed to 50 ℃ and the procedure was the same as in example 1. 31.0g of refined dichloropropanol is recovered, the recovery conversion rate is 31.0 percent, and the purity is 97.5 percent. 19.1g of fine epichlorohydrin product is obtained after saponification, and the purity is 99.2%.
Comparative example 2
The reaction at 120 ℃ for 30min in example 1 was changed to 120 ℃ for 15min, and the procedure was the same as in example 1. 50.1g of refined dichloropropanol is recovered, the recovery conversion rate is 50.1%, and the purity is 97.9%. After saponification, 34.9g of fine epichlorohydrin product with the purity of 99.4% is obtained.
Comparative example 3
The mixed hydrolyzate of example 1 (methanol: water: sodium hydroxide: MnCl)2The mass ratio of (10: 20:10:5) to (40 g) is changed into a mixed hydrolysate (methanol: water: sodium hydroxide: MnCl2In a mass ratio of 10:20:10:5) of 10g, and the rest of the steps are the same as those of example 1. And (3) recovering a refined dichloropropanol product 39.2.g, wherein the recovery conversion rate is 39.2 percent, and the purity is 98.1 percent. 25.3g of fine epichlorohydrin product is obtained after saponification, and the purity is 99.0%.
Comparative example 4
The procedure of example 1 was repeated except that 50g of 40 wt.% sodium chloride solution in example 1 was changed to 10g of 40 wt.% sodium chloride solution. 45.2g of refined recovered dichloropropanol product has the recovery conversion rate of 45.2% and the purity of 98.1%. 30.3g of fine epichlorohydrin product is obtained after saponification, and the purity is 99.5%.
Comparative example 5
The stirring reaction at 80 ℃ for 60min in example 1 was changed to 30 ℃ for 60min, and the rest of the procedure was the same as in example 1. 61.0g of refined dichloropropanol is recovered, the recovery conversion rate is 61.0 percent, and the purity is 98.3 percent. 41.8g of fine epichlorohydrin product is obtained after saponification, and the purity is 98.9%.
Comparative example 6
The stirring reaction at 80 ℃ for 60min in example 1 is changed to 30 ℃ for 15min, and the rest steps are the same as in example 1. 49.2g of refined dichloropropanol is recovered, the recovery conversion rate is 49.2%, and the purity is 99.0%. 32.4g of fine epichlorohydrin product is obtained after saponification, and the purity is 98.8%.
Claims (10)
1. A method for recycling trichloropropane in epichlorohydrin heavy components is characterized in that mixed hydrolysate is added into the epichlorohydrin heavy components for hydrolysis reaction, normal pressure distillation is carried out, analytic salt solution is added for analysis and layering, the upper oil phase is rectified to obtain a refined dichloropropanol product, and the refined dichloropropanol product is subjected to saponification reaction to obtain epichlorohydrin; the mixed hydrolysate consists of alcohol, water, sodium hydroxide and hydrolysis assistant.
2. The method for recycling trichloropropane in the heavy component of epichlorohydrin according to claim 1, wherein the alcohol is methanol or ethanol.
3. The method for recycling trichloropropane in epichlorohydrin heavy components according to claim 1, wherein the hydrolysis auxiliary agent is MnCl2、ZnCl2Or FeCl3One kind of (1).
4. The method for recycling trichloropropane in the heavy component of epichlorohydrin according to claim 1, wherein the mass ratio of the alcohol, the water, the sodium hydroxide and the hydrolysis auxiliary agent in the mixed hydrolysis solution is 5-10: 15-20: 5-10: 1-5.
5. The method for recycling trichloropropane in the epichlorohydrin heavy component according to claim 1, wherein the mass ratio of the epichlorohydrin heavy component to the mixed hydrolysate is 100: 25-40.
6. The method for recycling trichloropropane in the heavy component of epichlorohydrin according to claim 1, wherein the hydrolysis reaction temperature is 70-120 ℃, and the hydrolysis reaction time is 30-60 min.
7. The method for recycling trichloropropane in the heavy component of epichlorohydrin according to claim 1, wherein the solution of the resolving salt is a sodium chloride solution.
8. The method for recycling trichloropropane in the epichlorohydrin heavy component according to claim 1, wherein the mass concentration of the resolving salt solution is 35-45%.
9. The method for recycling trichloropropane in the epichlorohydrin heavy component according to claim 1, wherein the mass ratio of the epichlorohydrin heavy component to the resolving salt solution is 100: 20-50.
10. The method for recycling trichloropropane in the heavy component of epichlorohydrin according to claim 1, wherein the resolving temperature is 80-200 ℃ and the resolving time is 30-60 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911303386.2A CN111018665A (en) | 2019-12-17 | 2019-12-17 | Method for recycling trichloropropane in epichlorohydrin heavy component |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911303386.2A CN111018665A (en) | 2019-12-17 | 2019-12-17 | Method for recycling trichloropropane in epichlorohydrin heavy component |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111018665A true CN111018665A (en) | 2020-04-17 |
Family
ID=70210078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911303386.2A Pending CN111018665A (en) | 2019-12-17 | 2019-12-17 | Method for recycling trichloropropane in epichlorohydrin heavy component |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111018665A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114684989A (en) * | 2022-03-21 | 2022-07-01 | 安徽工业大学 | Method for treating triglycidyl isocyanurate production waste liquid |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5344945A (en) * | 1992-03-17 | 1994-09-06 | Solvay (Societe Anonyme) | Process for the production of epichlorohydrin |
| CN1845888A (en) * | 2003-09-01 | 2006-10-11 | 化学和冶金生产联合体股份公司 | Method of preparing dichloropropanols from glycerine |
| CN101323555A (en) * | 2008-07-24 | 2008-12-17 | 上海氯碱化工股份有限公司 | Method for preparing dichlorohydrin by glycerol hydrochlorination |
| CN101481365A (en) * | 2009-02-17 | 2009-07-15 | 上海氯碱化工股份有限公司 | Method for preparing epoxy chloropropane by using hydrochloric acid water solution of dichlorohydrin |
| CN101622215A (en) * | 2007-03-07 | 2010-01-06 | 索尔维公司 | Be used to produce the method for dichlorohydrine |
| CN101704707A (en) * | 2009-04-27 | 2010-05-12 | 南通泰禾化工有限公司 | Method for removing impurity from trichloropropane |
| CN101712661A (en) * | 2009-12-01 | 2010-05-26 | 宁波东港电化有限责任公司 | Method for producing epoxy chloropropane |
| CN102234224A (en) * | 2010-04-24 | 2011-11-09 | 广东理文化工研发有限公司 | Method for catalytic synthesis of dichloropropanol by hydrogen chloride-containing industrial waste gas and glycerol |
| CN102264681A (en) * | 2008-12-31 | 2011-11-30 | 三星精密化学株式会社 | Method of preparing dichloropropanol using glycerol with improved selectivity for dichloropropanol |
| CN103709124A (en) * | 2013-12-06 | 2014-04-09 | 中国天辰工程有限公司 | Method for producing epoxy chloropropane |
| CN103819304A (en) * | 2013-10-18 | 2014-05-28 | 中国石油化工股份有限公司 | Process for decolorizing high-boiling epoxy mixture and extracting trichloropropane in high-boiling epoxy mixture |
| CN108752292A (en) * | 2018-05-17 | 2018-11-06 | 山东民基化工有限公司 | The method for recycling epoxychloropropane based on epoxychloropropane light component |
-
2019
- 2019-12-17 CN CN201911303386.2A patent/CN111018665A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5344945A (en) * | 1992-03-17 | 1994-09-06 | Solvay (Societe Anonyme) | Process for the production of epichlorohydrin |
| CN1845888A (en) * | 2003-09-01 | 2006-10-11 | 化学和冶金生产联合体股份公司 | Method of preparing dichloropropanols from glycerine |
| CN101622215A (en) * | 2007-03-07 | 2010-01-06 | 索尔维公司 | Be used to produce the method for dichlorohydrine |
| CN101323555A (en) * | 2008-07-24 | 2008-12-17 | 上海氯碱化工股份有限公司 | Method for preparing dichlorohydrin by glycerol hydrochlorination |
| CN102264681A (en) * | 2008-12-31 | 2011-11-30 | 三星精密化学株式会社 | Method of preparing dichloropropanol using glycerol with improved selectivity for dichloropropanol |
| CN101481365A (en) * | 2009-02-17 | 2009-07-15 | 上海氯碱化工股份有限公司 | Method for preparing epoxy chloropropane by using hydrochloric acid water solution of dichlorohydrin |
| CN101704707A (en) * | 2009-04-27 | 2010-05-12 | 南通泰禾化工有限公司 | Method for removing impurity from trichloropropane |
| CN101712661A (en) * | 2009-12-01 | 2010-05-26 | 宁波东港电化有限责任公司 | Method for producing epoxy chloropropane |
| CN102234224A (en) * | 2010-04-24 | 2011-11-09 | 广东理文化工研发有限公司 | Method for catalytic synthesis of dichloropropanol by hydrogen chloride-containing industrial waste gas and glycerol |
| CN103819304A (en) * | 2013-10-18 | 2014-05-28 | 中国石油化工股份有限公司 | Process for decolorizing high-boiling epoxy mixture and extracting trichloropropane in high-boiling epoxy mixture |
| CN103709124A (en) * | 2013-12-06 | 2014-04-09 | 中国天辰工程有限公司 | Method for producing epoxy chloropropane |
| CN108752292A (en) * | 2018-05-17 | 2018-11-06 | 山东民基化工有限公司 | The method for recycling epoxychloropropane based on epoxychloropropane light component |
Non-Patent Citations (1)
| Title |
|---|
| 贾志坚: "《有机化学理论及发展研究》", 30 April 2018 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114684989A (en) * | 2022-03-21 | 2022-07-01 | 安徽工业大学 | Method for treating triglycidyl isocyanurate production waste liquid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106810450B (en) | Device and method for preparing dibutyl phthalate by catalytic reaction rectification | |
| CN102417162B (en) | Recycling method of hydrochloric acid-acetic acid waste liquid | |
| CN100519497C (en) | Method for extraction separation of dichloropropanol from dichloropropanol hydrochloric water solution | |
| CN106432732A (en) | Method for preparing hydroxy terminated high-boiling silicone oil through low-temperature continuous hydrolysis technology | |
| CN112409178A (en) | Method for preparing methyl methacrylate by taking methyl acetate as raw material | |
| CN106699511B (en) | Method for recycling organic/inorganic matters in glycerol chlorination distillate | |
| CN105111079A (en) | Method and device for separating acetic acid sec-butyl ester and sec-butyl alcohol | |
| CN103012332B (en) | Use the method for packing tower distillation separation of tetrahydrofuran-methanol-water solvent slop | |
| CN111018665A (en) | Method for recycling trichloropropane in epichlorohydrin heavy component | |
| CN104761452A (en) | Purification method for butyl acrylate crude product | |
| CN110452112B (en) | Catalytic hydrogenation treatment process for chloro pivaloyl chloride rectification residual liquid | |
| CN103626632A (en) | Method for purifying by-product crude glycerine of biodiesel prepared by using illegal cooking oil | |
| CN108689826B (en) | Method for separating and purifying levulinic acid from sulfuric acid hydrolysate of biomass | |
| CN103804125A (en) | Method for preparing policosanol through insect wax pressure reduction method | |
| CN112457193B (en) | Method for preparing methyl propionate by taking methyl acetate as raw material | |
| CN108689799B (en) | Green synthesis method of chlorocyclohexane | |
| CN113956219A (en) | Process flow for producing furfural from papermaking wastewater | |
| CN108752292B (en) | Method for recycling epichlorohydrin based on epichlorohydrin light component | |
| CN110642683A (en) | Synthesis method of cement grinding aid component using dichloroisopropyl ether as raw material | |
| CN111848353A (en) | Method for harmless recycling treatment of BDO organic waste liquid | |
| CN111253429A (en) | Recycling device and method for organic silicon cracking high ring and application | |
| CN109369386A (en) | A kind of catalytic distillation prepares the devices and methods therefor of methyl formate | |
| CN104341328A (en) | Method for producing ethanethiol by utilizing distilled crude methanol residue liquid in production process of sodium hydrosulfite | |
| CN113956158B (en) | Process for synthesizing methyl methacrylate by methyl acetate route | |
| CN115093331B (en) | Process for extracting benzylamine from high-boiling-point organic matters discharged from phenylglycine production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200417 |
|
| RJ01 | Rejection of invention patent application after publication |