CN101481298A - Production process for refining dichlorohydrin by glycerol reaction distillation - Google Patents
Production process for refining dichlorohydrin by glycerol reaction distillation Download PDFInfo
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- CN101481298A CN101481298A CNA2008100006125A CN200810000612A CN101481298A CN 101481298 A CN101481298 A CN 101481298A CN A2008100006125 A CNA2008100006125 A CN A2008100006125A CN 200810000612 A CN200810000612 A CN 200810000612A CN 101481298 A CN101481298 A CN 101481298A
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Abstract
The invention provides a production process for preparing dichloropropanol by reactive distillation of glycerol. The production process comprises the following steps: the raw material glycerol containing a homogeneous catalyst is sent to a reactive rectification tower from the top after heat exchange, hydrogen chloride gas enters from the lower part of a rectification section of the tubular reactive rectification tower, and the raw material glycerol and countercurrent flow of the hydrogen chloride gas are subject to absorption and chlorination reaction by a packing layer at the temperature of 90-120 DEG C and the temperature of 0.001-0.1MPa (absolute pressure) and are rectified; omonochloropropylene glycol at the bottom of the tubular reactive rectification tower, glycerol and glycerol oligomer are sent to a heavy constituent separation tower for decompressing and recovering the monochloropropylene glycol and the glycerol is returned to the raw material glycerol; and product gas on the top of tubular reactive rectification tower is cooled by a heat exchanger to obtain the dichloropropanol which is sent to a cyclization working procedure, and tail gas is further washed with lye, and is discharged from by a vacuum pump.
Description
1. technical field
The invention provides a kind of production technique of refining dichlorohydrin by glycerol reaction distillation, belong to field of fine chemical.
2. background technology
At present, epoxy chloropropane and presoma dichlorohydrine thereof mainly contain two kinds of production technique: propylene high-temperature chlorination process, vinyl carbinol method and glycerin chlorination method.The propylene high-temperature chlorination process is the main production method of epoxy chloropropane and presoma dichlorohydrine thereof in the world so far, production process flexibly, technical maturity, stable operation, but have transformation efficiency ground, by product is many, energy consumption is high, equipment corrosion is serious, waste water and dregs is many, the more and more high defective of propylene feedstocks price.Vinyl carbinol method reaction conditions gentleness, productive rate height, by product is few, sewage quantity is few, but reactions steps is many, catalyst life short, must prevent the acetate corrosion with stainless material, invests higher relatively.The glycerin chlorination method is produced dichlorohydrine and epoxy chloropropane by the hydrogenchloride single step reaction, need not to use chlorine, reaction conditions gentleness, productive rate height, by product is few, sewage quantity is few and glycerine source is more and more wider and cost is more and more lower along with the raising of yield of biodiesel, has been subjected to people's common concern.
The technology that the glycerin chlorination of Jiangsu polytechnical university exploitation is produced dichlorohydrine and epoxy chloropropane is interrupter method, utilize the hydrogen chloride gas preparation by tank reactor, the investment only be the propylene method 1/4th, cost is low, operational condition is gentle, safe and reliable, waste water only has 1/10th of propylene method, but transformation efficiency is relatively low, raw material consumption is bigger, by product is higher, and scale is difficult to maximize.Publication CN1882522A and CN1845888A are continuous processing production, be the full bed bioreactor that mixes of single or plural serial stage, end reaction product normal pressure or decompression separation, transformation efficiency, selectivity and yield are higher, but raw material consumption is big, by product is higher, scale is difficult to maximize.
3. summary of the invention
Purpose of the present invention is exactly the production technique that a kind of refining dichlorohydrin by glycerol reaction distillation is provided for the deficiency that overcomes the prior art existence.This advantages of simple technological process, reaction conditions temperature, system temperature are easy to control, and reaction conversion ratio, yield and selectivity height are easy to large-scale industrial production.
Technical scheme of the present invention:
The invention provides a kind of production technique of refining dichlorohydrin by glycerol reaction distillation.The raw material glycerine that contains homogeneous catalyst after the heat exchange enters from the reactive distillation top of tower, hydrogen chloride gas enters through gas distributor from the bottom of tubular reaction fractionating tower packing section, and raw material glycerine and hydrogen chloride gas adverse current at 90～120 ℃, 0.001～0.1MPa (absolute pressure) chlorination reaction rectifying take place down to absorb by packing layer; Reaction heat shifts out by the water coolant between tubulation, keeps temperature of reaction; Glycerine monochlorohydrin at the bottom of the tubular reaction fractionating tower, glycerine and glycerin oligomer send heavy constituent knockout tower reclaim under reduced pressure glycerine monochlorohydrin and glycerine to send back in the raw material glycerine; The product gas on tubular reaction fractionating tower top obtains dichlorohydrine through the interchanger cooling and send the cyclisation operation, and the further buck of tail gas is washed the back and effluxed with vacuum pump.
Tubular reaction fractionating tower can be a single-stage, also can be secondary or the plural serial stage reaction fractionating tower of higher level's tower bottom material as subordinate's cat head charging.
The structure of tubular reaction fractionating tower is that the rectifying section of tower is the tubular heat exchange structure, and filler is housed in the tubulation, is water coolant between pipe.
The material of tubular reaction fractionating tower, interchanger, vapor-liquid separation tank and heavy constituent knockout tower is acid-resistant alloy steel, liner enamel, polyvinyl chloride, polypropylene, polytetrafluoroethylmaterial material or resin-coated carbon steel.
Homogeneous catalyst is one or more in carboxylic acid, carboxylic acid anhydride, carboxylic acid amide, carboxylate salt or the carboxylicesters of 180 ℃ of atmospheric boiling points, and consumption is 2～10% of a glycerine.
Hydrogen chloride gas is that hydrochloric acid soln is produced by extracting rectifying, and extraction agent is one or more in sulfuric acid, sodium-chlor, calcium chloride, calcium sulfate, sodium sulfate of volumetric molar concentration 25～32.3% etc.
4, description of drawings
Accompanying drawing is a process flow sheet of the present invention.Fig. 1 is the technical process of single-stage reaction, and Fig. 2 is the technical process of third order reaction
Wherein: 1-tubular reaction fractionating tower, 2-filler, 3-liquid distributor, 4-tubulation, 5-interchanger, 6-vapor-liquid separation tank, 7-heavy constituent knockout tower, 8-caustic treater, 9-vacuum pump 10-gas distributor
5. embodiment
The present invention will be described in detail below in conjunction with accompanying drawing:
Embodiment 1: the raw material glycerine that contains homogeneous catalyst after the heat exchange enters from tubular reaction fractionating tower 1 top, hydrogen chloride gas enters through gas distributor 10 from the bottom of 2 sections of the fillers of tubular reaction fractionating tower 1, and raw material glycerine that gets off from liquid distributor 3 and hydrogen chloride gas adverse current at 90～120 ℃, 0.001～0.1MPa (absolute pressure) chlorination reaction rectifying take place down to absorb by 2 layers of fillers; Reaction heat shifts out by the water coolant of 4 of tubulations, keeps temperature of reaction; Glycerine monochlorohydrin, glycerine and the glycerin oligomer at 1 end of tubular reaction fractionating tower send heavy constituent knockout tower 7 reclaim under reduced pressure glycerine monochlorohydrins and glycerine to send back in the raw material glycerine; The product gas on tubular reaction fractionating tower 1 top reclaims the heat cooling through interchanger 5, obtains dichlorohydrine at vapor-liquid separation tank 6 and send the cyclisation operation, and tail gas further effluxes with vacuum pump 9 after caustic treater 8 bucks are washed.
Embodiment 2: the raw material glycerine that contains homogeneous catalyst after the heat exchange enters from one-level tubular reaction fractionating tower 1 top, hydrogen chloride gas enters through gas distributor 10 from the bottom of 2 sections of the fillers of tubular reaction fractionating tower 1, and raw material glycerine that gets off from liquid distributor 3 and hydrogen chloride gas adverse current at 90～120 ℃, 0.001～0.1MPa (absolute pressure) chlorination reaction rectifying take place down to absorb by 2 layers of fillers; Reaction heat shifts out by the water coolant of 4 of tubulations, keeps temperature of reaction; The liquid at 1 end of one-level tubular reaction fractionating tower send secondary tubular reaction fractionating tower 1 top as charging; One liquid at 1 end of secondary tubular reaction fractionating tower send three grades of tubular reaction fractionating towers, 1 top as charging; Glycerine monochlorohydrin, glycerine and the glycerin oligomer at three grades of 1 ends of tubular reaction fractionating tower send heavy constituent knockout tower 7 reclaim under reduced pressure glycerine monochlorohydrins and glycerine to send back in the raw material glycerine; The product gas on tubular reaction fractionating towers at different levels 1 top reclaims the heat cooling through interchanger 5, obtains dichlorohydrine at vapor-liquid separation tank 6 and send the cyclisation operation, and tail gas further effluxes with vacuum pump 9 after caustic treater 8 bucks are washed.
80% glycerine is used this production technique, and per pass conversion is about 99%, and the selectivity of dichlorohydrine is about 95%, and the consumption of caustic soda reduces greatly, and wastewater flow rate and dichlorohydrine cost reduce.
Claims (6)
1. the invention provides a kind of production technique of refining dichlorohydrin by glycerol reaction distillation, its technical characterictic is that the raw material glycerine that contains homogeneous catalyst after the heat exchange enters from the reactive distillation top of tower, hydrogen chloride gas enters from the bottom of tubular reaction fractionating tower packing section, and raw material glycerine and hydrogen chloride gas adverse current at 90～120 ℃, 0.001～0.1MPa (absolute pressure) chlorination reaction rectifying take place down to absorb by packing layer; Reaction heat shifts out by the water coolant between tubulation, keeps temperature of reaction; Glycerine monochlorohydrin at the bottom of the tubular reaction fractionating tower, glycerine and glycerin oligomer send heavy constituent knockout tower reclaim under reduced pressure glycerine monochlorohydrin and glycerine to send back in the raw material glycerine; The product gas on tubular reaction fractionating tower top obtains dichlorohydrine through the interchanger cooling and send the cyclisation operation, and the further buck of tail gas is washed the back and effluxed with vacuum pump.
2. according to the production technique of a kind of refining dichlorohydrin by glycerol reaction distillation that claim 1 provided, the structure that it is characterized in that tubular reaction fractionating tower is that the rectifying section of tower is the tubular heat exchange structure, and filler is housed in the tubulation, is water coolant between pipe.
3. according to the production technique of a kind of refining dichlorohydrin by glycerol reaction distillation that claim 1 provided, it is characterized in that the material of tubular reaction fractionating tower, static mixer and hydrolysis tower is acid-resistant alloy steel or liner enamel, polyvinyl chloride, polypropylene or polytetrafluoroethylmaterial material or resin-coated carbon steel.
4. according to the production technique of a kind of refining dichlorohydrin by glycerol reaction distillation that claim 1 provided, it is characterized in that tubular reaction fractionating tower can be a single-stage, also can be secondary or the plural serial stage reaction fractionating tower of higher level's tower bottom material as subordinate's cat head charging.
5. according to the production technique of a kind of refining dichlorohydrin by glycerol reaction distillation that claim 1 provided, it is characterized in that homogeneous catalyst is one or more in carboxylic acid, carboxylic acid anhydride, carboxylic acid amide, carboxylate salt or the carboxylicesters of 180 ℃ of atmospheric boiling points, consumption is 2～10% of a glycerine.
6. according to the production technique of a kind of refining dichlorohydrin by glycerol reaction distillation that claim 1 provided, it is characterized in that hydrogen chloride gas is that hydrochloric acid soln is produced by extracting rectifying, extraction agent is one or more in sulfuric acid, sodium-chlor, calcium chloride, calcium sulfate, sodium sulfate of volumetric molar concentration 25～32.3% etc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100006125A CN101481298A (en) | 2008-01-11 | 2008-01-11 | Production process for refining dichlorohydrin by glycerol reaction distillation |
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| CNA2008100006125A CN101481298A (en) | 2008-01-11 | 2008-01-11 | Production process for refining dichlorohydrin by glycerol reaction distillation |
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| CN101481298A true CN101481298A (en) | 2009-07-15 |
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| CNA2008100006125A Pending CN101481298A (en) | 2008-01-11 | 2008-01-11 | Production process for refining dichlorohydrin by glycerol reaction distillation |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709124A (en) * | 2013-12-06 | 2014-04-09 | 中国天辰工程有限公司 | Method for producing epoxy chloropropane |
| CN111499598A (en) * | 2020-04-27 | 2020-08-07 | 湖北三里枫香科技有限公司 | Production process for preparing epichlorohydrin by glycerol method |
| CN112194565A (en) * | 2019-07-07 | 2021-01-08 | 吴军祥 | Method for treating tail gas of potassium sulfate by virtue of Mannheim process and synthesizing dichloropropanol |
-
2008
- 2008-01-11 CN CNA2008100006125A patent/CN101481298A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709124A (en) * | 2013-12-06 | 2014-04-09 | 中国天辰工程有限公司 | Method for producing epoxy chloropropane |
| CN112194565A (en) * | 2019-07-07 | 2021-01-08 | 吴军祥 | Method for treating tail gas of potassium sulfate by virtue of Mannheim process and synthesizing dichloropropanol |
| CN111499598A (en) * | 2020-04-27 | 2020-08-07 | 湖北三里枫香科技有限公司 | Production process for preparing epichlorohydrin by glycerol method |
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Open date: 20090715 |