CN107935968A - A kind of epoxychloropropane preparation method based on biomass glycerol - Google Patents
A kind of epoxychloropropane preparation method based on biomass glycerol Download PDFInfo
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- CN107935968A CN107935968A CN201710968832.6A CN201710968832A CN107935968A CN 107935968 A CN107935968 A CN 107935968A CN 201710968832 A CN201710968832 A CN 201710968832A CN 107935968 A CN107935968 A CN 107935968A
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- epoxychloropropane
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/24—Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
- C07D301/26—Y being hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention discloses a kind of epoxychloropropane preparation method based on biomass glycerol, step is：It is first 1 by mass ratio:The biomass glycerol and organic acid of (0.03~0.06) are uniformly mixed, and are heated to temperature as 70~90 DEG C, and long-time heat preservation, and hydrogen chloride gas is then passed through into system and starts blistering reaction, the reaction time continues 72~120h, and tail gas is absorbed using lye；Then it is transferred to after resulting material is cooled to room temperature in another reactor, it is 0~30 DEG C to keep temperature, adds the Na that concentration is 12.4~24.8wt%2CO3Solution carries out 15~60min of reaction；The solid of generation is filtered off after reaction, and filtrate is epoxychloropropane solution.The method technique of the present invention is simple, raw material is easy to get, cost is low, has good industrial prospect.
Description
Technical field
The present invention relates to the preparation method of chemical intermediate epoxychloropropane, is to be related to one kind based on biology specifically
The epoxychloropropane preparation method of matter glycerine.
Background technology
Epoxychloropropane is that a kind of important fine chemistry industry raw material and chemical industry product Intermediate, use are fairly common.With
In production adhesive, cation exchange resin and fiberglass, chlorohydrin rubber, epoxy resin, insulated product, explosive.In biomass
Before diesel oil development, epoxychloropropane is once used to the of a relatively high glycerine of synthesis price, due to the improvement of technique, glycerine conduct
Biomass firewood oil product is up to more than 90%, and a large amount of supplies make glycerine price decline rapidly, and biodiesel is subject to the green grass or young crops of scientist
Look at, dichlorohydrin and epoxychloropropane are prepared by raw material of glycerine, research and develop other chemical products using glycerine as raw material and produce work
The opportune stage for having climbed up history of skill, can not only solve the overstock problem of accessory substance in production of biodiesel, moreover it is possible to increase
Add the environment and economic benefit of biodiesel.
Existing Patent No. CN 105272946A disclose a kind of preparation method of epoxychloropropane, and this method is continuous
Reaction, it is efficient.But its raw material is chloropropene and peroxide, cost is higher.
Existing Patent No. CN 104591967A disclose a kind of preparation method of epoxychloropropane, and this method uses thick
Glycerine is raw material, and first acidification carries out chlorination reaction again, and raw material is cheap.But its dichlorohydrin yield only 93%, to raw material
Utilization rate is not high enough.
The content of the invention
The purpose of the present invention is asked for epoxychloropropane manufacturing cost in the prior art is high, raw material availability is not high enough
A kind of topic, it is proposed that epoxychloropropane preparation method based on biomass glycerol.This method technique is simple, raw material is easy to get, cost
It is low, have good industrial prospect, glycerol conversion yield is up to 100% in chlorination process, and dichlorohydrin total recovery is reachable
More than 98%.And in epoxidation process, dichlorohydrin high conversion rate is in 95%, and epoxychloropropane yield is up to 92%.
To reach above-mentioned purpose, the present invention is achieved by following technical proposals：
A kind of epoxychloropropane preparation method based on biomass glycerol, includes the following steps：
(1) it is 1 by mass ratio:The biomass glycerol and organic acid of (0.03~0.06) are uniformly mixed, and are heated to temperature and are
70~90 DEG C, and long-time heat preservation, hydrogen chloride gas being then passed through into system and starts blistering reaction, the reaction time continues 72~
120h, tail gas are absorbed using lye；
(2) reaction in end step (1), is transferred to after resulting material is cooled to room temperature in another reactor, keeps
Temperature is 0~30 DEG C, then adds the Na that concentration is 12.4~24.8wt%2CO3Solution carries out 15~60min of reaction, wherein raw
Material glycerine and Na2CO3The mass volume ratio of solution is 1kg：(3~5) L；
(3) solid of generation is filtered off after reaction, and filtrate is epoxychloropropane solution.
Further, the organic acid described in step (1) is any of oxalic acid, adipic acid, decanedioic acid.
Further, it is 250~550mL/min that the hydrogen chloride gas described in step (1), which is passed through flow,.
Compared with prior art, the advantages of the present invention are：
1. raw material of the present invention is biomass glycerol, hydrogen chloride, sodium carbonate, cost is relatively low, security is higher and can be with biology
Diesel oil, chlorine industry coproduction.
2. the present invention uses long-time chlorination, glycerine can convert completely, and intermediate product dichlorohydrin yield is higher.
3. the present invention carries out epoxidation reaction using highly basic, reaction rate is fast, and accessory substance is few.
4. the present invention, without purifying intermediate products, reduces operation workshop section between chlorination process and epoxidation process.
5. the glycerol conversion yield of the invention in chlorination process is up to 100%, and dichlorohydrin total recovery is up to 98%.
6. the present invention is in epoxidation process, dichlorohydrin high conversion rate is in 95%, and epoxychloropropane yield is up to 92%.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, by the following examples, to the present invention
It is described in further detail.It should be appreciated that specific embodiment described herein is used only for explaining the present invention, and do not have to
It is of the invention in limiting.Its shown data does not represent the limitation to feature of present invention scope at the same time.
Embodiment 1
(1) 1kg glycerine, 50g adipic acids are mixed and heated to 90 DEG C and long-time heat preservation, hydrogen chloride gas is passed through into system
Body starts blistering reaction, and gas flow 300mL/min reacts and continues 120h, and tail gas is absorbed using lye.
(2) reaction in end step (1), is transferred to after material is cooled to room temperature in another reactor, with 30 DEG C of guarantors
Temperature, then adds 4.5L, the Na of 21.4wt%2CO3Solution is reacted, and is reacted and is continued 30min.
(3) solid of generation is filtered off after reaction, and filtrate is epoxychloropropane solution.
Embodiment 2
(1) 1kg glycerine, 40g adipic acids, 10g decanedioic acid are mixed and heated to 75 DEG C and long-time heat preservation, led into system
Enter hydrogen chloride gas and start blistering reaction, gas flow 300mL/min reacts and continues 72h, and tail gas is absorbed using lye.
(2) reaction in end step (1), is transferred to after material is cooled to room temperature in another reactor, with 0 DEG C of guarantor
Temperature, then adds 4L, the Na of 24.8wt%2CO3Solution is reacted, and is reacted and is continued 30min.
(3) solid of generation is filtered off after reaction, and filtrate is epoxychloropropane solution.
Embodiment 3
(1) 1kg glycerine, 40g adipic acids are mixed and heated to 85 DEG C and long-time heat preservation, hydrogen chloride gas is passed through into system
Body starts blistering reaction, and gas flow 300mL/min reacts and continues 95h, and tail gas is absorbed using lye.
(2) reaction in end step (1), is transferred to after material is cooled to room temperature in another reactor, with 0 DEG C of guarantor
Temperature, then adds 5L, the Na of 19.2wt%2CO3Solution is reacted, and is reacted and is continued 30min.
(3) solid of generation is filtered off after reaction, and filtrate is epoxychloropropane solution.
The beneficial effect of the embodiment of the present invention
The foregoing is intended to be a preferred embodiment of the present invention.Certainly, the present invention can also have other a variety of implementations
Example, in the case of without departing substantially from spirit of the invention and its essence, any one skilled in the art, when can be according to this
Various corresponding equivalent changes and deformation are made in invention, should all belong to the protection domain of appended claims of the invention.
Claims (5)
1. a kind of epoxychloropropane preparation method based on biomass glycerol, it is characterised in that include the following steps：
(1) it is 1 by mass ratio:The biomass glycerol and organic acid of (0.03~0.06) are uniformly mixed, be heated to temperature for 70~
90 DEG C, and long-time heat preservation, hydrogen chloride gas being then passed through into system and starts blistering reaction, the reaction time continues 72~
120h, tail gas are absorbed using lye；
(2) reaction in end step (1), is transferred to after resulting material is cooled to room temperature in another reactor, keeps temperature
For 0~30 DEG C, the Na that concentration is 12.4~24.8wt% is then added2CO3Solution carries out 15~60min of reaction, wherein biomass
Glycerine and Na2CO3The mass volume ratio of solution is 1kg：(3~5) L；
(3) solid of generation is filtered off after reaction, and filtrate is epoxychloropropane solution.
A kind of 2. epoxychloropropane preparation method based on biomass glycerol according to claim 1, it is characterised in that step
Suddenly the organic acid described in (1) is any of oxalic acid, adipic acid, decanedioic acid.
A kind of 3. epoxychloropropane preparation method based on biomass glycerol according to claim 1, it is characterised in that step
Suddenly the organic acid described in (1) be oxalic acid, adipic acid, any mass ratio in decanedioic acid it is several.
A kind of 4. epoxychloropropane preparation method based on biomass glycerol according to claim 1, it is characterised in that step
Suddenly it is 250~550mL/min that the hydrogen chloride gas described in (1), which is passed through flow,.
A kind of 5. epoxychloropropane preparation method based on biomass glycerol according to claim 1, it is characterised in that step
Suddenly the reaction time described in (2) is 30min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710968832.6A CN107935968A (en) | 2017-10-18 | 2017-10-18 | A kind of epoxychloropropane preparation method based on biomass glycerol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710968832.6A CN107935968A (en) | 2017-10-18 | 2017-10-18 | A kind of epoxychloropropane preparation method based on biomass glycerol |
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| CN107935968A true CN107935968A (en) | 2018-04-20 |
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| CN201710968832.6A Pending CN107935968A (en) | 2017-10-18 | 2017-10-18 | A kind of epoxychloropropane preparation method based on biomass glycerol |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009184943A (en) * | 2008-02-05 | 2009-08-20 | Daiso Co Ltd | Method for producing epichlorohydrin |
| EP2093221A1 (en) * | 2008-02-04 | 2009-08-26 | Biopetrol Industries AG | Method for manufacturing epichlorohydrin from glycerine |
| CN102171198A (en) * | 2008-08-25 | 2011-08-31 | 沃尔特·坎兹勒 | Process for preparing epichlorohydrin from glycerol |
| CN102617514A (en) * | 2012-03-09 | 2012-08-01 | 常州大学 | Clean process for using glycerin to synthesize epichlorohydrin |
| CN104370857A (en) * | 2014-11-11 | 2015-02-25 | 常州大学 | Synthesis method of epoxy chloropropane |
-
2017
- 2017-10-18 CN CN201710968832.6A patent/CN107935968A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2093221A1 (en) * | 2008-02-04 | 2009-08-26 | Biopetrol Industries AG | Method for manufacturing epichlorohydrin from glycerine |
| JP2009184943A (en) * | 2008-02-05 | 2009-08-20 | Daiso Co Ltd | Method for producing epichlorohydrin |
| CN102171198A (en) * | 2008-08-25 | 2011-08-31 | 沃尔特·坎兹勒 | Process for preparing epichlorohydrin from glycerol |
| CN102617514A (en) * | 2012-03-09 | 2012-08-01 | 常州大学 | Clean process for using glycerin to synthesize epichlorohydrin |
| CN104370857A (en) * | 2014-11-11 | 2015-02-25 | 常州大学 | Synthesis method of epoxy chloropropane |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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Application publication date: 20180420 |