CN101693646A - Process for preparing dichloropropanol through glycerol chlorination method - Google Patents
Process for preparing dichloropropanol through glycerol chlorination method Download PDFInfo
- Publication number
- CN101693646A CN101693646A CN 200910211171 CN200910211171A CN101693646A CN 101693646 A CN101693646 A CN 101693646A CN 200910211171 CN200910211171 CN 200910211171 CN 200910211171 A CN200910211171 A CN 200910211171A CN 101693646 A CN101693646 A CN 101693646A
- Authority
- CN
- China
- Prior art keywords
- resin
- acid
- reaction
- carboxylic acid
- water
- 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)
Abstract
A process for preparing dichloropropanol through a glycerol chlorination method belongs to a preparation process of dichloropropanol in the field of chemical engineering. Under the catalytic action of water-absorbing strong acid type macromolecule resins or resins and carboxylic acid composite catalysts, the method prepares the dichloropropanol by the reaction of glycerol and gaseous hydrogen chloride, adds the glycerol and the catalysts into a reaction kettle with stirrers to be heated and reacted and leads hydrogen chloride gas into the reaction kettle at a certain speed. When the weight of reaction liquid is increased to 150%, water is removed by conducting reduced pressure distillation; the hydrogen chloride gas is further led into the reaction liquid at a certain speed after water removal, reduced pressure distillation and water removal are conducted again, crude products are obtained by continuously conducting reduced pressure distillation, and the dichloropropanol is obtained by further fractional distillation and collecting fractions. The process has the advantages of high yield, moderate reaction condition, rapid reaction speed, non-corrosiveness, no produced waste acid liquid, easy separation for products, high selectivity, repeated use and the like.
Description
Technical field
The invention belongs to the preparation method of chemical field dichlorohydrine, particularly relate to a kind of method of process for preparing dichloropropanol through glycerol chlorination, this method can also prepare glycerine monochlorohydrin in the preparation dichlorohydrine.
Background technology
Dichlorohydrine claims DCP again, is the key intermediate of producing epoxy chloropropane, and industrial epoxy chloropropane all is to form with dichlorohydrine cyclisation under alkaline condition, so the production technology of dichlorohydrine is determining the production technology of epoxy chloropropane.The method of producing dichlorohydrine in the world wide mainly contains three kinds of propylene high-temperature chlorination processs, propylene acetate method, glycerin chlorination method.Propylene high-temperature chlorination process and propylene acetate method are very sophisticated production methods, the both is to be starting raw material with petroleum cracking product propylene, along with rising violently of the in short supply and oil price of petroleum resources, production cost is more and more higher, will be replaced by the glycerin chlorination method of rising in recent years.The glycerin chlorination method is that the by-product glycerol with biofuel is the raw material production dichlorohydrine, broken away from dependence to petroleum resources, and 21 century countries in the world all the development biofuel, the mass production of biofuel, cause coproduction glycerine price sharply to descend, therefore the glycerin chlorination method produces that the method for dichlorohydrine is inexpensive with raw material, advantages such as working condition is gentle, by product is few, productive rate height become the technology that each big chemical company of the world in recent years competitively researchs and develops, and also becomes the focus of research.The ultimate principle that the glycerin chlorination method is produced dichlorohydrine is under the effect of catalyzer carboxylic acid or derivatives thereof, and glycerine and hydrogenchloride or hydrochloric acid reaction generate dichlorohydrine, and reaction equation is:
Can be directly after products therefrom distillation dewaters under alkaline condition cyclisation prepare epoxy chloropropane, also can be further purified dichlorohydrine.
Czech chemical metallurgy company has announced with acetic acid in its patent WO2005021476 (or CN1845888A) and made catalyzer, a kind of continuous reaction process that glycerine and hydrogen chloride gas react in bubbler.The method that German Patent proposes for No. 1973081906 is a catalyzer with acetic acid or propionic acid.Solvay company has announced a kind of in its patent WO2005054167 (or Fr2862644) and the similar technology of Czech chemical metallurgy house journal, different is that its preferred catalyzer is not volatile hexanodioic acid, the loss of catalyzer is little, be gas and liquid reactants countercurrent flow in addition, the hydrogenchloride utilization ratio improves.On the whole, mostly make catalyzer in the technology of glycerine method production dichlorohydrine, remove the water that generates in the reaction process, reduce generating the restraining effect of water reaction by improving technical process or gas-liquid reactor structure with acetic acid.When selecting carboxylic-acid catalyzer such as acetic acid for use, these carboxylic acids are low or water-soluble strong because of boiling point, can steam with water in the process that distillation dewaters, leave reaction system, cause catalyst loss big, be difficult to recycle, strengthened the difficulty of production cost and last handling process.Jiangsu Yang Nong chemical industry discloses a kind of organic nitriles substance that is different from carboxylic acid and has made catalyzer in its patent CN101029000A, its effect and carboxylic-acid are suitable, but its boiling point is higher than the carboxylic-acid substance, in the use loss little, be convenient to reclaim and apply mechanically.Therefore, two hang-ups that prior art need solve are: the novel catalyzer of (1) research, and require not only excellent catalytic effect of catalyzer, and in use loss is little, and is easy to separate with product, be easy to regeneration, so that recycle; (2) adopt certain method in time to remove the water that generates in the reaction process, reduce generating the restraining effect of water, improve reaction to the irreversible degree that generates the dichlorohydrine direction to reaction.
Summary of the invention
Goal of the invention of the present invention is at problems of the prior art, a kind of method for preparing dichlorohydrine with glycerine and hydrogenchloride is provided, as catalyzer, or the combination of absorptive strong acid type macromolecule resin and high boiling point carboxylic acid is as catalyzer with absorptive strong acid type macromolecule resin for this method.
Realize the foregoing invention purpose by the following technical solutions:
A kind of method of process for preparing dichloropropanol through glycerol chlorination is characterized in that, under the katalysis of water-absorbent strong acid type macromolecule resin or resin and carboxylic acid combination catalyst, prepares dichlorohydrine with glycerine and gasiform hcl reaction, and its preparation method is:
A, water-absorbent strong acid type macromolecule resin catalyst consumption are: the mass ratio of water-absorbent strong acid type macromolecule resin and glycerine is 0.1～50, and suitable is 0.1～25, preferred 2～15;
B, resin and carboxylic acid combination catalyst consumption are: the mass ratio of water-absorbent strong acid type macromolecule resin and glycerine is 2～50; The mol ratio of carboxylic acid and glycerine is 0.01～1, and suitable is 0.01～0.5, preferred 0.01～0.1;
C, glycerine and catalyzer are joined reacting by heating in the reactor that has stirring, temperature of reaction is 20～300 ℃, suitable temperature of reaction is 50～140 ℃, preferred 70～115 ℃, this is reflected under the normal pressure and carries out, and the reaction times is 2～8 hours, feeds hydrogen chloride gas according to certain speed then, when reaction solution weightening finish to 150% the time, underpressure distillation dewaters;
D, the reaction solution after dewatering feed hydrogen chloride gas again according to certain speed, be reaction end when the weight of reaction solution no longer increases, underpressure distillation dewaters, and continues underpressure distillation again and gets crude product, fractionation again, collect 95-105 ℃ of (1.33-2.67kPa) cut and get dichlorohydrine, comprise two kinds of isomer, 1,3-dichlorohydrine and 2, the 3-dichlorohydrine is mainly 1, the 3-dichlorohydrine.
The water-absorbent strong acid type macromolecule resin that the present invention uses is strong solid acid catalyst, it is the reaction of catalyzing glycerol and hydrogenchloride effectively, and following outstanding advantage is arranged: (1) is because it is a kind of absorbent resin, therefore the water that produces in can absorption reaction process in time, reduced in the reaction system because the restraining effect of the generation of water reacting, promoted reaction to move to the direction that generates dichlorohydrine, improved transformation efficiency, if reasonable in design even usable resins is adsorbed the water of generation fully, also can save the step that distillation dewaters.(2) because it is a solid catalyst, reaction can not mix with product after finishing, and is easy to separate with product, only need simple process get final product reuse, can cause the loss of catalyzer hardly, greatly reduce production cost in use, having reduced waste liquid amount, is a kind of ideal environment-friendly type catalyzer.
Compare with the liquid acid catalyst that existing bibliographical information is adopted, the water-absorbent acid type macromolecule resin catalyzer that the present invention uses has following advantage: (1) productive rate height, reaction conditions gentleness, speed of response are fast; (2) non-corrosiveness, do not produce spent acid solution, product is easily separated, selectivity is high, can repeatedly use repeatedly; (3) simplify production operation, reduced waste liquid amount, reduced production cost, be more suitable for large-scale industrial continuous production.
Even when the combination of water-absorbent acid type macromolecule resin and organic carboxyl acid is used as catalyzer, can not influence above-mentioned advantage yet, because when both make up, strengthened catalytic effect separately mutually, and because the boiling point of organic carboxyl acid is higher than dichlorohydrine, can not steam, so can recycle with resin with product.
Embodiment
The present invention is described in further detail below in conjunction with specific embodiment.
Present embodiment is a kind of method of process for preparing dichloropropanol through glycerol chlorination, the technological process that is adopted is: glycerine and catalyzer are joined in the reactor that has stirring, and heating feeds hydrogen chloride gas according to certain speed then, when reaction solution weightening finish to 150% the time, underpressure distillation dewaters.Reaction solution after dewatering feeds hydrogen chloride gas again according to certain speed, be reaction end when the weight of reaction solution no longer increases, underpressure distillation dewaters, and continues underpressure distillation again and gets crude product, fractionation again, collect 95-105 ℃ of (1.33-2.67kPa) cut and get dichlorohydrine, comprise two kinds of isomer, 1,3-dichlorohydrine and 2, the 3-dichlorohydrine is mainly 1, the 3-dichlorohydrine.
In the time of when producing dichlorohydrine, can also producing glycerine monochlorohydrin, when the first time, underpressure distillation dewatered, tell a part of reaction solution and continue underpressure distillation, get crude product, fractionation is again collected 128-132 ℃ of (1.33-2.67kPa) cut and is got glycerine monochlorohydrin, be mainly 3-chloro-1, the 2-propylene glycol contains a spot of glycerin.
The cut that obtains that dewaters of underpressure distillation for the first time is the azeotrope of water and glycerine monochlorohydrin, the cut that obtains that dewaters of underpressure distillation for the second time is the azeotrope of water and dichlorohydrine, two kinds of cuts can adopt extracting operation to separate, separate and can merge with reaction solution after the oil phase obtain is removed solvent, distill pure product.
When the dichlorohydrine of being produced is used to produce epoxy chloropropane, can be without the fractionation purifying, crude product directly under alkaline condition cyclisation prepare epoxy chloropropane.
The raffinate that obtains of distillation is mainly catalyzer and a small amount of unreacted glycerine and by product, and when catalyzer was single resin, resin separated with raffinate after filtration, recycles behind the drying and dehydrating.When catalyzer was the combination of resin and carboxylic acid, the liquid portion of raffinate was mainly the catalyzer carboxylic acid, can directly recycle, and recycled after the dehydration of resin drying.
Water-absorbent acid type macromolecule resin catalyzer of the present invention comprises:
The perfluorinated sulfonic acid resinoid, as perfluorinated sulfonic resin, part replaces the perfluorinated sulfonic resin of proton, the perfluorinated sulfonic resin of loading type etc.Part replaces the perfluorinated sulfonic resin of proton such as the perfluorinated sulfonic resin that metal ions such as Hg2+, Rh3+ partly replace proton, the perfluorinated sulfonic resin of loading type can be multi-hole type or Nano type, as with aluminum oxide, silicon carbide, silicon-dioxide etc. being the perfluorinated sulfonic resin of the loading type of loaded article preparation.
The perfluorocarboxylic acid resinoid, as the perfluorinated carboxylic acid resin, part replaces the perfluorinated carboxylic acid resin of proton, loading type perfluorinated carboxylic acid resin etc.The loading type perfluorinated carboxylic acid resin can be multi-hole type or Nano type, as with aluminum oxide, silicon carbide, silicon-dioxide etc. being the loading type perfluorinated carboxylic acid resin of loaded article preparation.
Perfluorinated sulfonic acid-perfluori piated carboxylic acids compound resin, can be the resin that perfluorinated sulfonic acid and perfluorocarboxylic acid are composited, also can be to add ternary or the polynary compound resin that the reaction of other kind monomer copolymerization obtains in perfluorinated sulfonic acid and perfluorinated carboxylic acid resin's polymeric system.
Except that above-mentioned resin, all have the water-absorbent strong acid type macromolecule resin of catalytic activity or the catalyzer that all can be used as among the present invention through modified resins uses.
Water-absorbent strong acid type macromolecule resin and high boiling carboxylic acid combination catalyst that the present invention adopts comprise: monocarboxylic acid that above-mentioned water-absorbent strong acid type macromolecule resin and boiling point are higher than dichlorohydrine or di-carboxylic acid combination, monocarboxylic acid such as propionic acid, butyric acid, valeric acid, caproic acid, sad etc., di-carboxylic acid such as propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, suberic acid etc.
Among the present invention, the non-constant width of usage quantity scope of catalyzer, water-absorbent strong acid type macromolecule resin can be 0.1～50 times of qualities of glycerin, and suitable is 0.1～25 times, preferred 2～15 times.Carboxylic acid can be 0.01～1 of a glycerine mol ratio, and suitable is 0.01～0.5, preferred 0.01～0.1.
The present invention has no particular limits the source and the content of starting raw material glycerine, the source of glycerine can be a by-product glycerol of biological diesel oil, also can be the glycerine of vegeto-animal grease generation saponification, transesterify or hydrolysis reaction by-product, can also be biological process or chemical method synthetic glycerine, preferred biofuel and animal tallow transform the glycerine of by-product.Glycerine can be raw glycerine, also can be the glycerine of purifying, its content more than 50% all can, the impurity that contains in the by-product glycerol should and separate with final product easily not with hcl reaction.
Reaction can or add at normal pressure to depress to be carried out, and adds to depress speed of response and obviously accelerate.The reaction times of glycerine monochlorohydrin is 1～4 hour under the normal pressure, and the reaction times of dichlorohydrine is 2～8 hours.Pressure 0.1～2MPa during compressive reaction, preferred 0.1～1MPa, the glycerine monochlorohydrin reaction times is 0.5～4 hour, the dichlorohydrine reaction times is 1～4 hour.
The temperature that reaction is suitable for is 20～300 ℃, but the too high by product of temperature is many, and equipment corrosion increases, and it is slow excessively that temperature is crossed low reaction speed, and therefore suitable temperature of reaction is 50～140 ℃, preferred 70～115 ℃.
The reaction of glycerine and hydrogenchloride is the gas liquid reaction system, and common gas-liquid reaction equipment all can adopt, as reactor, turriform continuous flow reactor and loop reactor etc.
Specific embodiment:
Embodiment 1:
In having the four-hole bottle of stirring, add glycerine 122g (1.3mol), exsiccant perfluorinated sulfonic resin 12g, slowly be warmed up to 80 ℃, feed hydrogen chloride gas by certain speed, described certain ventilation speed is not overflow with tail gas to be advisable, and insulation was weighed once every half an hour, when the reaction solution gross weight was about 1.5 times of glycerine weight, underpressure distillation dewatered.Reaction solution after dewatering continues to feed hydrogen chloride gas with certain speed, when the reaction solution gross weight no longer increases, and stopped reaction.Underpressure distillation dewaters, and after dewatering, continues underpressure distillation, and the cut of collecting 95-105 ℃ is the product dichlorohydrine.
After the moisture of underpressure distillation for the first time extracted with benzene, oil phase added reaction solution after boiling off solvent; After the moisture of underpressure distillation for the second time extracted with benzene, oil phase added underpressure distillation in the whole liquid of reaction after boiling off solvent.
The still raffinate can be got back to reactive system after isolating resin, recycles after resin drying dewaters.
Embodiment 2:
In having the four-hole bottle of stirring, add glycerine 122g (1.3mol), the perfluorinated sulfonic resin 12g that reclaims among the embodiment 1, all the other are operated with embodiment 1.
Embodiment 3:
In having the four-hole bottle of stirring, add glycerine 122g (1.3mol), exsiccant perfluorinated carboxylic acid resin 12g, slowly be warmed up to 80 ℃, feed hydrogen chloride gas by certain speed, described ventilation speed is not overflowed with tail gas and is advisable, and insulation was weighed once every half an hour, when the reaction solution gross weight was about 1.5 times of glycerine weight, underpressure distillation dewatered.Reaction solution after dewatering continues to feed hydrogen chloride gas with certain speed, when the reaction solution gross weight no longer increases, and stopped reaction.Underpressure distillation dewaters, and after dewatering, continues underpressure distillation, and the cut of collecting 95-105 ℃ is the product dichlorohydrine.
After the moisture of underpressure distillation for the first time extracted with benzene, oil phase added reaction solution after boiling off solvent; After the moisture of underpressure distillation for the second time extracted with benzene, oil phase added underpressure distillation in the whole liquid of reaction after boiling off solvent.
The still raffinate can be got back to reactive system after isolating resin, recycles after resin drying dewaters.
Embodiment 4:
In having the four-hole bottle of stirring, add glycerine 122g (1.3mol), perfluorinated sulfonic acid ion exchange membrane 12g, slowly be warmed up to 80 ℃, feed hydrogen chloride gas by certain speed, described ventilation speed is not overflowed with tail gas and is advisable, and insulation was weighed once every half an hour, when the reaction solution gross weight was about 1.5 times of glycerine weight, underpressure distillation dewatered.Reaction solution after dewatering continues to feed hydrogen chloride gas with certain speed, when the reaction solution gross weight no longer increases, and stopped reaction.Underpressure distillation dewaters, and after dewatering, continues underpressure distillation, and the cut of collecting 95-105 ℃ is the product dichlorohydrine.
After the moisture of underpressure distillation for the first time extracted with benzene, oil phase added reaction solution after boiling off solvent; After the moisture of underpressure distillation for the second time extracted with benzene, oil phase added underpressure distillation in the whole liquid of reaction after boiling off solvent.
The still raffinate can be got back to reactive system after isolating resin, recycles after resin drying dewaters.
Embodiment 5:
In having the four-hole bottle of stirring, add glycerine 122g (1.3mol), perfluorinated sulfonic resin/SiO
2Composite catalyst 12g slowly is warmed up to 80 ℃, feeds hydrogen chloride gas by certain speed, and described ventilation speed is not overflowed with tail gas and is advisable, and insulation was weighed once every half an hour, and when the reaction solution gross weight was about 1.5 times of glycerine weight, underpressure distillation dewatered.Reaction solution after dewatering continues to feed hydrogen chloride gas with certain speed, when the reaction solution gross weight no longer increases, and stopped reaction.Underpressure distillation dewaters, and after dewatering, continues underpressure distillation, and the cut of collecting 95-105 ℃ is the product dichlorohydrine.
After the moisture of underpressure distillation for the first time extracted with benzene, oil phase added reaction solution after boiling off solvent; After the moisture of underpressure distillation for the second time extracted with benzene, oil phase added underpressure distillation in the whole liquid of reaction after boiling off solvent.
The still raffinate can be got back to reactive system after isolating resin, recycles after resin drying dewaters.
Perfluorinated sulfonic resin/SiO2 composite catalyst is prepared by sol-gel method by perfluor sulfoacid resin solution.
Embodiment 6:
In having the four-hole bottle of stirring, add glycerine 122g (1.3mol), hexanodioic acid 3g, exsiccant perfluorinated sulfonic resin/SiO2 composite catalyst 12g, slowly be warmed up to 80 ℃, feed hydrogen chloride gas by certain speed, ventilation speed is not overflowed with tail gas and is advisable, insulation, weigh once every half an hour, when the reaction solution gross weight was about 1.5 times of glycerine weight, underpressure distillation dewatered.Reaction solution after dewatering continues to feed hydrogen chloride gas with certain speed, when the reaction solution gross weight no longer increases, and stopped reaction.Underpressure distillation dewaters, and after dewatering, continues underpressure distillation, and the cut of collecting 95-105 ℃ is the product dichlorohydrine.
After the moisture of underpressure distillation for the first time extracted with benzene, oil phase added reaction solution after boiling off solvent; After the moisture of underpressure distillation for the second time extracted with benzene, the oil phase oil phase added underpressure distillation in the whole liquid of reaction after boiling off solvent.
After perfluorinated sulfonic resin/SiO2 mixture separated from the still raffinate, drying and dehydrating recycled with the still raffinate.
Embodiment 7 (hexanodioic acid is made catalyzer)
In having the four-hole bottle of stirring, add glycerine 122g (1.3mol), hexanodioic acid 6g, all the other are operated with embodiment 1, and different is the processing of still raffinate, but still raffinate direct reuse.
During the experimental result of embodiment 1～7 is listed in the table below.
More than disclosed be specific embodiments of the invention only, but the present invention is not limited thereto, any those skilled in the art can think variation, all should drop within protection scope of the present invention.
Claims (8)
1. the method for a process for preparing dichloropropanol through glycerol chlorination is characterized in that, under the katalysis of water-absorbent strong acid type macromolecule resin or resin and carboxylic acid combination catalyst, prepares dichlorohydrine with glycerine and gasiform hcl reaction, and its preparation method is:
A, water-absorbent strong acid type macromolecule resin catalyst consumption are: the mass ratio of water-absorbent strong acid type macromolecule resin and glycerine is 0.1～50, and suitable is 0.1～25, preferred 2～15;
B, resin and carboxylic acid combination catalyst consumption are: the mass ratio of water-absorbent strong acid type macromolecule resin and glycerine is 2～50; The mol ratio of carboxylic acid and glycerine is 0.01～1, and suitable is 0.01～0.5, preferred 0.01～0.1;
C, glycerine and catalyzer are joined reacting by heating in the reactor that has stirring, temperature of reaction is 20～300 ℃, suitable temperature of reaction is 50～140 ℃, preferred 70～115 ℃, this is reflected under the normal pressure and carries out, and the reaction times is 2～8 hours, feeds hydrogen chloride gas according to certain speed then, when reaction solution weightening finish to 150% the time, underpressure distillation dewaters;
D, the reaction solution after dewatering feed hydrogen chloride gas again according to certain speed, be reaction end when the weight of reaction solution no longer increases, underpressure distillation dewaters, and continues underpressure distillation again and gets crude product, fractionation again, collect 95-105 ℃ of (1.33-2.67kPa) cut and get dichlorohydrine, comprise two kinds of isomer, 1,3-dichlorohydrine and 2, the 3-dichlorohydrine is mainly 1, the 3-dichlorohydrine.
2. the method for a kind of process for preparing dichloropropanol through glycerol chlorination according to claim 1, it is characterized in that, described water-absorbent strong acid type macromolecule resin catalyzer comprises: perfluorinated sulfonic resin class material, perfluorinated carboxylic acid resin's class material, perfluorinated sulfonic acid-perfluorocarboxylic acid compound resin class material, or through the above-mentioned resene material of modification.
3. the method for a kind of process for preparing dichloropropanol through glycerol chlorination according to claim 1 is characterized in that, described resin and carboxylic acid combination catalyst comprise: the combination of water-absorbent strong acid type macromolecule resin and high boiling point carboxylic acid.
4. the method for a kind of process for preparing dichloropropanol through glycerol chlorination according to claim 1 and 2, it is characterized in that, the perfluorinated sulfonic resin class material of described water-absorbent strong acid type macromolecule resin catalyzer comprises: perfluorinated sulfonic resin, part replaces the perfluorinated sulfonic resin of proton, the perfluorinated sulfonic resin of loading type, part replaces the perfluorinated sulfonic resin Hg of proton
2+, R
h 3+Metal ion partly replaces the perfluorinated sulfonic resin of proton, and the perfluorinated sulfonic resin of loading type can be multi-hole type or Nano type, is the loading type perfluorinated sulfonic resin of loaded article preparation with aluminum oxide, silicon carbide, silicon-dioxide; Described perfluorinated carboxylic acid resin's class material comprises: the perfluorinated carboxylic acid resin, and part replaces the perfluorinated carboxylic acid resin of proton, loading type perfluorinated carboxylic acid resin; Described perfluorinated sulfonic acid-perfluorocarboxylic acid compound resin class material, can be the resin that perfluorinated sulfonic acid and perfluorocarboxylic acid are composited, also can be to add ternary or the polynary compound resin that the reaction of other kind monomer copolymerization obtains in perfluorinated sulfonic acid and perfluorinated carboxylic acid resin's polymeric system.
5. according to the method for claim 1 or 3 described a kind of process for preparing dichloropropanol through glycerol chlorination, it is characterized in that, the water-absorbent strong acid type macromolecule resin of described resin and carboxylic acid combination catalyst and the combination of high boiling point carboxylic acid comprise that water-absorbent strong acid type macromolecule resin and boiling point are higher than the combination of the monocarboxylic acid or the di-carboxylic acid of dichlorohydrine, wherein monocarboxylic acid comprises: propionic acid, butyric acid, valeric acid, caproic acid and sad, di-carboxylic acid comprises: propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid and suberic acid.
6. the method for a kind of process for preparing dichloropropanol through glycerol chlorination according to claim 1 is characterized in that, when described catalyzer was single resin, resin separated with raffinate after filtration, recycles behind the drying and dehydrating.
7. the method for a kind of process for preparing dichloropropanol through glycerol chlorination according to claim 1, it is characterized in that, when described catalyzer is the combination of resin and carboxylic acid, recycle after the dehydration of resin drying, the liquid portion of vinasse is mainly the catalyzer carboxylic acid, can directly recycle.
8. the method for a kind of process for preparing dichloropropanol through glycerol chlorination according to claim 1, it is characterized in that, reaction can be carried out adding to depress, pressure 0.1～2MPa during compressive reaction, preferred 0.1～1MPa, the glycerine monochlorohydrin reaction times is 0.5～4 hour, and the dichlorohydrine reaction times is 1～4 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910211171 CN101693646B (en) | 2009-11-06 | 2009-11-06 | Process for preparing dichloropropanol through glycerol chlorination method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910211171 CN101693646B (en) | 2009-11-06 | 2009-11-06 | Process for preparing dichloropropanol through glycerol chlorination method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101693646A true CN101693646A (en) | 2010-04-14 |
| CN101693646B CN101693646B (en) | 2012-05-30 |
Family
ID=42092661
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200910211171 Expired - Fee Related CN101693646B (en) | 2009-11-06 | 2009-11-06 | Process for preparing dichloropropanol through glycerol chlorination method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101693646B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109231637A (en) * | 2018-11-23 | 2019-01-18 | 江苏扬农锦湖化工有限公司 | A kind of processing method of epoxy resin production waste-water |
| CN112441879A (en) * | 2020-12-10 | 2021-03-05 | 山东泰和水处理科技股份有限公司 | Method for synthesizing dichloropropanol |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101570471B (en) * | 2008-04-29 | 2012-08-29 | 中国石油化工股份有限公司 | Method for synthesizing dichloropropanol by glycerine |
-
2009
- 2009-11-06 CN CN 200910211171 patent/CN101693646B/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109231637A (en) * | 2018-11-23 | 2019-01-18 | 江苏扬农锦湖化工有限公司 | A kind of processing method of epoxy resin production waste-water |
| CN112441879A (en) * | 2020-12-10 | 2021-03-05 | 山东泰和水处理科技股份有限公司 | Method for synthesizing dichloropropanol |
| CN112441879B (en) * | 2020-12-10 | 2022-07-22 | 山东泰和水处理科技股份有限公司 | Method for synthesizing dichloropropanol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101693646B (en) | 2012-05-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101475442B (en) | Method for preparing ethylene glycol from oxalic ester | |
| CN105622337B (en) | Novel reactive distillation coupling process and device for separating liquid-phase product of ethylene glycol prepared from coal | |
| WO2017133357A1 (en) | Method, process, and apparatus for separating ethylene glycol and 1,2-butylene glycol | |
| CN101138725A (en) | Catalyzer for the oxalic ester hydrogenation synthesizing of ethylene glycol and method of preparing the same | |
| CN102675047B (en) | Method for preparing dichloropropanol | |
| CN101337950A (en) | Method for continuously preparing epichlorohydrin by glycerine reaction fractional distillation | |
| CN102153465A (en) | Method for preparing low acid-value fatty acid methyl ester | |
| CN104045554A (en) | Method for preparing ethylene glycol diacetate | |
| CN103044257A (en) | Alcoholysis method and device system for producing dioctyl terephthalate by polyester wastes | |
| CN109970511B (en) | Method for synthesizing 1, 3-propylene glycol by resource utilization of HPPO byproduct | |
| CN111499598A (en) | Production process for preparing epichlorohydrin by glycerol method | |
| CN101979365B (en) | Method for continuously preparing dichlorohydrin | |
| CN102060767B (en) | Method for producing caprolactam by methylbenzene | |
| CN101830788A (en) | Method for separating azeotropic mixture of ethyl methyl ketone and water through variable-pressure rectification | |
| CN105541555B (en) | Reactive distillation method and device for separating ethylene glycol, propylene glycol and butanediol | |
| CN101693646B (en) | Process for preparing dichloropropanol through glycerol chlorination method | |
| CN101570471A (en) | Method for synthesizing dichloropropanol by glycerine | |
| CN102887816B (en) | Method for preparing dichloropropanol with chemical reaction-pervaporation coupling method | |
| CN107698423A (en) | A kind of method for preparing ethylene glycol and by-product halogenated alkane | |
| CN102351648B (en) | Process for producing 1,6-hexanediol and coproducing epsilon-caprolactone | |
| CN108863793B (en) | Preparation method of isopropyl acetate | |
| CN114181040B (en) | Preparation method of dichloropropanol | |
| CN1224621C (en) | Tetrahydrofuran refining process | |
| CN203007176U (en) | Alcoholysis device system for preparing dioctyl terephthalate from Dacron wastes | |
| CN106146299A (en) | Produce acetas and the method for ethylene glycol |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120530 Termination date: 20151106 |
|
| EXPY | Termination of patent right or utility model |