CN101182283B - Method for preparing dichloropropanol by glycerol - Google Patents
Method for preparing dichloropropanol by glycerol Download PDFInfo
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- CN101182283B CN101182283B CN 200710185468 CN200710185468A CN101182283B CN 101182283 B CN101182283 B CN 101182283B CN 200710185468 CN200710185468 CN 200710185468 CN 200710185468 A CN200710185468 A CN 200710185468A CN 101182283 B CN101182283 B CN 101182283B
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- glycerine
- dichlorohydrine
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Abstract
A method of preparing for dichloropropanol from glycerol is that the glycerol and catalyst are added into a spraying type reactor; a liquid circulating pump is used to pump the glycerol and the catalyst our from the spraying type reactor, then the glycerol and the catalyst are sent into the spraying type reactor from the top of the spraying type reactor by the manner of spraying; HCl gas which is absorbed from the lateral part of the spraying type reactor is mixed completely and react with the materials of the glycerol and the catalyst inside the spraying type reactor; at the same time the negative pressure produced by spraying brings a resultant inside the spraying type reactor in the form of an azeotropic matter of water, the dichloropropanol and the HCl; the water and the dichloropropanol in the azeotropic matter are condensed down by a condenser, and the unreacted HCl gas and the complementary HCl gas are sent into the spraying type reactor together for cyclic reaction. The invention has the advantages of the improvement of the reaction velocity and high glycerol transformation rate.
Description
Technical field
The invention belongs to a kind of method for preparing dichlorohydrine, relate in particular to a kind of method for preparing dichlorohydrine from glycerine.
Background technology
The main method of producing dichlorohydrine at present is the propylene high-temperature chlorination process of U.S. Shell company in exploitation in 1948, and reaction principle is as follows:
CH
2＝CH-CH
3+Cl
2→CH
2＝CH-CH
2Cl+HCl
CH
2＝CH-CH
2Cl+Cl
2+H
2O→CH
2Cl-CHOH-CH
2Cl+CH
2Cl-CHCl-CH
2OH
The characteristics of this method are that production process is flexible, technical maturity, and stable operation is produced multiple organic intermediate, but exists transformation efficiency low, and by product is many, energy consumption height, shortcoming such as equipment corrosion is serious, and waste water and dregs is many.
The less technology of another kind of application is the propylene acetate method, and reaction principle is as follows:
CH
2＝CH-CH
2OH+Cl
2→CH
2ClCHClCH
2OH
Compare with the propylene high-temperature chlorination process of Shell company, aforesaid method has the reaction conditions gentleness, productive rate height, characteristics such as by product is few, and sewage quantity is few.But this technological reaction step is more, and catalyst life is short, needs to prevent the acetate corrosion with stainless material, invests higher relatively shortcoming.
Above-mentioned two kinds of commercial runs are raw material with non-renewable petroleum resources all, go back mass consumption chlorine, and environmental pollution are serious.Along with the surging biofuel as the alternative energy of international oil price enjoys favor, a large amount of glycerine of by-product in the production of biodiesel process, every production 10t biofuel just can produce 1t glycerine; For glycerine being carried out the cost of deep processing reduction biofuel, also to seek new source and produced the glycerine method for the intermediate epoxy chloropropane of producing Resins, epoxy, the glycerine ratio juris is as follows:
The method of patent DE197308 research is to be catalyzer with acetic acid or propionic acid, at 100 ℃ of left and right sides HCl gases and glycerine reaction 20-40h, obtains yield and be 75% dichlorohydrine, the carrying out of the water inhibited reaction of generation.
A kind of continuous circulating reacting process is disclosed among the patent WO2005021476.Glycerine and HCl gas react in bubbling reactor as catalyzer with acetic acid, and reactant enters in the vacuum still, and the upper strata overhead fraction is dichlorohydrine and water, and lower floor's tower stilling branch pumps into and carries out circulating reaction in the reactor.React not solubilizing agent, distillation tower is removed water and the dichlorohydrine in the reactant in the dependence reaction cycle, and balance is carried out to the product direction, but underpressure distillation steams HCl, causes HCl concentration to reduce, and speed of reaction is low, acetic acid is also steamed simultaneously, causes catalyst loss.
Patent WO2005054167 discloses another kind of continuous circulation process.Glycerine and HCl gas enter as the catalyzer adverse current with carboxylic acid etc. and react in single still or the many stills reactor, and to the gas phase thing in the reactor and liquid phase thing respectively gas carry and unreacted reactant returned into reactor.The countercurrent flow of gas liquid reaction thing, the HCl utilization ratio improves, and the reactant gases of utilization own is taken away the water in the reaction system, and preferably not volatile catalyzer, and catalyst levels is little, but process energy consumption is still high, and plant factor is low.
Existing in a word technology is reacted in traditional reactor such as bubbling still or stirring tank, and the form of reactor has determined mass-transfer efficiency low, and speed of reaction is low; The HCl utilization ratio is low; Need add equipment such as rectifying tower in addition, facility investment is big, the energy consumption height.
Summary of the invention
The objective of the invention is the above-mentioned shortcoming at existing technology, provide a kind of energy consumption low, facility investment is little, and what speed of reaction was high prepares the method for dichlorohydrine from glycerine.
The present invention from the method that glycerine prepares dichlorohydrine is:
At first glycerine is added injection-type reactor with catalyzer, the liquid phase recycle pump is extracted glycerine and catalyzer out in injection-type reactor, enter injection-type reactor from the injection-type reactor top with spray regime again, suck HCl gas from the injection-type reactor sidepiece and injection-type reactor, react with material glycerine and catalyzer thorough mixing; The negative pressure that spray to produce simultaneously with resultant in the injection-type reactor with water, the azeotrope form of dichlorohydrine and HCl is taken out of, water in the azeotrope and dichlorohydrine condensation are got off through condenser, and unreacted HCl gas and the HCl gas that replenishes together enter injection-type reactor and carry out circulating reaction.
Glycerine can be early-products or purified product.Common glycerol content 40～99 weight % of early-products, preferred content is the glycerine of 70～95 weight %; The common content of purification of glycerol is 80～99.9 weight %, and preferred content is the glycerine of 90～95 weight %.Glycerine can be economical obtain by renewable resources, derive from the glycerine of renewable raw materials but this patent is not limited to preferred the use, but also can contain glycerine monochlorohydrin.
The mol ratio of glycerine and HCl gas is 1: 2～10, be preferably 1: 2.2～and 4.
Because the present invention relates to corrosives carries out in injection-type reactor, reactor is made or is applied by the material that tolerates HCl with this understanding.Material can be enamel material, polymkeric substance, resin coating, or some metal or alloy, also can use pottery or sintering metal and refractory materials, preferred enamel material.
Catalyzer is based on carboxylic acid or carboxylic acid derivative and poly carboxylic acid.Carboxylic acid in the catalyzer contains 1～20 carbon atom usually, preferably contain 1～8 carbon atom, and carboxylic acid preferably contains 4 above carbon atoms; The preferred succsinic acid of poly carboxylic acid, pentanedioic acid and hexanodioic acid, preferred hexanodioic acid.Boiling point is more than or equal to 150 ℃ under the normal pressure, is preferably greater than or equals 200 ℃ catalyzer, and catalyzer dissolves in reactant under temperature of reaction, and preferred catalyst discord water generates azeotrope.Catalyst levels accounts for 1～30 weight % of amounts of glycerol, preferred 1～10 weight %.
Reaction usually between 40～180 ℃, preferred 60～140 ℃, between preferred especially 90～120 ℃.The too high meeting of temperature of reaction causes by product such as Polyglycerine to generate, higher temperature even can cause burnt shape thing to generate.The residence time of reactant in injection reactor is 4～20h, preferably 5～10h.
The present invention compared with prior art has following advantage:
1, the present invention utilizes injection-type reactor as reactor
2, speed of reaction improves, the glycerol conversion yield height
3, catalyzer can use repeatedly
4, dichloropropanol content height in the product that directly steams.
Embodiment
Embodiment 1
In injection-type reactor, add 986g industry glycerol (91.9 weight %, 9.84mol) and hexanodioic acid 98g, catalytic amount is 9.9%, is heated to 110 ℃, feeds HCl gas and reacts, feed 2.05h with 7.7mol HCl/h earlier, feed 3.18h with 3.3molHCl/h again, amount to and feed 24.4mol HCl, the mol ratio of glycerine and HCl gas is 1: 2.5.Temperature is controlled at 115 ℃ in the reaction.The hydrogenchloride aeration time is 5.23h, obtains chlorated liquid 764g, cool off in the reaction process distillate 1134g.Consisting of of reaction product:
| Name of material | Weight (g) | Dichlorohydrine (%) | Glycerine monochlorohydrin (%) |
| Chlorated liquid | 764 | ?56.0 | ?34.3 |
| Distillate | 1134 | ?32.8 | ?0.80 |
Embodiment 2
Follow embodiment 1 continuous 3 revision tests, condition is all same with the condition of embodiment 1, does not emit at the bottom of the still, just adds industry glycerol (91.9 weight %), and adds hexanodioic acid and hydrogen chloride gas.Addition sees the following form:
| Number of times | Industry glycerol (g) | Hexanodioic acid (g) | Hydrogenchloride (g) |
| For the first time | 1412 | ?20 | ?1445 |
| For the second time | 845 | ?0 | ?770 |
| For the third time | 1010 | ?20 | ?925 |
Consisting of of reaction product:
| Number of times | Weight (g) | Dichlorohydrine (%) | Glycerine monochlorohydrin (%) |
| For the first time | 3072 | ?30.11 | ?0.39 |
| For the second time | 1139 | ?31.52 | ?0.40 |
| For the third time | 1133 | ?31.05 | ?0.40 |
| Chlorated liquid | 1573 | ?53.90 | ?32.98 |
Embodiment 3
In injection-type reactor, add 1200g industry glycerol (91.9 weight %, 12.0mol) and acetic acid 57.5ml (60.4g), catalytic amount is 5.5%, is heated to 110 ℃, feeds HCl gas and reacts, feed 3h with 3.3mol HCl/h earlier, feed 5.9h with 1.7molHCl/h again, amount to and feed HCl gas 19.8mol, the mol ratio of glycerine and HCl gas is 1: 1.6.Temperature is controlled at 115 ℃ in the reaction.The hydrogenchloride aeration time is 8.9h, obtains chlorated liquid 882g, cool off in the reaction process distillate 1102g.
Consisting of of reaction product:
| Name of material | Weight (g) | Dichlorohydrine (%) | Glycerine monochlorohydrin (%) |
| Chlorated liquid | 882 | ?53.9 | ?33.0 |
| Distillate | 1102 | ?21.8 | ?5.91 |
Reference examples 1:
In having the there-necked flask of prolong, add refining glycerine 232g (98 weight %, 2.47mol) and hexanodioic acid 22.5g, catalytic amount is 9.9%, and heated and stirred to 110 ℃ feeds HCl gas and reacts, feed 3.2h with 1.2molHCl/h, amount to and feed 3.8molHCl, the mol ratio of glycerine and HCl gas is 1: 1.5, and temperature is controlled at 115 ℃ in the reaction.The hydrogenchloride aeration time is 3.2h, obtains chlorated liquid 358g, steams the distillate 34.3g that contains dichlorohydrine and water in the reaction process altogether.
Consisting of of reaction product:
| Name of material | Weight (g) | Dichlorohydrine (%) | Glycerine monochlorohydrin (%) |
| Chlorated liquid | 358 | ?9.35 | ?40.6 |
| Distillate | 34.3 | ?6.94 | ?27.0 |
Reference examples 2:
The mixture adding of 454g glycerine (4.92mol) and 28.10ml Glacial acetic acid (29.5g) is had in the there-necked flask of condensing works, catalytic amount is 6.5%, stirring is warming up to 110 ℃, feed HCl gas then and react, feed 2h with 5.2mol HCl/h earlier, feed 100min with 3.8molHCl/h again, feed 380min with 1.3mol HCl/h at last, amount to and feed hydrogenchloride 23.6mol, the mol ratio of glycerine and HCl gas is 1: 4.8, and temperature is controlled at 115 ℃ in the reaction.The hydrogenchloride aeration time is 10h, obtains chlorated liquid 476g, steams the effluent liquid 558g that contains dichlorohydrine and water in the reaction process altogether.
Consisting of of reaction product:
| Name of material | Weight (g) | Dichlorohydrine (%) | Glycerine monochlorohydrin (%) |
| Chlorated liquid | 476 | ?35.30 | ?18.80 |
| Distillate | 558 | ?23.19 | ?6.90 |
Claims (11)
1. one kind prepares the method for dichlorohydrine from glycerine, it is characterized in that comprising the steps:
At first glycerine is added injection-type reactor with catalyzer, the liquid phase recycle pump is extracted glycerine and catalyzer out in injection-type reactor, enter injection-type reactor from the injection-type reactor top with spray regime again, suck HCl gas from the injection-type reactor sidepiece and injection-type reactor, react with material glycerine and catalyzer thorough mixing; The negative pressure that spray to produce simultaneously with resultant in the injection-type reactor with water, the azeotrope form of dichlorohydrine and HCl is taken out of, water in the azeotrope and dichlorohydrine condensation are got off through condenser, and unreacted HCl gas and the HCl gas that replenishes together enter injection-type reactor and carry out circulating reaction.
2. as claimed in claim 1ly a kind ofly prepare the method for dichlorohydrine from glycerine, it is characterized in that described glycerine is early-products or purified product, early-products glycerol content 40～99 weight %, purification of glycerol content are 80～99.9 weight %.
3. as claimed in claim 2ly a kind ofly prepare the method for dichlorohydrine, it is characterized in that described early-products glycerol content is 70～95 weight % from glycerine; Purification of glycerol content is 90～95 weight %.
4. as claimed in claim 1ly a kind ofly prepare the method for dichlorohydrine from glycerine, the mol ratio that it is characterized in that described glycerine and HCl gas is 1: 2～10.
5. as claimed in claim 4ly a kind ofly prepare the method for dichlorohydrine from glycerine, the mol ratio that it is characterized in that described glycerine and HCl gas is for being 1: 2.2～4.
6. as claimed in claim 1ly a kind ofly prepare the method for dichlorohydrine, it is characterized in that described catalyzer is carboxylic acid or carboxylic acid derivative from glycerine.
7. as claimed in claim 6ly a kind ofly prepare the method for dichlorohydrine, it is characterized in that described carboxylic acid contains 1～20 carbon atom from glycerine.
8. as claimed in claim 7ly a kind ofly prepare the method for dichlorohydrine, it is characterized in that described carboxylic acid contains 1～8 carbon atom from glycerine.
9. as claimed in claim 8ly a kind ofly prepare the method for dichlorohydrine, it is characterized in that described carboxylic acid contains 4-8 carbon atom from glycerine.
10. as claimed in claim 6ly a kind ofly prepare the method for dichlorohydrine, it is characterized in that described carboxylic acid is succsinic acid, pentanedioic acid or hexanodioic acid from glycerine.
11. as claimed in claim 1ly a kind ofly prepare the method for dichlorohydrine, it is characterized in that described catalyst levels accounts for 1～30 weight % of amounts of glycerol from glycerine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710185468 CN101182283B (en) | 2007-12-21 | 2007-12-21 | Method for preparing dichloropropanol by glycerol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710185468 CN101182283B (en) | 2007-12-21 | 2007-12-21 | Method for preparing dichloropropanol by glycerol |
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| Publication Number | Publication Date |
|---|---|
| CN101182283A CN101182283A (en) | 2008-05-21 |
| CN101182283B true CN101182283B (en) | 2011-03-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200710185468 Expired - Fee Related CN101182283B (en) | 2007-12-21 | 2007-12-21 | Method for preparing dichloropropanol by glycerol |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040479B (en) * | 2008-09-09 | 2013-07-31 | 南京工业大学 | System for preparing dichloropropanol by autocatalytic reaction of glycerol and hydrogen chloride |
| CN101747151B (en) * | 2008-12-19 | 2013-03-06 | 南京大学 | Novel technique for preparing dichlorohydrin from glycerin |
| CN112479817A (en) * | 2020-11-25 | 2021-03-12 | 浙江巨化技术中心有限公司 | Method for preparing dichloropropanol by using HCl-containing tail gas |
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