CN101992125B - Method for regenerating heteropoly acid quaternary ammonium salt catalyst - Google Patents
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- CN101992125B CN101992125B CN2009101634569A CN200910163456A CN101992125B CN 101992125 B CN101992125 B CN 101992125B CN 2009101634569 A CN2009101634569 A CN 2009101634569A CN 200910163456 A CN200910163456 A CN 200910163456A CN 101992125 B CN101992125 B CN 101992125B
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- 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 provides a method for regenerating a heteropoly acid quaternary ammonium salt catalyst. The method comprises the following steps of: firstly, washing an inactivated heteropoly acid quaternary ammonium salt catalyst with a solvent to remove residual reactants and impurities with a high boiling point; then, dissolving the catalyst with a mixed solvent containing an aqueous hydrogen peroxide solution and halogenated hydrocarbon; and finally, adding phosphoric acid and quaternary ammonium salt to regenerate the catalyst. The method can recover the original activity of the catalyst, achieve the hydrogen peroxide conversion larger than 98 percent and the selectivity higher than 97 percent and keep the stable activity of the catalyst for a long time being same with a fresh catalyst.
Description
Technical field
The present invention relates to a kind of method of heteropoly acid quaternary ammonium salt catalyst regeneration.
Background technology
The heteropoly acid quaternary ammonium salt catalyst is widely used in the epoxidation Reaction of Alkenes.
CN 1155587C is oxygen source with the molecular oxygen, is catalyst with the heteropoly acid quaternary ammonium salt, and activate molecular oxygen in organic solvent makes chloropropene selective oxidation system epoxychloropropane.
CN 1161346C H
2O
2The aqueous solution is oxygen source, is catalyst with phosphorus tungsten or phosphato-molybdic heteropolyacid quaternary ammonium salt, with the cyclohexene ring oxidation, and the preparation 7-oxa-bicyclo[4.1.0.
CN 1900071A is with H
2O
2The aqueous solution is oxygen source, is catalyst with phosphorus tungsten or phosphato-molybdic heteropolyacid quaternary ammonium salt, under solvent-free condition, with chloro propylene epoxidation, prepares the epoxidation chloropropane.
CN 101016281A is with H
2O
2The aqueous solution is oxygen source, is catalyst with quaternary ammonium salt phosphor-tungstic heteropoly acid and APES, preparation epoxidation chloropropane under solvent-free condition.
It is reaction raw materials that CN 101279961A adopts with hydrogen peroxide and chloropropene; With the phosphorus heteropoly tungstic acid quaternary salt is catalyst; The preparation epoxychloropropane; Solve was that oxygen source prepares that the epoxychloropropane technology exists because the introducing of a large amount of methanol solvates, complicated operation, the problem that separating energy consumption is big with the hydrogen peroxide in the past.
But, know that the heteropoly acid quaternary ammonium salt catalyst can carrying out and lose activity gradually with reaction.
Hill etc. are at " Mechanism and Dynamics in the H
3[PW
12O
40]-Catalyzed Selective Epoxidation of Terminal Olefins by H
2O
2.Formation, Reactivity, and Stability of{PO
4[WO (O
2)
2]
4}
3-" (J.Am.Chem.Soc.1995,117, point out that 681-691) this quaternary ammonium salt phosphor-tungstic heteropoly acid catalyst is after recycling 500 times, its activity significantly reduces, and reaction speed is very slow.But there is not to propose to make the method for catalyst activity recovery.
Xi Zuwei etc. are at " On the nature of reaction-controlled phase transfer catalysts for epoxidation of olefin:a
31P NMR investigation " (Catalysis Letters.2004,93,41-46) in, the variation in course of reaction is analyzed to the heteropoly acid quaternary ammonium salt, point out catalyst in course of reaction at H
2O
2Effect under, can become gradually high P/W than and hang down the species of P/W, wherein its reactivity of species of low P/W is very low, thereby activity of such catalysts is reduced.There is not to propose to make the method for catalyst activity recovery yet.
For will olefin(e) compound is applied to industrial preparation oxyalkylene or epoxides through with hydroperoxidation process for epoxidation taking place in the presence of the heteropoly acid quaternary ammonium salt containing, need to use repeatedly the regeneration techniques of catalyst.
Summary of the invention
The purpose of this invention is to provide the method that makes the regeneration of heteropoly acid quaternary ammonium salt catalyst; In the method; With the mixed solvent catalyst-solvent that contains aqueous hydrogen peroxide solution and halogenated hydrocarbon; Add phosphoric acid and quaternary ammonium salt then, make catalyst regeneration, and activity of such catalysts and the raw catelyst of regeneration is active identical.
To achieve these goals, the invention provides a kind of method of heteropoly acid quaternary ammonium salt catalyst regeneration, this method comprises:
I) wash with the heteropoly acid quaternary ammonium salt catalyst of solvent inactivation, reactant and high-boiling-point impurity that flush away is remaining, wherein solvent load is 0.5~100 times of weight of catalyst, the temperature of washing: 0 ℃~100 ℃; Wash time: 0.1~72 hour;
Ii) the catalyst through washing dissolves with the mixed solvent of hydrogen peroxide solution and halogenated hydrocarbons, and wherein the concentration of hydrogen peroxide solution is 0.1~40 weight %, and the addition of halogenated hydrocarbons is 1~50 times of the weight of catalyst; Add phosphoric acid and quaternary ammonium salt then, the phosphoric acid addition is a catalyst weight 0.1%~10.0%, and the addition of quaternary ammonium salt is a catalyst weight 1%~20%, and 10~150 ℃ of temperature, stirring down, reaction made catalyst regeneration in 1~72 hour.
Preferred version of the present invention:
I) wash with the heteropoly acid quaternary ammonium salt catalyst of solvent inactivation, reactant and high-boiling-point impurity that flush away is remaining, wherein solvent load is 5~20 times of weight of catalyst, 15 ℃~60 ℃ of temperature, wash time 0.5~48 hour;
Ii) the catalyst through washing dissolves with the mixed solvent of hydrogen peroxide solution and halogenated hydrocarbons, and wherein the concentration of hydrogen peroxide solution is 10~30 weight %, and the addition of halogenated hydrocarbons is 5~20 times of the weight of catalyst; Add phosphoric acid and quaternary ammonium salt then, the phosphoric acid addition is a catalyst weight 0.1%~10.0%, and the addition of quaternary ammonium salt is a catalyst weight 1%~20%, and 20~60 ℃ of temperature, stirring down, reaction made catalyst regeneration in 6~24 hours.
Heteropoly acid quaternary ammonium salt catalyst of the present invention comprises: phosphotungstic acid quaternary catalyst, phosphomolybdic acid quaternary ammonium salt catalyst, phosphorus vanadic acid quaternary ammonium salt catalyst.
Solvent of the present invention is selected from water or chloroform or carrene or carbon tetrachloride or dichloroethanes or hexane or cyclohexane or No. 6 solvent naphthas or benzinum or methyl alcohol or ethanol or the propyl alcohol or the butanols of pH value 1~2
Halogenated hydrocarbons of the present invention is selected from chloroform or carrene or carbon tetrachloride or dichloroethanes.
Quaternary ammonium salt of the present invention is chloro-hexadecane yl pyridines or bromohexadecane yl pyridines.
According to method of the present invention, when the mixed solvent that comprises hydrogen peroxide solution and halogenated hydrocarbon when use is regenerated the used heteropoly acid quaternary ammonium salt catalyst of epoxidation reaction of olefines that utilizes hydrogen peroxide, can remove the impurity in the catalyst effectively; And, after reaction is accomplished, can recover the original activity of catalyst, the conversion ratio of hydrogen peroxide is greater than 98%, and selectivity is higher than 97%, and is identical with fresh catalyst, and activity of such catalysts can keep stable for a long time.
The specific embodiment
Following embodiment will further explain the present invention, but therefore not limit scope of the present invention.
Embodiment 1
With H
2O
2The aqueous solution is oxygen source, and the phosphotungstic acid cetyl pyridinium is a catalyst, under solvent-free condition, with the chloropropene oxidation, prepares epoxychloropropane.After epoxidation reaction is carried out the long period; Work as catalysqt deactivation; Its catalytic activity is reduced to predeterminated level or predeterminated level when following, and it is 60 ℃ in temperature that the catalyst that reaction is separated out uses the aqueous hydrochloric acid solution of pH value 1-2, and pressure is the reactant and the impurity of erase residual under 1 atmospheric condition; The weight ratio of sour water and catalyst is 5: 1, wash time 0.5 hour.In the catalyst through the preliminary treatment washing, add dichloroethanes, the weight ratio of dichloroethanes and catalyst is 20: 1, adds 30.0% H again
2O
2The aqueous solution, H
2O
2The weight ratio of the aqueous solution and catalyst is 10: 1, adds 85% phosphoric acid then, and the addition of phosphoric acid is 1.0% of a catalyst; The chloro-hexadecane yl pyridines that adds catalytic amount 10%; 20 ℃ of temperature, stirred 6 hours under 1 atmospheric condition, leave standstill again; Tell water, organic facies is deviate from the catalyst of dichloroethanes reclaiming.Regenerated catalyst and fresh catalyst are respectively applied for the conversion ratio of chloro propylene epoxidation reaction hydrogen peroxide and the selectivity such as the table 1 of epoxychloropropane.
[table 1]
H 2O 2Conversion ratio (%) | The selectivity of epoxychloropropane (%) | |
Fresh catalyst | 99.0 | 97.5 |
Regenerated catalyst | 99.0 | 97.6 |
Can clearly be seen that from table 1 activity of regenerated catalyst is identical with fresh catalyst.
Embodiment 2
With H
2O
2The aqueous solution is oxygen source, and phosphorus vanadic acid cetyl pyridinium is a catalyst, with the chloroform be under the condition of solvent with cyclohexene oxide, the preparation 7-oxa-bicyclo[4.1.0.After epoxidation reaction is carried out the long period; Work as catalysqt deactivation; Its catalytic activity is reduced to predeterminated level or predeterminated level when following, and it is 60 ℃ in temperature that the catalyst that reaction is separated out uses the aqueous hydrochloric acid solution of pH value 1-2, and pressure is the reactant and the impurity of erase residual under 1 atmospheric condition; The weight ratio of sour water and catalyst is 5: 1, wash time 0.5 hour.In the catalyst through the preliminary treatment washing, add chloroform, the weight ratio of chloroform and catalyst is 20: 1, adds 30.0% H
2O
2The aqueous solution, H
2O
2The weight ratio of the aqueous solution and catalyst is 10: 1, adds 85% phosphoric acid then, and the addition of phosphoric acid is 1.0% of a catalyst; The bromohexadecane yl pyridines that adds catalytic amount 10%; 20 ℃ of temperature, stirred 6 hours under 1 atmospheric condition, leave standstill again; Tell water, organic facies is deviate from the catalyst of chloroform reclaiming.Regenerated catalyst and fresh catalyst are respectively applied for the conversion ratio of cyclohexene ring oxidation reaction hydrogen peroxide and the selectivity such as the table 2 of 7-oxa-bicyclo[4.1.0.
[table 2]
H 2O 2Conversion ratio (%) | The selectivity of 7-oxa-bicyclo[4.1.0 (%) | |
Fresh catalyst | 98.6 | 98.0 |
Regenerated catalyst | 98.8 | 98.1 |
Embodiment 3
According to making catalyst regeneration with embodiment 1 identical method, different is to adopt phosphomolybdic acid cetyl pyridinium catalyst.Regenerated catalyst is used for the conversion ratio of chloro propylene epoxidation reaction hydrogen peroxide and the selectivity such as the table 3 of epoxychloropropane.
Embodiment 4
According to making catalyst regeneration with embodiment 1 identical method, different is that first step cleaning uses chloroform to carry out.Regenerated catalyst is used for the conversion ratio of chloro propylene epoxidation reaction hydrogen peroxide and the selectivity such as the table 3 of epoxychloropropane.
Embodiment 5
According to making catalyst regeneration with embodiment 2 identical methods, the weight ratio of different is chloroform and catalyst is 8: 1,25 ℃ of wash temperatures, wash time 6h.Regenerated catalyst is used for the conversion ratio of chloro propylene epoxidation reaction hydrogen peroxide and the selectivity such as the table 3 of epoxychloropropane.
Embodiment 6
According to making catalyst regeneration with embodiment 1 identical method, different is that first step cleaning uses benzinum to carry out.Regenerated catalyst is used for the conversion ratio of chloro propylene epoxidation reaction hydrogen peroxide and the selectivity such as the table 3 of epoxychloropropane.
Embodiment 7
According to making catalyst regeneration with embodiment 1 identical method, different is that first step cleaning uses methyl alcohol to carry out.Regenerated catalyst is used for the conversion ratio of chloro propylene epoxidation reaction hydrogen peroxide and the selectivity such as the table 3 of epoxychloropropane.
Embodiment 8
According to making catalyst regeneration with embodiment 4 identical methods, the weight ratio of different is methyl alcohol and catalyst is 20: 1,15 ℃ of wash temperatures, wash time 48h.Regenerated catalyst is used for the conversion ratio of chloro propylene epoxidation reaction hydrogen peroxide and the selectivity such as the table 3 of epoxychloropropane.
Embodiment 9
According to making catalyst regeneration with embodiment 5 identical methods, different is 30 ℃ of wash temperatures, wash time 30h.Regenerated catalyst is used for the conversion ratio of chloro propylene epoxidation reaction hydrogen peroxide and the selectivity such as the table 3 of epoxychloropropane.
[table 3]
H 2O 2Conversion ratio (%) | The selectivity of epoxychloropropane (%) | |
Embodiment 3 | 99.1 | 98.1 |
Embodiment 4 | 99.0 | 97.6 |
Embodiment 5 | 99.0 | 97.7 |
Embodiment 6 | 98.7 | 97.5 |
Embodiment 7 | 98.9 | 97.5 |
Embodiment 8 | 99.0 | 98.0 |
Embodiment 9 | 99.0 | 98.0 |
Embodiment 10
According to making catalyst regeneration with embodiment 9 identical methods, different is that the halogenated hydrocarbons that uses in the second step regeneration step is chloroform.Regenerated catalyst is used for the conversion ratio of chloro propylene epoxidation reaction hydrogen peroxide and the selectivity such as the table 4 of epoxychloropropane.
Embodiment 11
According to making catalyst regeneration with embodiment 10 identical methods, the weight ratio of different is in second step regeneration step chloroform and catalyst is 5: 1.Regenerated catalyst is used for the conversion ratio of chloro propylene epoxidation reaction hydrogen peroxide and the selectivity such as the table 4 of epoxychloropropane.
Embodiment 12
According to making catalyst regeneration with embodiment 10 identical methods, the weight ratio of different is in second step regeneration step chloroform and catalyst is 10: 1.Regenerated catalyst is used for the conversion ratio of chloro propylene epoxidation reaction hydrogen peroxide and the selectivity such as the table 4 of epoxychloropropane.
Embodiment 13
According to making catalyst regeneration with embodiment 10 identical methods, that different is H in the second step regeneration step
2O
2The concentration of the aqueous solution is 10%, H
2O
2The weight ratio of the aqueous solution and catalyst 20: 1.Regenerated catalyst is used for the conversion ratio of chloro propylene epoxidation reaction hydrogen peroxide and the selectivity such as the table 4 of epoxychloropropane.
Embodiment 14
According to making catalyst regeneration with embodiment 10 identical methods, the addition of different is phosphoric acid in the second step regeneration step is 0.1% of a catalyst.Regenerated catalyst is used for the conversion ratio of chloro propylene epoxidation reaction hydrogen peroxide and the selectivity such as the table 4 of epoxychloropropane.
Embodiment 15
According to making catalyst regeneration with embodiment 10 identical methods, the addition of different is phosphoric acid in the second step regeneration step is 10% of a catalyst.Regenerated catalyst is used for the conversion ratio of chloro propylene epoxidation reaction hydrogen peroxide and the selectivity such as the table 4 of epoxychloropropane.
Embodiment 16
According to making catalyst regeneration with embodiment 10 identical methods, the addition of different is cetylpyridinium chloride in the second step regeneration step is 1% of a catalyst.Regenerated catalyst is used for the conversion ratio of chloro propylene epoxidation reaction hydrogen peroxide and the selectivity such as the table 4 of epoxychloropropane.
Embodiment 17
According to making catalyst regeneration with embodiment 10 identical methods, the addition of different is cetylpyridinium chloride in the second step regeneration step is 20% of a catalyst.Regenerated catalyst is used for the conversion ratio of chloro propylene epoxidation reaction hydrogen peroxide and the selectivity such as the table 4 of epoxychloropropane.
Embodiment 18
According to making catalyst regeneration with embodiment 10 identical methods, the temperature that different is in the second step regeneration step is 30 ℃.Regenerated catalyst is used for the conversion ratio of chloro propylene epoxidation reaction hydrogen peroxide and the selectivity such as the table 4 of epoxychloropropane.
Embodiment 19
According to making catalyst regeneration with embodiment 10 identical methods, the temperature that different is in the second step regeneration step is 60 ℃.Regenerated catalyst is used for the conversion ratio of chloro propylene epoxidation reaction hydrogen peroxide and the selectivity such as the table 4 of epoxychloropropane.
Embodiment 20
According to making catalyst regeneration with embodiment 10 identical methods, different is to stir 15h in the second step regeneration step.Regenerated catalyst is used for the conversion ratio of chloro propylene epoxidation reaction hydrogen peroxide and the selectivity such as the table 4 of epoxychloropropane.
Embodiment 21
According to making catalyst regeneration with embodiment 10 identical methods, different is to stir 24h in the second step regeneration step.Regenerated catalyst is used for the conversion ratio of chloro propylene epoxidation reaction hydrogen peroxide and the selectivity such as the table 4 of epoxychloropropane.
[table 4]
H 2O 2Conversion ratio (%) | The selectivity of epoxychloropropane (%) | |
Embodiment 10 | 99.1 | 98.1 |
Embodiment 11 | 99.0 | 97.6 |
Embodiment 12 | 99.0 | 97.7 |
Embodiment 13 | 98.7 | 97.5 |
Embodiment 14 | 98.9 | 97.5 |
Embodiment 15 | 99.0 | 98.0 |
Embodiment 16 | 98.8 | 97.8 |
Embodiment 17 | 98.9 | 98.0 |
Embodiment 18 | 98.7 | 98.0 |
Embodiment 19 | 98.8 | 97.7 |
Embodiment 20 | 99.0 | 98.0 |
Embodiment 21 | 99.1 | 98.2 |
Claims (5)
1. the method for heteropoly acid quaternary ammonium salt catalyst regeneration; It is characterized in that: i) wash with the heteropoly acid quaternary ammonium salt catalyst of solvent to inactivation; Reactant and high-boiling-point impurity that flush away is remaining; Wherein solvent load is 0.5~100 times of weight of catalyst, the temperature of washing: 0 ℃~100 ℃; Wash time: 0.1~72 hour; Ii) the catalyst through washing dissolves with the mixed solvent of hydrogen peroxide solution and halogenated hydrocarbons, and wherein the concentration of hydrogen peroxide solution is 0.1~40 weight %, and the addition of halogenated hydrocarbons is 1~50 times of the weight of catalyst; Add phosphoric acid and quaternary ammonium salt then, the phosphoric acid addition is a catalyst weight 0.1%~10.0%, and the addition of quaternary ammonium salt is a catalyst weight 1%~20%, and 10~150 ℃ of temperature, stirring down, reaction made catalyst regeneration in 1~72 hour; Wherein said heteropoly acid quaternary ammonium salt catalyst is phosphotungstic acid quaternary catalyst or phosphomolybdic acid quaternary ammonium salt catalyst or phosphorus vanadic acid quaternary ammonium salt catalyst.
2. method according to claim 1; It is characterized in that: i) wash with the heteropoly acid quaternary ammonium salt catalyst of solvent to inactivation; Reactant and high-boiling-point impurity that flush away is remaining; Wherein solvent load is 5~20 times of weight of catalyst, 15 ℃~60 ℃ of temperature, wash time 0.5~48 hour; Ii) the catalyst through washing dissolves with the mixed solvent of hydrogen peroxide solution and halogenated hydrocarbons, and wherein the concentration of hydrogen peroxide solution is 10~30 weight %, and the addition of halogenated hydrocarbons is 5~20 times of the weight of catalyst; Add phosphoric acid and quaternary ammonium salt then, the phosphoric acid addition is a catalyst weight 0.1%~10.0%, and the addition of quaternary ammonium salt is a catalyst weight 1%~20%, and 20~60 ℃ of temperature, stirring down, reaction made catalyst regeneration in 6~24 hours; Wherein said heteropoly acid quaternary ammonium salt catalyst is phosphotungstic acid quaternary catalyst or phosphomolybdic acid quaternary ammonium salt catalyst or phosphorus vanadic acid quaternary ammonium salt catalyst.
3. method according to claim 1 and 2 is characterized in that: described solvent is selected from aqueous hydrochloric acid solution or chloroform or carrene or carbon tetrachloride or dichloroethanes or hexane or cyclohexane or No. 6 solvent naphthas or benzinum or methyl alcohol or ethanol or the propyl alcohol or the butanols of pH value 1~2.
4. method according to claim 1 and 2 is characterized in that: described halogenated hydrocarbons is selected from chloroform or carrene or carbon tetrachloride or dichloroethanes.
5. method according to claim 1 and 2 is characterized in that: described quaternary ammonium salt is chloro-hexadecane yl pyridines or bromohexadecane yl pyridines.
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CN101993423A (en) * | 2010-10-27 | 2011-03-30 | 中国石油化工股份有限公司 | Method for producing epoxy chloropropane |
CN108295908B (en) * | 2018-01-23 | 2020-09-22 | 北京工业大学 | Method for recovering solid catalyst after asymmetric Aldol reaction |
CN108993616B (en) * | 2018-07-20 | 2021-06-29 | 江苏扬农化工集团有限公司 | Regeneration method of phosphomolybdic/tungstic heteropoly acid quaternary ammonium salt catalyst |
CN108714436B (en) * | 2018-08-03 | 2021-03-30 | 江苏扬农化工集团有限公司 | Method for recovering activity of heteropoly acid catalyst for synthesizing epoxy chloropropane |
CN110156726A (en) * | 2019-06-03 | 2019-08-23 | 江苏扬农化工集团有限公司 | A kind of method of the residual comprehensive utilization of epoxychloropropane rectifying still |
CN113351260B (en) * | 2020-03-04 | 2022-08-05 | 上海迅凯新材料科技有限公司 | Regeneration method of perfluorosulfonic acid resin catalyst |
CN114824648A (en) * | 2022-03-18 | 2022-07-29 | 扬州大学 | PW 12 @ PDADMAC/WMCNT modified polypropylene diaphragm and application thereof in lithium-sulfur battery |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1110604A1 (en) * | 1996-09-11 | 2001-06-27 | Mitsubishi Chemical Mkv Company | Process for recovering rhodium |
CN1900071A (en) * | 2005-07-21 | 2007-01-24 | 中国科学院大连化学物理研究所 | Process for preparing epoxy chloropropane |
CN101205219A (en) * | 2006-12-22 | 2008-06-25 | 中国科学院大连化学物理研究所 | Preparation method of epoxypropane |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1110604A1 (en) * | 1996-09-11 | 2001-06-27 | Mitsubishi Chemical Mkv Company | Process for recovering rhodium |
CN1900071A (en) * | 2005-07-21 | 2007-01-24 | 中国科学院大连化学物理研究所 | Process for preparing epoxy chloropropane |
CN101205219A (en) * | 2006-12-22 | 2008-06-25 | 中国科学院大连化学物理研究所 | Preparation method of epoxypropane |
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