CN102030724B - Method for producing epoxy chloropropane by preparing hydrogen chloride - Google Patents
Method for producing epoxy chloropropane by preparing hydrogen chloride Download PDFInfo
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- CN102030724B CN102030724B CN2010105430101A CN201010543010A CN102030724B CN 102030724 B CN102030724 B CN 102030724B CN 2010105430101 A CN2010105430101 A CN 2010105430101A CN 201010543010 A CN201010543010 A CN 201010543010A CN 102030724 B CN102030724 B CN 102030724B
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- epoxy chloropropane
- phosphorus
- hydrogen chloride
- glycerine
- hydrogenchloride
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Abstract
The invention discloses a method for preparing epoxy chloropropane by a glycerol process with self-prepared hydrogen chloride. The method comprises the following steps of: generating a large amount of continuous and stable hydrogen chloride gas by polychlorinated phosphorus and hydrochloric acid or water which serve as raw materials in the process of controlling temperature and time; reacting the hydrogen chloride gas with heating glycerol under the action of a catalyst to produce dichloropropanol and a small amount of chloropropanol; and saponifying the rectified and purified dichloropropanol and an alkali to obtain the epoxy chloropropane. By the method, the epoxy chloropropane is produced by a glycerol method without relying on chlor-alkali enterprises, so that the requirement of supplying a downstream reaction from an upstream reaction continuously and stably is met, generated by-products have high added value, and in the method, a pollution-free, clean and environmentally-friendly production mode is adopted.
Description
Technical field
The present invention relates to produce the method for epoxy chloropropane, relate in particular to a kind of a large amount of production decision of continous-stable that hydrogenchloride is applied to the industry of glycerine production epoxy chloropropane with the hydrogenchloride of preparation.
Background technology
Producing epoxy chloropropane with biodiesel byproduct article glycerine is a kind of production technique of low-carbon (LC) less energy-consumption environmental protection; The main developing direction of representing following epoxy chloropropane to produce; But one of this industrial main raw material is a hydrogen chloride gas, only under the situation that a large amount of hydrogen chloride gas steady and continuous supplies are arranged, could realize glycerine method production epoxy chloropropane.Therefore; The a large amount of hydrogen chloride gas that utilize chlor-alkali production enterprise to produce; Near chlor-alkali plant, setting up the glycerine method to produce the epoxy chloropropane device is can stablize to obtain hydrogen chloride gas in large quantities; But because chlor-alkali plant is a high pollution high energy-consuming enterprises, have a lot of places that the existence of chlor-alkali plant can not be arranged in China, therefore producing epoxy chloropropane in the place that does not have chlor-alkali enterprise with the glycerine method becomes an impassable difficult problem.If adopt steel cylinder transportation hydrogenchloride to exist cost high, dangerous, therefore, how cheapness obtains hydrogenchloride continuously in large quantities, just becomes the glycerine method and produces the key issue that can epoxy chloropropane technology build in non-chlor-alkali enterprise location.Sub product hydrogenchloride when having the factory that produces phosphorous acid to produce phosphorous acid falls as a kind of industry waste disposal, has wasted the part of its value added that has virtually.
Summary of the invention
The present invention provides a kind of and can steady and continuous produce hydrogen chloride gas in a large number for addressing the above problem, and brings a lot of useful sub products simultaneously, and productive rate is high, the hydrogenchloride industrial process of safely cleaning.
Technical scheme of the present invention is: the method that a kind of continuous generation hydrogenchloride is produced epoxy chloropropane with supply glycerine; It is characterized in that; With phosphorus trichloride or phosphorus pentachloride and hydrochloric acid is main raw material, utilizes phosphorus trichloride or phosphorus pentachloride hydrolysis to produce hydrogen chloride gas, comprising following steps:
Step 1: in reactor drum, add hydrochloric acid or water; The mode that is hydrolyzed through continuous adding phosphorus trichloride or phosphorus pentachloride makes it produce hydrogen chloride gas continuously; Temperature is controlled at below 80 ℃ during reaction; Best scope is 60 ℃-80 ℃, constantly draws hydrogen chloride gas in the reactor drum upper port, collects through gas trap;
Step 2: the continuous feeding of hydrogen chloride gas is added with in the glycerine of catalyzer, and reaction generates a dichlorohydrine and a propylene chlorohydrin mixture under 60 ℃～130 ℃ temperature, is mainly dichlorohydrine;
Step 3: carry out saponification with alkali behind the rectification and purification dichlorohydrine and promptly obtain epoxy chloropropane.
The mol ratio of phosphorus trichloride or phosphorus pentachloride and water or hydrochloric acid is 1: 0.5～1.5, and optimum range is that the mol ratio of phosphorus trichloride or phosphorus pentachloride and water or hydrochloric acid is 1: 1.
Said glycerin catalytic agent mixed solution constantly stirs glycerine in the process of heating and insulation, and the temperature of glycerin liquid remains on 90 ℃-125 ℃ in entire reaction course, and wherein the best temperature scope is 90 ℃-125 ℃.
Said many phosphorus chloride is phosphorus trichloride and phosphorus pentachloride, with phosphorus trichloride coproduction sub product phosphorous acid, with phosphorus pentachloride coproduction sub product phosphoric acid.
Said reactor drum makes its continuous hydrolysis produce the reactor drum of hydrogenchloride in realizing phosphorus trichloride or phosphorus pentachloride and hydrochloric acid or water mixed by a certain percentage in order, and the reactor drum of override use is many mouthfuls of reaction kettles and injection reactor.
The invention has the beneficial effects as follows: break away from by this method and rely on chlor-alkali enterprise production hci and come with glycerine method production epoxy chloropropane; Constantly supply the needs of downstream reaction continuously and stably from upstream reaction, the sub product value added of generation is high, not pollute be the mode of production of cleaning ambient syntonic type.
Embodiment
In order to make the object of the invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with reaching embodiment.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
Embodiment 1:
Step 1: in reactor drum, add concentrated hydrochloric acid 30kg and be put in 60 liters the reaction kettle; The mode that is hydrolyzed through continuous adding phosphorus trichloride makes it produce hydrogen chloride gas continuously, and the intermediary outlet connects whisking appliance, and another one mouth tipping 48kg phosphorus trichloride drips sealed can; The mouth on top connects 100 liters hydrogen chloride gas receiving flask; Upper port at reactor drum is constantly drawn hydrogen chloride gas, and in this process, temperature is controlled at 60 ℃-80 ℃ during reaction.The time that control drips is approximately 18 hours, continues to stir to make hydrogen chloride gas overflow more thoroughly in 2 hours.
Step 2: reaction generates a dichlorohydrine and a propylene chlorohydrin mixture under 60 ℃～130 ℃ temperature, is mainly dichlorohydrine;
Step 3: carry out saponification with alkali behind the rectification and purification dichlorohydrine and promptly obtain epoxy chloropropane.
The mol ratio of phosphorus trichloride or phosphorus pentachloride and water or hydrochloric acid is 1: 0.5～1: 1.5, and optimum range is that the mol ratio of phosphorus trichloride or phosphorus pentachloride and water or hydrochloric acid is 1: 1.
Said many phosphorus chloride is phosphorus trichloride and phosphorus pentachloride, with phosphorus trichloride coproduction sub product phosphorous acid, with phosphorus pentachloride coproduction sub product phosphoric acid.
Said reactor drum constantly adds phosphorus trichloride or phosphorus pentachloride in hydrochloric acid or the water for realizing, makes its continuous hydrolysis produce the reactor drum of hydrogenchloride, and the reactor drum that override uses is many mouthfuls of reaction kettles and injection reactor.
Reaction finishes, and takes by weighing that phosphorous acid mixed solution amount is about 32kg in the reaction flask, calculates that actual to produce hydrogenchloride be 46kg, and theoretical hydrogenchloride output 49kg, hydrogenchloride yield reach 94%, and its dichloropropanol content of glycerine reaction liquid mensuration is 70%.
Embodiment 2:
Step 1: phosphorus pentachloride 43kg is put into 60 liters of three mouthfuls of reaction kettles, and middle port connects whisking appliance, and a mouth tipping 29kg concentrated hydrochloric acid drips sealed can, and a mouth connects 100 liters of hydrogen chloride gas receiving flasks; There is an outlet to connect receiving flask and leads in 60 liters of four-hole reactor drums of the 35kg glycerine that is added with catalyzer, concentrated hydrochloric acid is added drop-wise in the phosphorus pentachloride, notice that control hydrochloric acid solution hydrolysis temperature is at 60 ℃-80 ℃.
Step 2: when phosphorus pentachloride becomes liquid; Begin to stir; The time that control drips is approximately 18 hours, continues to stir to make hydrogenchloride overflow more thoroughly in 2 hours, and the hydrogenchloride that produces is passed in the glycerine of continuous stirring heating; Reaction generates a dichlorohydrine and an a small amount of propylene chlorohydrin mixture under 60 ℃～130 ℃ temperature, and the optimum temps of glycerine reaction is controlled at 90 ℃-125 ℃;
Step 3: carry out good fortune in alkali behind the rectification and purification dichlorohydrine and can obtain epoxy chloropropane.
Reaction finishes, and takes by weighing in the reaction flask phosphoric acid and mixes liquid measure and be about 26.3kg, calculates that actual to produce hydrogenchloride be 45.7kg, and theoretical hydrogenchloride output 48.3kg, hydrogenchloride yield reach 94.6%, and its dichloropropanol content of glycerine reaction liquid mensuration is 70%.
Visible by top two embodiment, phosphorus trichloride and phosphorus pentachloride and concentrated hydrochloric acid hydrolysis, hydrolysis hydrogen chloride gas yield is about 94%; Phosphorus trichloride is owing to be liquid; Simple during reaction, but the open-air moisture absorption produces acid mist, and certain risk is arranged; Phosphorus pentachloride is a crystal, and the storage transportation is also more comparatively safe.
The above is merely preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of within spirit of the present invention and principle, being done, is equal to and replaces and improvement etc., all should be included within the protection domain of the utility model.
Claims (7)
1. one kind produces continuously the method that hydrogenchloride is produced epoxy chloropropane with supply glycerine, it is characterized in that, and be main raw material with phosphorus trichloride, phosphorus pentachloride and hydrochloric acid, utilize phosphorus trichloride, phosphorus pentachloride hydrolysis to produce hydrogen chloride gas, comprising following steps:
Step 1: in reactor drum, add hydrochloric acid or water; The mode that is hydrolyzed through continuous adding phosphorus trichloride, phosphorus pentachloride makes it produce hydrogen chloride gas continuously; Temperature is controlled at 60 ℃-80 ℃ during reaction, constantly draws hydrogen chloride gas in the reactor drum upper port, collects through gas trap;
Step 2: the continuous feeding of hydrogen chloride gas is added with in the glycerine of catalyzer, and reaction generates a dichlorohydrine and a propylene chlorohydrin mixture under 60 ℃～130 ℃ temperature, is mainly dichlorohydrine;
Step 3: carry out saponification with alkali behind the rectification and purification dichlorohydrine and promptly obtain epoxy chloropropane.
2. the method for producing epoxy chloropropane according to the said continuous generation hydrogenchloride of claim 1 with supply glycerine is characterized in that the mol ratio of phosphorus trichloride or phosphorus pentachloride and water or hydrochloric acid is 1: 0.5～1: 1.5.
3. the method for producing epoxy chloropropane according to the said continuous generation hydrogenchloride of claim 2 with supply glycerine is characterized in that the mol ratio of phosphorus trichloride or phosphorus pentachloride and water or hydrochloric acid is 1: 1
4. the method for producing epoxy chloropropane according to the said continuous generation hydrogenchloride of claim 1 with supply glycerine; It is characterized in that; Said glycerin catalytic agent mixed solution constantly stirs glycerine in the process of heating and insulation, and the temperature of glycerin liquid remains on 90 ℃-125 ℃ in entire reaction course.
5. the method for producing epoxy chloropropane according to the said continuous generation hydrogenchloride of claim 1-4 with supply glycerine; It is characterized in that; Said many phosphorus chloride is phosphorus trichloride and phosphorus pentachloride, with phosphorus trichloride coproduction sub product phosphorous acid, with phosphorus pentachloride coproduction sub product phosphoric acid.
6. the method for producing epoxy chloropropane according to the said continuous generation hydrogenchloride of claim 1 with supply glycerine; It is characterized in that; Said reactor drum makes the reactor drum of its continuous hydrolysis generation hydrogenchloride in realizing phosphorus trichloride or phosphorus pentachloride and hydrochloric acid or water mixed by a certain percentage in order.
7. produce the method that hydrogenchloride is produced epoxy chloropropane with supply glycerine continuously according to claim 6, it is characterized in that said reactor drum is many mouthfuls of reaction kettles and injection reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2010105430101A CN102030724B (en) | 2010-11-12 | 2010-11-12 | Method for producing epoxy chloropropane by preparing hydrogen chloride |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010105430101A CN102030724B (en) | 2010-11-12 | 2010-11-12 | Method for producing epoxy chloropropane by preparing hydrogen chloride |
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| CN102030724A CN102030724A (en) | 2011-04-27 |
| CN102030724B true CN102030724B (en) | 2012-07-18 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102250046B (en) * | 2011-06-12 | 2013-12-25 | 珠海长先化学科技有限公司 | System for producing epoxy chloropropane through glycerine method |
| CN109879748A (en) * | 2019-04-08 | 2019-06-14 | 常州市武进永升化工有限公司 | A kind of production technology of 3- chlorpromazine chloride |
| CN112142690A (en) * | 2020-10-22 | 2020-12-29 | 丹阳市助剂化工厂有限公司 | Process for producing epichlorohydrin by using chlorinated paraffin and chlorine-containing tail gas glycerin method |
| CN113247862A (en) * | 2021-06-18 | 2021-08-13 | 湖北和远气体股份有限公司 | High-purity electronic-grade hydrogen chloride production device and process |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003523A (en) * | 2007-01-25 | 2007-07-25 | 中国林业科学研究院林产化学工业研究所 | Method for preparing epoxy chloropropane by using glycerol method |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003523A (en) * | 2007-01-25 | 2007-07-25 | 中国林业科学研究院林产化学工业研究所 | Method for preparing epoxy chloropropane by using glycerol method |
Non-Patent Citations (1)
| Title |
|---|
| 辜高龙.以甘油和工业盐酸为原料合成环氧氯丙烷新工艺.《精细化工中间体》.2008,第38卷(第4期),49-52. * |
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