CN1847205A - Method of separating 1,2-dichloropropane with DD mixture - Google Patents
Method of separating 1,2-dichloropropane with DD mixture Download PDFInfo
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Abstract
The process of separating 1, 2-dichloropropane from DD mixture has the 1, 3-trichloropropane in DD mixture reacted with acrylic acid or methacrylic acid, alkali, catalyst and polymerization inhibitor to convert into 3-chloro-2-propenyl acrylate or 3-chloro-2-propenyl-2-methacrylate with boiling point different obviously to that of 1, 2-trichloropropane and distilled for separation from 1, 2-dichloropropane. The technological process includes the steps of: pre-treatment of the material, catalytic esterification reaction, and product separation. The present invention provides one comprehensive utilizing way of DD mixture, and the separated 1, 2-dichloropropane is one important organic intermediate and solvent.
Description
Technical Field
The invention belongs to the technical field of organic chemical industry, and relates to a comprehensive utilization method of a chemical byproduct claw DD (D-methyl-d) mixture, in particular to a method for separating 1, 2-dichloropropane by using the DD mixture.
Background
The DD mixing agent is a high-boiling point byproduct generated in the production of 3-chloropropene by a propylene thermal chlorination method, the main components of the DD mixing agent are 1, 2-dichloropropane and 1, 3-dichloropropene (including cis-isomer and trans-isomer), and the 3-chloropropene is mainly used for producing epichlorohydrin. At present, the production capacity of epichlorohydrin in China is 4.5 ten thousand tons per year, about 230 kilograms of DD mixed agent is generated when one ton of epichlorohydrin is produced, and nearly ten thousand tons of DD mixed agent are generated every year. And the production device of the epichlorohydrin is increased, and the generation amount of the DD mixing agent is correspondingly increased, so that the problem of treatment and utilization of the DD mixing agent is to be solved.
In 1943, Kate (Carter) first discovered the nematicidal effect of DD mixture, and had been widely used in various countries. The DD mixed agent has been used as nematicide in the last seventies of China, and the insecticidal effect and the yield increasing effect are obvious. The effective component for killing the nematodes in the DD mixed agent is 1, 3-dichloropropene, and a large amount of ineffective 1, 2-dichloropropane is dispersed in soil and air, which causes serious pollution to the environment, so that the DD mixed agent is limited to be used as the nematicide at home and abroad in recent years.
The DD mixed agent can also be used as paint thinner or equipment cleaning agent after simple distillation. Even the DD blend introduced into the propylene chlorination plant of Japan by Qilu petrochemical has been disposed of by incineration in the past. From the viewpoint of environmental protection, the treatment modes are the transfer of three wastes, which wastes resources andpollutes the environment. The purity of 1, 3-dichloropropene fraction can be improved to more than 90% by adopting a rectification method in Japan, and the product is used for synthesizing pesticides or other fine chemical intermediates, and the sale price of the product is higher than that of epichlorohydrin. In China, a rectification method is tried to separate 1, 3-dichloropropene and 1, 2-dichloropropane in a DD mixed agent and carry out small-scale production, but because the boiling points of all components are close (the boiling points of the 1, 2-dichloropropane are 97 ℃, the boiling points of the cis-1, 3-dichloropropene are 102 ℃ and the boiling points of the trans-1, 3-dichloropropene are 110 ℃), all components are difficult to be completely rectified and separated, and HCl can be decomposed after the DD mixed agent is heated, so that high requirements are provided for the tower efficiency and the corrosion resistance of a rectification device. In conclusion, the treatment methods of the DD mixture are not complete at present. The development of a more effective comprehensive utilization way of the DD mixed agent has important practical significance for reducing environmental pollution and improving the utilization rate of resources.
Disclosure of Invention
Aiming at the current situation of treatment and utilization of the DD mixed agent, the invention provides a method for separating 1, 2-dichloropropane by using the DD mixed agent.
The invention uses DD mixed agent as main raw material, and uses acrylate or methacrylate to produce selective esterification reaction with 1, 3-dichloropropene in the DD mixed agent to synthesize acrylic acid-3-chloro-2-propenyl ester or 2-methacrylic acid-3-chloro-2-propenyl ester. The boiling points of the acrylic acid-3-chloro-2-propylene ester and the 2-methacrylic acid-3-chloro-2-propylene ester are far higher than that of the 1, 2-dichloropropane, so that the separation of the 1, 2-dichloropropane and the acrylic acid-3-chloro-2-propylene ester or the 2-methacrylic acid-3-chloro-2-propylene ester can be realized through distillation, a useful chemical product is obtained, 1, 2-dichloropropane is grasped, and the aim of fully utilizing the DD mixture is fulfilled.
The method of the invention utilizes the chemical by-product claw DD mixing agent as the main raw material, and the main component is 1, 2-dichloropropane (CH)3CHClCH2Cl) and 1, 3-dichloropropene (ClCH ═ CHCH)2Cl), contains four forms of chloride ion, but there are significant differences in their chemical activities, with allyl chloride being the most reactive for chemical reactions. Using acrylic acid or methacrylic acid, alkali, polymerization inhibitor and catalyst to act with DD mixture, 1, 3-dichloropropene (ClCH ═ CHCH)2Cl) will take part in the esterification reaction to generate acrylic acid-3-chlorine-2-propylene ester (CH)2＝CHCOOCH2CH ═ CHCl) or 2-methacrylic acid 3-chloro-2-propenyl ester (CH)2＝CCH3COOCH2CH ═ CHCl), the basic reaction formula is as follows:
or
Or
The invention comprises four process steps: raw material pretreatment, catalytic esterification reaction and product separation.
1. Feedstock and pretreatment of feedstock
The DD mixed agent is an industrial byproduct dark brown oily liquid, the contents of main components 1, 2-dichloropropane and 1, 3-dichloropropene (including cis-isomer and trans-isomer) are more than 95%, and a small amount of 3-chloropropene, carbonized impurities, water and the like are also contained. Therefore, the DD mixed agent needs to be dehydrated and simply distilled to remove impurities, and 97-110 ℃ fractions are received. Because the content of the 1, 3-dichloropropene in each DD mixed agent is different, the content of each DD mixed agent needs to be analyzed by gas chromatography, and the DD mixed agent is used as the basis for the proportion of the reaction raw materials, and generally comprises 37-75% of 1, 2-dichloropropane and 63-23% of 1, 3-dichloropropene (including cis-isomer and trans-isomer).
According to the measured content of 1, 3-dichloropropene in the DD mixed agent, a certain amount of acrylic acid or methacrylic acid is adopted as another main raw material, and industrial products of the acrylic acid or the methacrylic acid are refined by reduced pressure distillation before use to remove polymers and impurities possibly contained, and a proper amount of polymerization inhibitor is added to prevent further polymerization.
The polymerization inhibitor for acrylic acid or methacrylic acid in the present invention includes various polymerization inhibitors for radical polymerization such as hydroquinone, p-hydroxyanisole or phenothiazine, and is preferably a radical type polymerization inhibitor such as DPPH. The polymerization inhibitor needs to be added before the catalytic esterification reaction, and the dosage of the polymerization inhibitor is 0.001-0.1% of the mass of acrylic acid or methacrylic acid.
The alkali used in the process of the invention can be sodium hydroxide, potassium hydroxide, sodium carbonate or other alkaline compounds, and can also be aqueous solution of the corresponding alkali. Themolar ratio of the acrylic acid or the methacrylic acid to the alkali is 1: 1-1.5.
The catalyst adopted in the catalytic esterification reaction is triethylamine, cuprous chloride or a phase transfer catalyst, such as polyethylene glycol and various quaternary ammonium salts, and the dosage of the catalyst is 1-10% of the mass of acrylic acid or methacrylic acid.
2. Catalytic esterification reaction
The catalytic esterification process of the present invention may be a two-step process or a one-step process.
The two-step method includes neutralizing alkali with acrylic acid or methacrylic acid to prepare corresponding acrylate or methacrylate, mixing the salt with DD mixture, catalyst and polymerization inhibitor in esterification reactor, stirring and heating to reaction temperature for catalytic esterification. The reaction temperature can be 60-100 ℃, the reaction time can be 3-8 hours, and the reaction is carried out under normal pressure. Secondly, adding alkali into the DD mixed agent for hydrolysis to convert the 1, 3-dichloropropene into the 3-chloroallyl alcohol. Adding acrylic acid or methacrylic acid, polymerization inhibitor and catalyst into the esterification reactor, stirring and heating to reaction temperature, and carrying out catalytic esterification reaction. The reaction temperature can be 60-100 ℃, the reaction time can be 3-8 hours, and the reaction is carried out under normal pressure.
The one-step method is that DD mixed agent, acrylic acid or methacrylic acid, polymerization inhibitor, alkali and catalyst are added into an esterification reactor in sequence according to a certain proportion, stirred and heated to the reaction temperature, and catalytic esterification reaction is carried out. The reaction temperature can be 60-100 ℃, the reaction time can be 3-8 hours, and the reaction is carried out under normal pressure.
In the catalytic esterification reaction, the characteristic of azeotropy of the DD mixing agent and water can be utilized, the moisture contained in the system is removed at the reflux temperature, namely the reaction temperature, and the DD mixing agent returns to the system for reaction after standing and layering so as to utilize the completeness of the esterification reaction.
The temperature rising mode of the catalytic esterification reaction can adopt conventional heating technologies such as water bath heating, oil bath heating, electric heating, steam heating and the like, and can also adopt a microwave heating technology.
3. Product separation
After the catalytic esterification reaction is finished, the system is cooled to room temperature and stands, inorganic salt generated by the reaction is precipitated and can be directly filtered and separated out; or adding a proper amount of water into the system to dissolve the generated inorganic salt, standing for layering, and removing the water phase. If the organic phase contains a small amount of water, a proper amount of drying agent such as anhydrous magnesium sulfate can be added for drying.
The organic phase after the desalting mainly contains 1, 2-dichloropropane and acrylic acid-3-chlorine-2-propylene ester or 2-methacrylic acid-3-chlorine-2-propylene ester, distillation is carried out at normal pressure, and a fraction at 95-100 ℃ is collected to obtain the 1, 2-dichloropropane, wherein the separation rate is 80-100%, and the purity is 95-100%.
After separating out 1, 2-dichloropropane, the product mainly containing acrylic acid 3-chlorine-2-propylene ester or 2-methacrylic acid-3-chlorine-2-propylene ester can be obtained at the same time. The component content of the raw material DD mixture and the purity of the 1, 2-dichloropropane, acrylic acid-3-chloro-2-propenyl ester or 2-methacrylic acid-3-chloro-2-propenyl ester can be analyzed and determined by a gas chromatograph.
The compositional analysis and structural characterization methods were as follows:
the DD mixture raw material composition and the product purity are detected and analyzed by a 103 type gas chromatography produced by Shanghai analytical instrument factory, and a chromatographic column: peg.15%, red 102 vehicle. The gas chromatographic analysis conditions of the DD mixed agent and the 1, 2-dichloropropane are as follows; the temperature of the column chamber is 90 ℃, the temperature of the heat conduction pool is 110 ℃, and the gasification temperature is 150 ℃; the gas chromatographic analysis conditions of the acrylic acid 3-chloro-2-propenyl ester or the 2-methacrylic acid 3-chloro-2-propenyl ester are as follows: the temperature of the column chamber is 110 ℃, the temperature of the heat conduction pool is 150 ℃, and the gasification temperature is 180 ℃. The infrared spectroscopic analysis was carried out by means of an IR-435 type infrared spectrometer of Shimadzu Japan.
Carrying out reduced pressure distillation under the vacuum degree of 20mmHg, and collecting fractions at 57-65 ℃, namely the acrylic acid-3-chloro-2-propenyl ester. The physical property data are as follows:
the boiling range is 57-65 ℃/1.33KPa
Density (25 ℃ C.) 1.173g/cm3
Refractive index (25 ℃ C.) 1.4546
The physical property data of the 2-methacrylic acid-3-chlorine-2-propylene ester are as follows:
the boiling range is 73-82 ℃/1.33KPa
Density (25 ℃ C.) 1.160g/cm3
Refractive index (25 ℃ C.) 1.4582
The other product of acrylic acid-3-chlorine-2-propylene ester or 2-methacrylic acid-3-chlorine-2-propylene ester obtained by the method comprises cis-isomer and trans-isomer, has similar physicochemical properties, contains two carbon-carbon double bonds in the structure, and does not need to be separated when in application. Can be used for producing high molecular resin materials by utilizing the self polymerization, in particular, the copolymerization with other vinyl monomers. For example, the product is initiated to polymerize at about 80 ℃ under the action of a free radical initiator benzoyl peroxide to form an elastic resin which can swell but cannot be dissolved in aromatic hydrocarbon and halogenated hydrocarbon and cannot be melted by heating. The product can be used as a cross-linking agent of thermoplastic resin, a modifier of paint and adhesive.
The method can realize the effective separation of 1, 2-dichloropropane in the industrial byproduct DD mixed agent, and is an effective way for realizing the comprehensive utilization of the DD mixed agent. The separated 1, 2-dichloropropane is more important organic synthesis intermediate and solvent, and can be converted into useful chemical products by chemical reactions of chlorination, ammoniation, hydrolysis, elimination and the like.
Drawings
The attached figure is an infrared spectrogram of acrylic acid-3-chlorine-2-propylene ester.
Detailed Description
Example 1 (two-step method)
The DD mixture was dehydrated and briefly distilled to remove impurities, and the contents of its components were analyzed by gas chromatography. Acrylic acid is refined by reduced pressure distillation, polymers and impurities which may be contained are removed, and a proper amount of polymerization inhibitor is added to prevent the polymerization.
After a stirring device, a water separator and a condenser are arranged on a three-mouth bottle, 0.5mol of acrylic acid and 0.04g of polymerization inhibitor DPPH0 are added, stirred and cooled, and then 0.5mol of sodium hydroxide is added for neutralization. Then, the product was azeotropically dehydrated with benzene and dried in vacuo to obtain about 47g of sodium acrylate.
A stirring device, a condenser and a thermometer are arranged on a 500ml three-mouth bottle, and 241.3g (containing 23 percent of 1, 3-dichloropropene and 0.5mol) of DD mixed agent, 47g (0.5mol) of sodium acrylate, 0.04g of DPPH0 and 3ml of triethylamine are added in turn under stirring. Heating the mixture to 85-90 ℃ in an oil bath, and reacting for 5 hours at constant temperature. After the esterification reaction is finished, cooling to room temperature, and filtering to remove the generated inorganic salt precipitate. (or adding water to dissolve inorganic salt, standing for layering, and removing a water phase.) adding a proper amount of anhydrous magnesium sulfate into an organic phase to remove residual water, adding 0.1g of hydroquinone, distilling at normal pressure, collecting a fraction at 95-100 ℃ to obtain 1, 2-dichloropropane, analyzing and determining the purity of the 1, 2-dichloropropane by using a gas chromatograph to be 95.2%, and calculating the yield to be 84.5%. And distilling and refining the remainder under the vacuum degree of 1.3KPa, collecting fractions at 57-65 ℃, namely acrylic acid-3-chloro-2-propenyl ester, analyzing and determining the purity of the acrylic acid-3-chloro-2-propenyl ester by a gas chromatograph, and calculating the yield of the acrylic acid-3-chloro-2-propenyl ester to be 75.6%.
Example 2 (two-step method)
The procedure was carried out as in example 1. The conditions for the esterification reaction were changed as follows: the reaction temperature is 75-80 ℃, the reaction time is 4 hours, the consumption of triethylamine is 2.5ml, the purity of 1, 2-dichloropropane is 95.5 percent, and the calculated yield is 82.5 percent.
Example 3 (two-step method)
The procedure was carried out as in example 1. The conditions for the esterification reaction were changed as follows: the reaction temperature is 75-80 ℃, the reaction time is 5 hours, the consumption of triethylamine is 3.0ml, the purity of 1, 2-dichloropropane is 95.0 percent, and the calculated yield is 83.0 percent.
Example 4 (two-step method)
The procedure was carried out as in example 1. The conditions for the esterification reaction were changed as follows: the reaction temperature is 75-80 ℃, the reaction time is 6 hours, the consumption of triethylamine is 3.5ml, the purity of 1, 2-dichloropropane is 95.2 percent, and the calculated yield is 83.5 percent.
Example 5 (two-step method)
The procedure was carried out as in example 1. The conditions for the esterification reaction were changed as follows: the reaction temperature is 85-90 ℃, the reaction time is 5 hours, the consumption of triethylamine is 2.5ml, the purity of 1, 2-dichloropropane is 94.7 percent, and the calculated yield is 83.0 percent.
Example 6 (two-step method)
The procedure was carried out as in example 1. The conditions for the esterification reaction were changed as follows: the reaction temperature is 85-90 ℃, the reaction time is 6 hours, the consumption of triethylamine is 3.0ml, the purity of 1, 2-dichloropropane is 96.0 percent, and the calculated yield is 83.1 percent.
Example 7 (two-step method)
The procedure was carried out as in example 1. The conditions for the esterification reaction were changed as follows: the reaction temperature is 85-90 ℃, the reaction time is 4 hours, the consumption of triethylamine is 3.5ml, the purity of 1, 2-dichloropropane is 93.9 percent, and the calculated yield is 84.2 percent.
Example 8 (two-step method)
The procedure was carried out as in example 1. The conditions for the esterification reaction were changed as follows: the reaction temperature is 95-100 ℃, the reaction time is 6 hours, the consumption of triethylamine is 2.5ml, the purity of 1, 2-dichloropropane is 95.9 percent, and the calculated yield is 85.1 percent.
Example 9 (two-step method)
The procedure was carried out as in example 1. The conditions for the esterification reaction were changed as follows: the reaction temperature is 95-100 ℃, the reaction time is 4 hours, the consumption of triethylamine is 3.0ml, the purity of 1, 2-dichloropropane is 95.8 percent, and the calculated yield is 85.5 percent.
Example 10 (two-step method)
The procedure was carried out as in example 1. The conditions for the esterification reaction were changed as follows: the reaction temperature is 95-100 ℃, the reaction time is 5 hours, the consumption of triethylamine is 3.5ml, the purity of 1, 2-dichloropropane is 94.8 percent, and the calculated yield is 83.7 percent.
Example 11 (two-step method)
The feedstock pretreatment was the same as in example 1.
0.5mol of methacrylic acid reacts with 0.5mol of sodium hydroxide to prepare 0.5mol of sodium methacrylate, and 102.8g of DD mixed agent (containing 54 percent of 1, 3-dichloropropene and 0.5mol of sodium methacrylate), 0.5mol of DPPH0.05g and 3.0ml of triethylamine are added in turn under stirring after a stirring device, a water separator and a condenser are arranged on a 500ml three-necked bottle. Heating the mixture to 95-100 ℃ in an oil bath, and reacting the mixture for 6 hours at constant temperature, wherein the rest steps are the same as those of the example 1. The purity of the 1, 2-dichloropropane is 96.0 percent through gas chromatograph analysis and determination, and the calculated yield is 84.5 percent; the purity of the 2-methacrylic acid-3-chloro-2-propenyl ester was 97.0% by gas chromatograph analysis, calculated as a yield of 64.8%.
Example 12 (one-step method)
The raw material pretreatment process is the same as above.
After a stirring device, a water separator and a condenser are arranged on a 500ml three-mouth bottle, 241.3g (containing 23 percent of 1, 3-dichloropropene and 0.5mol of acrylic acid), 0.5mol of DPPH0.04g and 0.5mol of sodium hydroxide are added into a DD mixing agent under stirring, and the rest is the same as the embodiment 9, so that the yield of the 1, 2-dichloropropane is 81.2 percent and the yield of the 3-chloro-2-propenyl acrylate is 23.5 percent.
Example 13 (one-step Process)
The raw material pretreatment process is the same as above.
After a stirring device, a water separator and a condenser are arranged on a 500ml three-necked bottle, 100.9g (containing 55 percent of 1, 3-dichloropropene and 0.5mol) of DD mixed agent, 0.5mol of methacrylic acid, 0.06g of DPPH0, 0.5mol of sodium hydroxide and 3.0ml of triethylamine are added in turn under stirring, the mixture is heated to 95-100 ℃ in an oil bath and reacts for 6 hours at constant temperature, and the other steps are the same as the step of example 9. The purity of the 1, 2-dichloropropane is 96.0 percent through gas chromatograph analysis and determination, and the calculated yield is 84.5 percent; the purity of 2-methacrylic acid-3-chloro-2-propenyl ester was 97.0% by gas chromatograph analysis, calculated as a yield of 66.8%.
Claims (5)
1. A method for separating 1, 2-dichloropropane by using DD mixed agent is characterized by comprising the following process steps:
(1) pretreatment of raw materials
Removing impurities from the DD mixed agent through dehydration and simple distillation, receiving fractions at 97-110 ℃, and refining acrylic acid or methacrylic acid through reduced pressure distillation before use;
(2) catalytic esterification reaction
Firstly, neutralizing with alkali and acrylic acid or methacrylic acid to prepare corresponding acrylate or methacrylate, then taking the generated salt as a raw material of an esterification reaction, mixing the salt with a DD mixing agent, a catalyst and a polymerization inhibitor in an esterification reactor, stirring and heating to a reaction temperature, carrying out catalytic esterification reaction at the reaction temperature of 60-100 ℃ for 3-8 hours, and carrying out the reaction under normal pressure; secondly, adding alkali into the DD mixed agent for hydrolysis to convert 1, 3-dichloropropene into 3-chloroallyl alcohol, adding acrylic acid or methacrylic acid, a polymerization inhibitor and a catalyst into an esterification reactor, stirring and heating to a reaction temperature, and carrying out catalytic esterification reaction at the reaction temperature of 60-100 ℃ for 3-8 hours, wherein the reaction is carried out at normal pressure;
the one-step method is that DD mixed agent, acrylic acid or methacrylic acid, polymerization inhibitor, alkali and catalyst are added into an esterification reactor in sequence according to a certain proportion, stirred and heated to the reaction temperature, catalytic esterification reaction is carried out, the reaction temperature is 60-100 ℃, the reaction time is 3-8 hours, and the reaction is carried out under normal pressure;
(3) product separation
After the catalytic esterification reaction is finished, cooling the system to room temperature, standing, precipitating inorganic salt generated by the reaction, and directly filtering to separate out the inorganic salt; or adding a proper amount of water into the system to dissolve the generated inorganic salt, standing for layering, and removing the water phase; distilling the organic phase subjected to the desalting at normal pressure, and collecting a fraction at 95-100 ℃, namely 1, 2-dichloropropane.
2. The method for separating 1, 2-dichloropropane from DD mixture as claimed in claim 1, wherein the polymerization inhibitor for acrylic acid or methacrylic acid is selected from free radical polymerization inhibitors including hydroquinone, p-hydroxyanisole or phenothiazine, or free radical polymerization inhibitor DPPH, and is added before catalytic esterification, in an amount of 0.001-0.1% by mass of acrylic acid.
3. The method for separating 1, 2-dichloropropane from DD mixture according to claim 1, wherein the alkali used in the preparation process is sodium hydroxide, potassium hydroxide, sodium carbonate or other alkaline compounds, or aqueous solution of corresponding alkali, and the molar ratio of the alkali to acrylic acid or methacrylic acid is 1: 1-1.5.
4. The method for separating 1, 2-dichloropropane by using the DD mixed agent as claimed in claim 1, wherein the catalyst used for the catalytic esterification reaction is triethylamine, cuprous chloride or a phase transfer catalyst, and comprises polyethylene glycol and various quaternary ammonium salts, and the using amount of the catalyst is 1-10% of the mass of acrylic acid or methacrylic acid.
5. The process for separating 1, 2-dichloropropane as claimed in claim 1, which comprises mixing the components in a stoichiometric ratio of 1: 1, based on the molar ratio of 1, 3-dichloropropene to acrylic acid or methacrylic acid in the DD mixture.
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| CN200510046147.5 | 2005-03-31 | ||
| CN 200510046147 CN1687006A (en) | 2005-03-31 | 2005-03-31 | 2-methacrylic acid-3-chlorine-2-propylene |
| CNB2006102003033A CN100402476C (en) | 2005-03-31 | 2006-03-30 | Method of separating 1,2-dichloropropane with DD mixture |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432426A (en) * | 2011-12-14 | 2012-05-02 | 青岛科技大学 | Method for separating and purifying dichloropropane and dichloropropylene |
| CN105254470A (en) * | 2015-11-18 | 2016-01-20 | 陕西神光化学工业有限公司 | Method for removing impurities 1,1,2,2,3,3,4,5-octafluorocyclopentane |
| CN111807925A (en) * | 2020-07-23 | 2020-10-23 | 山东海益化工科技有限公司 | D-D mixture rectification separation process |
-
2006
- 2006-03-30 CN CNB2006102003033A patent/CN100402476C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432426A (en) * | 2011-12-14 | 2012-05-02 | 青岛科技大学 | Method for separating and purifying dichloropropane and dichloropropylene |
| CN102432426B (en) * | 2011-12-14 | 2013-11-06 | 青岛科技大学 | Method for separating and purifying dichloropropane and dichloropropylene |
| CN105254470A (en) * | 2015-11-18 | 2016-01-20 | 陕西神光化学工业有限公司 | Method for removing impurities 1,1,2,2,3,3,4,5-octafluorocyclopentane |
| CN111807925A (en) * | 2020-07-23 | 2020-10-23 | 山东海益化工科技有限公司 | D-D mixture rectification separation process |
| CN111807925B (en) * | 2020-07-23 | 2021-11-02 | 山东海益化工科技有限公司 | D-D mixture rectification separation process |
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