CN101003523A - Method for preparing epoxy chloropropane by using glycerol method - Google Patents
Method for preparing epoxy chloropropane by using glycerol method Download PDFInfo
- Publication number
- CN101003523A CN101003523A CN 200710019456 CN200710019456A CN101003523A CN 101003523 A CN101003523 A CN 101003523A CN 200710019456 CN200710019456 CN 200710019456 CN 200710019456 A CN200710019456 A CN 200710019456A CN 101003523 A CN101003523 A CN 101003523A
- Authority
- CN
- China
- Prior art keywords
- alkaline
- earth metal
- solid super
- basic catalyst
- oxide
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Compounds (AREA)
Abstract
This invention discloses a glycerol method for preparing epoxy chloropropane. The method comprises: (1) introducing dried HCl gas through 95% glycerol at 90-110 deg.C in the presence of absolute acetic acid, and reacting for 1-3 h; (2) adding the obtained dichloropropanol into a round bottom flask loaded with solid super-strong alkali catalyst, equipping condensing and drying tubes, stirring, heating to 70-90 deg.C, reacting for 3-5 h, filtering, and separating the catalyst to obtain chloropropane.
Description
Technical field
The present invention relates to a kind of method for preparing epoxy chloropropane, more specifically to a kind of method of preparing epoxy chloropropane by using glycerol method.
Background technology
Glycerine is the important source material of military project, light industry, chemical industry, in recent years along with grease chemical article expanding production continuously of biofuel particularly, seriously drug on the market to cause its by-product glycerin, price significantly glides, be that the exploitation that raw material carries out derived product is the method that well solves the glycerine surplus with glycerine, if can develop the production method of suitable derived product, can reduce the production cost of derived product again.(3-Chloro-1 2-epoxypropene) has another name called Epicholorohydrin to epoxy chloropropane, is a kind of important Organic Chemicals and fine chemical product, and purposes is very extensive.It is the main raw material of Resins, epoxy, chlorohydrin rubber, nitroglycerine explosive, glass reinforced plastic, electrical isolation goods, can be used for producing tackiness agent, Zeo-karb etc., also can be used as the solvent of softening agent, stablizer, tensio-active agent, medicine and Mierocrystalline cellulose vinegar, ether of cellulose and resin etc.In recent years, domestic epoxy chloropropane consumption rapid growth, output can not satisfy domestic needs far away, and import volume increases fast, and price rises steadily.At present, it is several that the production method of industrial epoxy chloropropane mainly contains propylene high-temperature chlorination process, allyl acetate method and glycerine method etc., and the product yield of propylene high-temperature chlorination process and allyl acetate method less than 90% all, also exist shortcomings such as transformation efficiency is low, by product is many, unit consumption is high, equipment corrosion is serious, many disposal of three wastes of waste water and dregs expense height simultaneously, invest also bigger.Excessive along with the grease chemical article by-product glycerin, preparing epoxy chloropropane by using glycerol method promptly is that the feedstock production epoxy chloropropane then becomes the method that ideal prepares epoxy chloropropane with glycerine, and the method for existing preparing epoxy chloropropane by using glycerol method promptly is that basic catalyst commonly used in the feedstock production epoxy chloropropane technology is liquid base such as NaOH with glycerine, KOH, its reaction formation is the homogeneous phase reactive liquid solution, the alkali lye that reaction needed is excessive, by product is more simultaneously, have problems making with extra care on the separating treatment that reaches catalyzer of product, the transformation efficiency of product separation well, selectivity, quality product and production cost all need to optimize.
Summary of the invention
The objective of the invention is to solve deficiency and the problem that exists in the above-mentioned present technology, a kind of method of preparing epoxy chloropropane by using glycerol method is provided, this method adopts solid super basic catalyst, make the catalytic activity height of reaction, good product selectivity, the product purity height, production cost is low.
Technical scheme of the present invention is as follows:
A kind of method of preparing epoxy chloropropane by using glycerol method may further comprise the steps:
A) be 95% glycerine with purity in the presence of anhydrous acetic acid (consumption be equivalent to qualities of glycerin 10%), fed the dry hydrogen chloride gas precursor reactants of crossing continuously 1～3 hour down, obtain dichlorohydrine in 90～110 ℃;
B) dichlorohydrine that obtains is joined in the round-bottomed flask of the solid super basic catalyst of putting well in advance again, install prolong and drying tube, be warming up to 70～90 ℃ of reactions 3～5 hours under stirring, stopped reaction obtains epoxy chloropropane behind the filtering separation catalyzer.
The consumption of the anhydrous acetic acid the method for above-mentioned preparing epoxy chloropropane by using glycerol method, its steps A) is 10% of a glycerine weight, step B) described in the consumption of solid super basic catalyst be 1～5% of dichlorohydrine weight.
Used solid super basic catalyst in a kind of method of preparing epoxy chloropropane by using glycerol method, this solid super basic catalyst is made up of alkaline earth metal oxide and alkalimetal oxide and porous carrier, described alkaline-earth metal is magnesium (Mg), calcium (Ca), in strontium (Sr) and the barium (Ba) one or more, described basic metal is lithium (Li), sodium (Na), in potassium (K) and the rubidium (Rb) one or more, wherein the mol ratio of basic metal and alkaline-earth metal is not more than 2, and the consumption of porous carrier is 100～200% of alkalimetal oxide and an alkaline earth metal oxide gross weight.Wherein said porous carrier is gac, calcined hydrotalcite, aluminum oxide, zirconium white, titanium oxide or magnesium oxide, preferred aluminum oxide, most preferably gama-alumina.
The preparation method of used solid super basic catalyst in a kind of method of preparing epoxy chloropropane by using glycerol method, its step is as follows:
1) dissolving
All be dissolved in alkaline earth metal oxide, alkalimetal oxide in the polar solvent, form saturated alkaline-earth metal salt solution, alkali metal salt soln, described alkaline-earth metal is one or more in magnesium (Mg), calcium (Ca), strontium (Sr) and the barium (Ba), described basic metal is one or more in lithium (Li), sodium (Na), potassium (K) and the rubidium (Rb), preferred metals is drawn together Ca, K, wherein the mol ratio of basic metal and alkaline-earth metal is not more than 2, described polar solvent is water or alcohol, and described alcohol is preferably methyl alcohol, ethanol, propyl alcohol, ethylene glycol or propylene glycol.
Some calcium salt of the present invention be can be used for and calcium chloride, nitrocalcite comprised.Usually can be used for sylvite of the present invention and comprise potassium oxide, saltpetre, vitriolate of tartar, salt of wormwood.
2) become glue
Under the violent stirring effect, above-mentioned two kinds of saturated alkaline-earth metal salt solutions, alkali metal salt soln blending dispersion are even, and add 10～100% organic compound of alkaline-earth metal and alkali-metal weight, after mixing, 100～200% the porous carrier that adds alkaline-earth metal and alkali-metal weight again floods, after to be impregnated being uniformly dispersed, removing under 0～200 ℃ of temperature and desolvate, making the colloidal solid product is colloidal sol; Described organic compound is one or more the mixture in tensio-active agent, organic amine compound, polyoxyethylene glycol, polyvinyl alcohol, glucose or the starch, preferred trolamine, described porous carrier is gac, calcined hydrotalcite, aluminum oxide, zirconium white, titanium oxide or magnesium oxide, preferred aluminum oxide, more preferably gama-alumina.
3) aging
Colloidal sol just wears out once forming, and promptly leaves standstill 1 hour to 3 weeks obtaining gel; Preferred 4 hours to 100 hours, more preferably 6 hours to 60 hours.
4) drying
Gel is carried out drying remove solvent, obtain the exsiccant gel; Described drying means preferably includes vacuum-drying, lyophilize, spraying drying, rotary evaporator or dry air; Described vacuum-drying is carried out under the pressure range of 10～550mmHg, described lyophilize in nitrogen or argon gas, temperature in is that 125 ℃～200 ℃ and temperature out are to carry out under 75 ℃～150 ℃, described rotary evaporator is to carry out under 25 ℃～90 ℃ temperature, the 10～760mmHg pressure range bathing temperature, and described dry air is to carry out in 25 ℃-90 ℃ temperature range;
5) calcining
The exsiccant gel was calcined 0.5～30 hour under 350 ℃～850 ℃ conditions, obtained solid super basic catalyst.
The temperature that calcining is carried out is generally 350 ℃～850 ℃, and preferred 400 ℃～700 ℃, more preferably 500 ℃～640 ℃.The time that calcining is carried out will be suitable for forming above-mentioned catalyzer.Usually, in order to obtain needed improved oxometallic acid salt catalyst, calcining was carried out 0.5～30 hour, preferred 1～25 hour, more preferably carried out 1～15 hour.In preferred operator scheme, calcining was undertaken by two stages.In the fs, sintering is 15 minutes～8 hours in the oxidative environment (for example air) of catalyzer under 200 ℃～400 ℃ preferred 275 ℃～325 ℃ temperature, preferred 1～3 hour.In subordinate phase, sintering is 15 minutes～48 hours in the non-oxidizable environment (for example rare gas element) of the material that will make the fs under 500 ℃～750 ℃ preferred 550 ℃～650 ℃, and preferred 1～24 hour, most preferably 2～10 hours.Described rare gas element is nitrogen, argon gas, xenon, helium or their mixture.Preferred rare gas element is xenon or nitrogen.
In particularly preferred Implementation Modes, will the incinerating material place in the needed oxidizing atmosphere at room temperature, be elevated to the fs calcining temperature then, and needed calcination time of lasting fs.Replacing former atmosphere with the needed non-oxidizing atmosphere of second calcination stage then is elevated to subordinate phase with temperature and calcines needed temperature and continue subordinate phase and calcine the needed time.
The invention has the beneficial effects as follows:
1, catalytic activity height, the reaction conditions gentleness; 2, target product selectivity is good, the product purity height, and per pass conversion can reach 90%, and product purity can reach 97%; 3, catalyzer easily separates with product, and technology is simple; 4, catalyzer is reusable, also can use continuously; 5, little to conversion unit corrodibility; 6 production costs are low, and economic benefit is good, so glycerine production epoxy chloropropane route has the bigger market competitiveness.
Embodiment
Embodiment 1
Under the stirring action, 5.02 gram calcium nitrate tetrahydrates are dissolved in 10.78 ml deionized water, continue to stir 60 minutes.The 180 ml deionized water solution that are dissolved with 8.33 gram salt of wormwood slowly are added drop-wise in the above-mentioned solution, and adding 5.02 restrains trolamines under stirring action, add the gama-alumina of the fully calcined mistake of 9.82 grams after fully being uniformly dispersed again, form white gelatinoid.Left standstill 72 hours in shady place under 20 ℃.With deionized water wash 5 times.By remove with rotary evaporator anhydrate after, with solid matter further dry a whole night in 25 ℃ vacuum drying oven, reclaim and obtain the 12g solid catalyst precursor.Then with this solid catalyst precursor calcining of 6g.Calcining is performed such, and solid matter is placed in the air atmosphere, is heated to 275 ℃ and keep 1 hour with the speed of 10 ℃/min in 275 ℃ air atmosphere then; Then air atmosphere is changed to argon gas and material is heated to 600 ℃ and this material was kept 2 hours with the speed of 2 ℃/min from 275 ℃ 800 ℃ of argon gas.Finally obtain granule type solid super alkaline catalysts CK1.
With the glycerine of 10 grams, 95% purity down, fed dry hydrogen chloride gas down continuously 2 hours in 100 ℃, obtain 12.5 and restrain dichlorohydrines at anhydrous acetic acid (consumption be equivalent to qualities of glycerin 10%).Join in 200 milliliters the round-bottomed flask of the 0.25 gram CK1 that puts well in advance again, install prolong and drying tube, be warming up to 80 ℃ of reactions 4 hours under stirring, stopped reaction obtains 9.1 gram epoxy chloropropane, its purity 95%.
Embodiment 2
To calcine in the following manner by the 6g solid catalyst precursor of embodiment 1 preparation: solid matter is placed in the air atmosphere, is heated to 275 ℃ and in 275 ℃ air atmosphere, kept 1 hour with the speed of 10 ℃/min then; Then air atmosphere is changed to argon gas and material is heated to 600 ℃ and this material was kept 5 hours with the speed of 2 ℃/min from 275 ℃ 600 ℃ of argon gas.Finally obtain granule type solid super alkaline catalysts CK2.
With the glycerine of 10 grams, 95% purity down, fed dry hydrogen chloride gas down continuously 2 hours in 100 ℃, obtain 12.5 and restrain dichlorohydrines at anhydrous acetic acid (consumption be equivalent to qualities of glycerin 10%).Join in 200 milliliters the round-bottomed flask of the 0.5 gram CK2 that puts well in advance again, install prolong and drying tube, be warming up to 70 ℃ of reactions 5 hours under stirring, stopped reaction obtains 9.2 gram epoxy chloropropane, its purity 96%.
Embodiment 3
Under the stirring action, with 5.26 gram calcium nitrate tetrahydrates, 1.68 gram SODIUMNITRATE and 0.84 gram Repone K are dissolved in 250 milliliters and go in the ethanol, continue to stir 30 minutes.The 200 ml deionized water solution that are dissolved with 10.26 gram yellow soda ash slowly are added drop-wise in the above-mentioned solution, and adding 7.21 restrains trolamines under stirring action, add the gama-alumina of the fully calcined mistake of 12.82 grams after fully being uniformly dispersed again, form white gelatinoid.Left standstill 72 hours in shady place under 20 ℃.With deionized water wash 5 times.By remove with rotary evaporator anhydrate after, with solid matter further dry a whole night in 25 ℃ vacuum drying oven, reclaim and obtain the 18g solid catalyst precursor.Then with this solid catalyst precursor calcining of 9g.Calcining is performed such, and solid matter is placed in the air atmosphere, is heated to 275 ℃ and keep 1 hour with the speed of 10 ℃/min in 275 ℃ air atmosphere then; Then air atmosphere is changed to argon gas and material is heated to 600 ℃ and this material was kept 2 hours with the speed of 2 ℃/min from 275 ℃ 800 ℃ of argon gas.Finally obtain granule type solid super alkaline catalysts CK3.
With the glycerine of 10 grams, 95% purity down, fed dry hydrogen chloride gas down continuously 2 hours in 100 ℃, obtain 12.5 and restrain dichlorohydrines at anhydrous acetic acid (consumption be equivalent to qualities of glycerin 10%).Join in 200 milliliters the round-bottomed flask of the 0.15 gram CK3 that puts well in advance again, install prolong and drying tube, be warming up to 80 ℃ of reactions 4 hours under stirring, stopped reaction obtains 8.9 gram epoxy chloropropane, its purity 96%.
Embodiment 4
To calcine in the following manner by the 9g solid catalyst precursor of embodiment 3 methods preparations: solid matter is placed in the air atmosphere, is heated to 275 ℃ and in 275 ℃ air atmosphere, kept 1 hour with the speed of 10 ℃/min then; Then air atmosphere is changed to argon gas and material is heated to 600 ℃ and this material was kept 15 hours with the speed of 2 ℃/min from 275 ℃ 600 ℃ of argon gas.Finally obtain granule type solid super alkaline catalysts CK4.
With the glycerine of 10 grams, 95% purity down, fed dry hydrogen chloride gas down continuously 3 hours in 100 ℃, obtain 12.5 and restrain dichlorohydrines at anhydrous acetic acid (consumption be equivalent to qualities of glycerin 10%).Join in 200 milliliters the round-bottomed flask of the 0.25 gram CK4 that puts well in advance again, install prolong and drying tube, be warming up to 90 ℃ of reactions 3 hours under stirring, stopped reaction obtains 8.8 gram epoxy chloropropane, its purity 97%.
Claims (10)
1, a kind of method of preparing epoxy chloropropane by using glycerol method may further comprise the steps:
A) with purity be 95% glycerine in the presence of anhydrous acetic acid, fed the dry hydrogen chloride gas precursor reactants of crossing continuously 1～3 hour down in 90～110 ℃, obtain dichlorohydrine;
B) dichlorohydrine that obtains is joined in the round-bottomed flask of the solid super basic catalyst of putting well in advance again, install prolong and drying tube, be warming up to 70～90 ℃ of reactions 3～5 hours under stirring, stopped reaction obtains epoxy chloropropane behind the filtering separation catalyzer.
2, the method for preparing epoxy chloropropane by using glycerol method according to claim 1, it is characterized in that steps A) described in the consumption of anhydrous acetic acid be 10% of glycerine weight, step B) described in the consumption of solid super basic catalyst be 1～5% of dichlorohydrine weight.
3, used solid super basic catalyst in the method for a kind of preparing epoxy chloropropane by using glycerol method according to claim 1, it is characterized in that: this solid super basic catalyst is made up of alkaline earth metal oxide and alkalimetal oxide and porous carrier, described alkaline-earth metal is magnesium (Mg), calcium (Ca), in strontium (Sr) and the barium (Ba) one or more, described basic metal is lithium (Li), sodium (Na), in potassium (K) and the rubidium (Rb) one or more, wherein the mol ratio of basic metal and alkaline-earth metal is not more than 2, and the consumption of porous carrier is 100～200% of alkalimetal oxide and an alkaline earth metal oxide gross weight.
4, solid super basic catalyst according to claim 3 is characterized in that described porous carrier is gac, calcined hydrotalcite, aluminum oxide, zirconium white, titanium oxide or magnesium oxide.
5, the preparation method of used solid super basic catalyst in the method for a kind of preparing epoxy chloropropane by using glycerol method according to claim 1 is characterized in that step is as follows:
1) dissolving
All be dissolved in alkaline earth metal oxide, alkalimetal oxide in the polar solvent, form saturated alkaline-earth metal salt solution, alkali metal salt soln, described alkaline-earth metal is one or more in magnesium (Mg), calcium (Ca), strontium (Sr) and the barium (Ba), described basic metal is one or more in lithium (Li), sodium (Na), potassium (K) and the rubidium (Rb), wherein the mol ratio of basic metal and alkaline-earth metal is not more than 2, and described polar solvent is water or alcohol;
2) become glue
Under the violent stirring effect, above-mentioned two kinds of saturated alkaline-earth metal salt solutions, alkali metal salt soln blending dispersion are even, and add 10～100% organic compound of alkaline-earth metal and alkali-metal weight, after mixing, 100～200% the porous carrier that adds alkaline-earth metal and alkali-metal weight again floods, after to be impregnated being uniformly dispersed, removing under 0～200 ℃ of temperature and desolvate, making the colloidal solid product is colloidal sol;
3) aging
Colloidal sol just wears out once forming, and promptly leaves standstill 1 hour to 3 weeks obtaining gel;
4) drying
Gel is carried out drying remove solvent, obtain the exsiccant gel;
5) calcining
The exsiccant gel was calcined 0.5～30 hour under 350 ℃～850 ℃ conditions, obtained solid super basic catalyst.
6, the preparation method of solid super basic catalyst according to claim 5 is characterized in that the alcohol described in the step 1) dissolving is methyl alcohol, ethanol, propyl alcohol, ethylene glycol or propylene glycol; Step 2) becoming the organic compound described in the glue is one or more mixture in tensio-active agent, organic amine compound, polyoxyethylene glycol, polyvinyl alcohol, glucose or the starch, and described porous carrier is gac, calcined hydrotalcite, aluminum oxide, zirconium white, titanium oxide or magnesium oxide; Time of repose described in step 3) is aging is 4 hours to 100 hours; Drying means described in the step 4) drying comprises vacuum-drying, lyophilize, spraying drying, rotary evaporator or dry air; Calcining temperature described in the step 5) calcining is 400 ℃-700 ℃, and calcination time is 1～25 hour.
7, the preparation method of solid super basic catalyst according to claim 6 is characterized in that step 2) to become the organic amine compound described in the glue be trolamine, described porous carrier is an aluminum oxide; Time of repose described in step 3) is aging is 6 hours to 60 hours; The dry described vacuum-drying of step 4) is carried out under the pressure range of 10～550mmHg, described lyophilize in nitrogen or argon gas, temperature in is that 125 ℃～200 ℃ and temperature out are to carry out under 75 ℃～150 ℃, described rotary evaporator is to carry out under 25 ℃～90 ℃ temperature, the 10～760mmHg pressure range bathing temperature, and described dry air is to carry out in 25 ℃-90 ℃ temperature range; Calcining temperature described in the step 5) calcining is 500 ℃～640 ℃, and calcination time is 1～15 hour.
8, the preparation method of solid super basic catalyst according to claim 7 is characterized in that step 2) to become the aluminum oxide described in the glue be gama-alumina.
9, the preparation method of the described solid super basic catalyst of claim 5 is characterized in that the calcining described in the step 5) calcining undertaken by two stages, and the fs, sintering is 15 minutes～8 hours in the air of catalyzer under 200 ℃～400 ℃ temperature; Subordinate phase, sintering is 15 minutes～48 hours in the rare gas element of the material that will make the fs under 500 ℃～750 ℃, and described rare gas element is nitrogen, argon gas, xenon, helium or their mixture.
10, the preparation method of the described solid super basic catalyst of claim 9 is characterized in that the fs described in the step 5) calcining is a sintering 1～3 hour in the air of catalyzer under 275 ℃～325 ℃ temperature; Subordinate phase is sintering in the rare gas element of material under 550 ℃～650 ℃ that will make the fs 1～24 hour, and described rare gas element is nitrogen or xenon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100194562A CN100513401C (en) | 2007-01-25 | 2007-01-25 | Method for preparing epoxy chloropropane by using glycerol method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100194562A CN100513401C (en) | 2007-01-25 | 2007-01-25 | Method for preparing epoxy chloropropane by using glycerol method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101003523A true CN101003523A (en) | 2007-07-25 |
| CN100513401C CN100513401C (en) | 2009-07-15 |
Family
ID=38702946
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100194562A Expired - Fee Related CN100513401C (en) | 2007-01-25 | 2007-01-25 | Method for preparing epoxy chloropropane by using glycerol method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100513401C (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010295A (en) * | 2010-11-12 | 2011-04-13 | 珠海长先化学科技有限公司 | Method for preparing dichloropropanol by glycerol method |
| CN102030724A (en) * | 2010-11-12 | 2011-04-27 | 珠海长先化学科技有限公司 | Method for producing epoxy chloropropane by preparing hydrogen chloride |
| CN103709124A (en) * | 2013-12-06 | 2014-04-09 | 中国天辰工程有限公司 | Method for producing epoxy chloropropane |
| CN104059031A (en) * | 2014-06-20 | 2014-09-24 | 中国天辰工程有限公司 | Method for removing gas phase hydrogen chloride from dichloropropanol to produce epichlorohydrin |
| CN104370857A (en) * | 2014-11-11 | 2015-02-25 | 常州大学 | Synthesis method of epoxy chloropropane |
| CN104592165A (en) * | 2014-12-26 | 2015-05-06 | 南京大学 | Method for producing epoxy chloropropane by gas-phase saponification of dichloropropanol |
| CN105153067A (en) * | 2015-08-28 | 2015-12-16 | 江苏大学 | Method for preparing epichlorohydrin and magnesium chloride |
| CN105566253A (en) * | 2014-10-11 | 2016-05-11 | 中科院大连化学物理研究所淮安化工新材料研究中心 | Method for synthesizing chloropropylene oxide from glycerin |
| CN108514872A (en) * | 2018-04-09 | 2018-09-11 | 太原理工大学 | A kind of preparation method for carbon nanotube base metal catalysts |
| CN113480496A (en) * | 2021-06-09 | 2021-10-08 | 江苏瑞恒新材料科技有限公司 | Comprehensive utilization method of epoxy chloropropane by-product by hydrogen peroxide method |
| CN113831304A (en) * | 2021-10-09 | 2021-12-24 | 江苏索普工程科技有限公司 | Method for efficiently preparing epoxy chloropropane through biomass glycerol |
| CN118527137A (en) * | 2024-07-23 | 2024-08-23 | 山东海科创新研究院有限公司 | Molybdenum-bismuth supported catalyst for synthesizing epoxypropane, preparation method and application |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792424B (en) * | 2010-04-06 | 2012-02-29 | 山东海力化工股份有限公司 | Environment-friendly preparation process for producing epoxy chloropropane by complexation and extraction |
-
2007
- 2007-01-25 CN CNB2007100194562A patent/CN100513401C/en not_active Expired - Fee Related
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030724A (en) * | 2010-11-12 | 2011-04-27 | 珠海长先化学科技有限公司 | Method for producing epoxy chloropropane by preparing hydrogen chloride |
| CN102030724B (en) * | 2010-11-12 | 2012-07-18 | 珠海长先化学科技有限公司 | Method for producing epoxy chloropropane by preparing hydrogen chloride |
| CN102010295B (en) * | 2010-11-12 | 2013-05-01 | 珠海长先化学科技有限公司 | Method for preparing dichloropropanol by glycerol method |
| CN102010295A (en) * | 2010-11-12 | 2011-04-13 | 珠海长先化学科技有限公司 | Method for preparing dichloropropanol by glycerol method |
| CN103709124A (en) * | 2013-12-06 | 2014-04-09 | 中国天辰工程有限公司 | Method for producing epoxy chloropropane |
| CN104059031A (en) * | 2014-06-20 | 2014-09-24 | 中国天辰工程有限公司 | Method for removing gas phase hydrogen chloride from dichloropropanol to produce epichlorohydrin |
| CN105566253A (en) * | 2014-10-11 | 2016-05-11 | 中科院大连化学物理研究所淮安化工新材料研究中心 | Method for synthesizing chloropropylene oxide from glycerin |
| CN104370857A (en) * | 2014-11-11 | 2015-02-25 | 常州大学 | Synthesis method of epoxy chloropropane |
| CN104592165B (en) * | 2014-12-26 | 2017-01-18 | 南京大学 | Method for producing epoxy chloropropane by gas-phase saponification of dichloropropanol |
| CN104592165A (en) * | 2014-12-26 | 2015-05-06 | 南京大学 | Method for producing epoxy chloropropane by gas-phase saponification of dichloropropanol |
| CN105153067A (en) * | 2015-08-28 | 2015-12-16 | 江苏大学 | Method for preparing epichlorohydrin and magnesium chloride |
| CN105153067B (en) * | 2015-08-28 | 2017-06-27 | 江苏大学 | A kind of method for preparing epoxychloropropane and magnesium chloride |
| CN108514872A (en) * | 2018-04-09 | 2018-09-11 | 太原理工大学 | A kind of preparation method for carbon nanotube base metal catalysts |
| CN108514872B (en) * | 2018-04-09 | 2021-04-20 | 太原理工大学 | Preparation method of alkali metal catalyst for carbon nano tube |
| CN113480496A (en) * | 2021-06-09 | 2021-10-08 | 江苏瑞恒新材料科技有限公司 | Comprehensive utilization method of epoxy chloropropane by-product by hydrogen peroxide method |
| CN113831304A (en) * | 2021-10-09 | 2021-12-24 | 江苏索普工程科技有限公司 | Method for efficiently preparing epoxy chloropropane through biomass glycerol |
| CN118527137A (en) * | 2024-07-23 | 2024-08-23 | 山东海科创新研究院有限公司 | Molybdenum-bismuth supported catalyst for synthesizing epoxypropane, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100513401C (en) | 2009-07-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100513401C (en) | Method for preparing epoxy chloropropane by using glycerol method | |
| CN109942827B (en) | Method for modifying covalent organic framework material | |
| CN107855130A (en) | A kind of solar energy fixed nitrogen photochemical catalyst and application thereof and preparation method | |
| CN107335454B (en) | Load type Pd3Preparation and application of Cl cluster catalyst | |
| CN111250074B (en) | Method for synthesizing MOF derivative semiconductor heterojunction material by solvothermal method | |
| CN102060760B (en) | Preparation method of N-pyridine oxide | |
| CN108706565A (en) | A kind of preparation method of difluorophosphate | |
| KR101793530B1 (en) | Catalyst for producing glycerol carbonate from glycerol and carbon dioxide and preparation method of the same | |
| CN111004205A (en) | Synthetic method for preparing piperonyl butoxide under catalysis of composite alkali | |
| CN102718624A (en) | Method for synthesizing triphenylchloromethane | |
| CN108586390A (en) | The method that dichlorohydrin prepares epoxychloropropane | |
| CN101899012B (en) | Method for improving synthesis process of Acipimox | |
| CN104447531B (en) | Preparation method of 3,5-dibromopyridine-N-oxide | |
| CN114957207A (en) | Application of water-soluble photocatalyst in photocatalytic reaction | |
| CN111203267B (en) | Solid acid catalyst for catalyzing decarboxylation of gamma-valerolactone to prepare butene, and preparation method and application thereof | |
| CN105732487B (en) | A kind of metal organic frame containing five core ytterbium cluster molecule construction units and its preparation method and application | |
| JP2023520547A (en) | Method for producing catalyst for dehydration reaction of 3-hydroxypropionic acid, catalyst for dehydration reaction of 3-hydroxypropionic acid, and method for producing acrylic acid using the same | |
| CN113149827A (en) | Method for synthesizing alkynoic acid by using terminal alkyne and carbon dioxide | |
| CN108043442B (en) | Carbon-supported ruthenium nano material, preparation method thereof and application of carbon-supported ruthenium nano material in catalyzing reaction of alcohol and aromatic diamine | |
| CN105001049A (en) | Preparation method for abietic acid derivative | |
| CN114558596B (en) | Preparation method of metal doped titanium pyrophosphate composite material, product and application thereof | |
| CN110078733B (en) | Double-functionalized alkaline ionic liquid catalyst and preparation method and application thereof | |
| CN106045847A (en) | Preparation method of oxandrolone intermediate of 17beta-hydroxyl-17alpha-methyl-1-oxo-1,2-open loop-A nor-5alpha-androstane-2-oxygen-containing carboxylic acid | |
| CN102633624A (en) | Method for preparing methylcinnamic acid | |
| CN118164832B (en) | Preparation method of 1, 6-hexanedialdehyde |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090715 Termination date: 20100225 |