CN108863718A - A kind of synthetic method of dichlorohydrin - Google Patents
A kind of synthetic method of dichlorohydrin Download PDFInfo
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- CN108863718A CN108863718A CN201810754234.3A CN201810754234A CN108863718A CN 108863718 A CN108863718 A CN 108863718A CN 201810754234 A CN201810754234 A CN 201810754234A CN 108863718 A CN108863718 A CN 108863718A
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- acid
- glycerol
- dichlorohydrin
- hydrogen chloride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
- B01J31/30—Halides
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of synthetic method of dichlorohydrin.Specifically utilize organic carboxyl acid/inorganic lewis acid composite catalyst, under the conditions of 100 ~ 120 DEG C of temperature, through nucleophilic substitution synthesizing dichloropropanol step by step, the azeotropic mixture that the water and hydrogen chloride, a small amount of dichlorohydrin for reacting generation are formed separates to enter from reaction tower in time isolates and purifies device for concerted catalysis glycerol and hydrogen chloride gas.Hydrogen chloride gas is acetic acid and phosphorus trichloride is the byproduct on Material synthesis water treatment agent hydroxy ethylene diphosphonic acid production line.The technological reaction rate is fast, and dichlorohydrin yield is up to 95% or more, and selectivity of product is high, and raw material is easy to get, production cost is low, realizes that by-product is turned waste into wealth, and process condition is mild, safety and environmental protection, easily realization scale industrial production.
Description
Technical field
The invention belongs to Field of Fine Chemicals, it is related to a kind of synthesis technology of novel dichloro propyl alcohol, more particularly to a kind of
The application of organic carboxyl acid and inorganic lewis acid composite catalyst in dichlorohydrin synthesis technology.
Background technique
Dichlorohydrin is colourless liquid, has the chloro- 2- propyl alcohol of 1,3- bis- and 2,3- bis- trimethylewne chlorohydrin 3-s, two kinds of structural isomerisms
Body can carry out saponification with lye such as limewash or sodium hydroxides, slough an one's share of expenses for a joint undertaking hydrogen chloride, cyclisation generates epoxy chloropropionate
Alkane.Currently, industrially the method for production dichlorohydrin mainly has propylene high-temperature chloridising and acetate propylene method, both methods is all
It is faced with catalyst technology problem, and yield, less than 90%, disposal of waste gas, water and industrial residue is costly, and industrially scalable is small, and by-product is more, ring
Border is seriously polluted, simultaneously as the insufficient supply of primary raw material propylene and chlorine, seriously limits product epoxy chloropropionate downstream
The further development of alkane.
With the continuous development of biodiesel new industry and the mass production of biodiesel, the market of by-product glycerin
Price reduces year by year.And as glycerol downstream product dichlorohydrin it is the important intermediate of synthesizing epoxy chloropropane, have good
Market prospects become domestic and international using by-product glycerin and hydrogen chloride synthesis dichlorohydrin as a kind of green chemistry process
The hot spot of research and development.
Earlier 1900s, Deutsche Bundespatent（GB197308,1906）Disclose it is a kind of using glycerol and hydrogen chloride gas through vinegar
The method that acid or propionic acid catalytic chlorination prepare dichlorohydrin, reaction yield is only 75%.Dow house journal US 2144612
It, will by the organic matter that addition polyhalohydrocarbon, chlorobenzene and butyl ether etc. form azeotropic with water in glycerol and hcl reaction system
Water constantly takes reaction system out of, and yield is improved to 87%, but in this method a large amount of organic solvents use, cause production and after
Processing cost increases.Then, the numerous patents such as WO 2005/021476, WO 2006/020234, WO 2005/054167 disclose
It is generated under the conditions of glycerol is reported existing for the catalyst such as aliphatic carboxylic acid, acid anhydrides, acyl chlorides, lactone, amide by chlorination reaction
The method of dichlorohydrin.
About the method for glycerol method synthesizing dichloropropanol, also there are many reports in the country.CN 101029000A is with organic nitrile
Catalyst, catalyzing glycerol and hydrogen chloride gas precursor reactant synthesizing dichloropropanol.CN101570471A patent disclosure uses highly acid sun
Or mixtures thereof ion exchange resin and active carbon, silica gel, aluminium oxide load p-methyl benzenesulfonic acid solid acid catalysis glycerol with have
Machine acid carries out esterification and generates organic acid esters ester, the method for preparing dichlorohydrin through chlorination hydrogen chloride.CN 101704722A
It is middle to utilize dicarboxylic acid-rare earth chloride trisodium cerium chloride and lanthanum trichloride for composite catalyst catalyzing glycerol and hydrogen chloride gas
Dichlorohydrin is generated, takes the water of reaction system generation out of using organic solvent, the use of benzene and methylbenzene water-taking agent not only increases life
Cost is produced, and is easy to cause adverse effect to environment.By two hydrated stannous chlorides and stannous chloride group in CN 103464178A
At catalyst, be used for glycerol hydrogen chlorine method synthesizing dichloropropanol.A kind of utilization glycerol and hydrogen chloride are disclosed in CN102040479
The technique of preparing dichloropropanol by autocatalysis reaction, which completes by high temperature, condition of high voltage, and the conversion ratio of glycerol is not
Stablize.A kind of attapulgite modified utilization, ethyl orthosilicate, dehydrated alcohol, phosphotungstic acid are disclosed in CN 106466615A and are gone
According to certain mass than mixing, catalyst made from aged, dry, high-temperature roasting, catalyzing glycerol for chlorination method synthesizes ionized water
Dichlorohydrin.This method catalyst preparation process is cumbersome, is not easy to realize scale industrial production.Liu Fang etc.（Fine chemistry industry,
2009, vol.26（4）：370-372）It has studied with the Polyaromatic Ether Sulfone Ether Ketone Ketone resin with carboxyl side group（PESEKK-A）For main reminder
Agent, phosphorus trichloride are co-catalyst to the catalytic effect of glycerol chloro method synthesizing dichloropropanol, and toluene and dichloro is respectively adopted
Ethane is as water entrainer, glycerol conversion yield 89.8%.
Summary of the invention
The purpose of the present invention is what is realized as follows：
A kind of synthetic method of dichlorohydrin specifically utilizes organic carboxyl acid/inorganic lewis acid composite catalyst, 100 ~
Under the conditions of 120 DEG C of temperature, concerted catalysis glycerol and hydrogen chloride gas are through nucleophilic substitution synthesizing dichloropropanol step by step, reaction life
At the azeotropic mixture that is formed of water and hydrogen chloride, a small amount of dichlorohydrin separated from reaction tower isolated and purified recycling in time.
Wherein, the composite catalyst that catalyst can be combined for organic carboxyl acid and inorganic lewis acid by any ingredient,
Middle organic carboxyl acid can choose any one of glacial acetic acid, adipic acid, octanoic acid and decanedioic acid；Inorganic lewis acid can be chlorination
Any one of aluminium, zinc chloride, stannous chloride, tin tetrachloride, iron chloride, frerrous chloride.
Preferred composite catalyst collocation is adipic acid/stannous chloride, adipic acid/iron chloride, adipic acid/zinc chloride, pungent
Acid/stannous chloride, octanoic acid/iron chloride or decanedioic acid/stannous chloride.
Wherein the mass ratio of organic carboxyl acid and glycerol is 0.1 ~ 3:100；Inorganic lewis acid and qualities of glycerin ratio are 0.1 ~ 2:
100；
Preferably, organic carboxyl acid and qualities of glycerin ratio are preferable over 0.5 ~ 2:100, inorganic lewis acid and qualities of glycerin are than preferred
In 0.5 ~ 1:100.
Wherein, for substitution reaction temperature controlling range at 100 ~ 120 DEG C, preferred temperature controls model step by step for glycerol and hydrogen chloride
Enclose is 105 ~ 110 DEG C.
Wherein, the flow of hydrogen chloride gas is 2.5 ~ 5.0 mL/（min·gGlycerol）.
The catalytic cycle of catalyst is 3-5h.
Beneficial effects of the present invention：
1. organic carboxyl acid/inorganic lewis acid composite catalyst is selectively good, high catalytic efficiency, catalysis time is long；
2. yield is high, reach 90% or more；
It is continued to use 3. hydrogen chloride gas can be recycled as raw material of the invention；
4. the raw materials used in the present invention is cheap, technical process is simple and easy to control, is not required to add organic water entrainer, there is good warp
Ji value.
Specific embodiment
In order to further illustrate essentiality content of the invention, it is illustrated in connection with specific embodiments,
It is explained that the content of present invention includes but are not limited to following embodiment.
Embodiment 1
（1）Mixing is added to by 736Kg glycerol and by the composite catalyst that 14.72Kg adipic acid and 7.36Kg stannous chloride form
Kettle is uniformly mixed, and establishes connection through constant flow pump, mass flowmenter and first order reaction top of tower after heated device preheating；
（2）The by-product hydrogen chloride gas come out from HEDP production line, through cooling system, surge tank, heater, gas flowmeter meter
Connection is established with first order reaction tower respectively, second order reaction tower, third-order reaction tower bottom after amount；
（3）The control valve for establishing connection with first order reaction tower is opened, is passed through hydrogen chloride gas continuously from reaction tower bottom, with
The glycerin catalytic agent mixed liquor of continuous spray injection is reacted at 105 ~ 110 DEG C of temperature at the top of from reaction tower, the water of generation and chlorination
Hydrogen, a small amount of dichlorohydrin azeotropic mixture are continual to be separated from tower top in time into separating-purifying device, the glycerol chloro thing of generation
The continual hydrogen chloride gas for successively entering reaction system from second order reaction tower, third-order reaction top of tower and being passed through from their bottoms
Nucleophilic displacement of fluorine chlorination reaction step by step occurs for body.
（4）The reaction product come out from third-order reaction tower enters rectifier unit through reboiler, and dichlorohydrin is from rectifying tower
Top is collected to dichlorohydrin collection device, and tower bottom liquid back-mixing material kettle is recycled.
Embodiment 2
Mixing kettle is added in 3.68Kg adipic acid and 3.68Kg zinc chloride to be uniformly mixed with glycerol, hydrogen chloride gas flow is 2.5
mL/（min·gGlycerol）, 110-115 DEG C of temperature.Other consersion units and operating method are the same as embodiment 1.
Embodiment 3
Mixing kettle is added in 11.04Kg octanoic acid and 3.68Kg iron chloride to be uniformly mixed with glycerol, hydrogen chloride gas flow is 4.0
mL/（min·gGlycerol）, other consersion units and operating method are the same as embodiment 1.
Embodiment 4
Mixing kettle is added in 3.68Kg adipic acid and 3.68Kg iron chloride to be uniformly mixed with glycerol, other consersion units and operation side
Method is the same as embodiment 1.
Embodiment 5
Mixing kettle is added in 11.04Kg decanedioic acid and 3.68Kg stannous chloride to be uniformly mixed with glycerol, other consersion units and behaviour
Make method with embodiment 1.
Embodiment 6
Mixing kettle is added in 14.72Kg glacial acetic acid and 7.36Kg stannous chloride to be uniformly mixed with glycerol, other consersion units and behaviour
Make method with embodiment 1.
Embodiment 7
Mixing kettle is added in 22.08Kg glacial acetic acid and 14.72Kg aluminium chloride to be uniformly mixed with glycerol, hydrogen chloride gas flow is it
Its consersion unit and operating method are the same as embodiment 1.
By above embodiments catalyst effect data record at table：
Claims (4)
1. a kind of synthetic method of novel dichloro propyl alcohol, which is characterized in that the compound catalysis of organic carboxyl acid/inorganic lewis acid
Agent, at a temperature of 100-120 DEG C, catalyzing glycerol and hydrogen chloride gas precursor reactant synthesizing dichloropropanol.
2. synthetic method according to claim 1, which is characterized in that the composite catalyst is organic carboxyl acid and nothing
The composite catalyst of machine lewis acid configuration, wherein organic carboxyl acid can choose appointing for glacial acetic acid, adipic acid, octanoic acid and decanedioic acid
It anticipates one kind；Inorganic lewis acid can be times of aluminium chloride, zinc chloride, stannous chloride, tin tetrachloride, iron chloride, frerrous chloride
It anticipates one kind.
3. synthetic method according to claim 1, which is characterized in that the mass ratio of organic carboxyl acid and glycerol is 0.1-3:
100；Inorganic lewis acid and qualities of glycerin ratio are 0.1-2:100.
4. synthetic method according to claim 1, which is characterized in that the flow of the hydrogen chloride gas is 2.5 ~ 5.0
mL/（min·gGlycerol）.
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| CN201810754234.3A CN108863718A (en) | 2018-07-11 | 2018-07-11 | A kind of synthetic method of dichlorohydrin |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN114181040A (en) * | 2021-12-14 | 2022-03-15 | 山东鲁泰控股集团有限公司石墨烯高分子复合材料研发中心 | Preparation method of dichloropropanol |
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|---|---|---|---|---|
| CN101773851A (en) * | 2009-01-13 | 2010-07-14 | 德纳（南京）化工有限公司 | Dichloropropanol catalyst prepared by glycerol method |
| CN101774886A (en) * | 2009-01-13 | 2010-07-14 | 德纳（南京）化工有限公司 | Method for preparing dichlorohydrin and reaction device |
| CN101805243A (en) * | 2010-05-07 | 2010-08-18 | 宁波东港电化有限责任公司 | Production method of dichloropropanol |
| CN102295529A (en) * | 2011-07-11 | 2011-12-28 | 江西省化学工业研究所 | Method for continuously preparing dichlorohydrin by using glycerin and hydrochloric acid |
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2018
- 2018-07-11 CN CN201810754234.3A patent/CN108863718A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101773851A (en) * | 2009-01-13 | 2010-07-14 | 德纳（南京）化工有限公司 | Dichloropropanol catalyst prepared by glycerol method |
| CN101774886A (en) * | 2009-01-13 | 2010-07-14 | 德纳（南京）化工有限公司 | Method for preparing dichlorohydrin and reaction device |
| CN101805243A (en) * | 2010-05-07 | 2010-08-18 | 宁波东港电化有限责任公司 | Production method of dichloropropanol |
| CN102295529A (en) * | 2011-07-11 | 2011-12-28 | 江西省化学工业研究所 | Method for continuously preparing dichlorohydrin by using glycerin and hydrochloric acid |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN113831304B (en) * | 2021-10-09 | 2024-06-18 | 江苏索普工程科技有限公司 | Method for efficiently preparing epichlorohydrin by biomass glycerol |
| CN114181040A (en) * | 2021-12-14 | 2022-03-15 | 山东鲁泰控股集团有限公司石墨烯高分子复合材料研发中心 | Preparation method of dichloropropanol |
| CN114181040B (en) * | 2021-12-14 | 2023-12-12 | 山东鲁泰控股集团有限公司石墨烯高分子复合材料研发中心 | Preparation method of dichloropropanol |
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