CN109134197B - Method for separating dichloropropanol from dichloropropanol hydrochloric acid solution by using alkane entrainer - Google Patents
Method for separating dichloropropanol from dichloropropanol hydrochloric acid solution by using alkane entrainer Download PDFInfo
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- CN109134197B CN109134197B CN201811218643.8A CN201811218643A CN109134197B CN 109134197 B CN109134197 B CN 109134197B CN 201811218643 A CN201811218643 A CN 201811218643A CN 109134197 B CN109134197 B CN 109134197B
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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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
- C07C29/82—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation by azeotropic distillation
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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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
Abstract
The invention discloses a method for separating dichloropropanol from dichloropropanol hydrochloric acid solution by using an alkane entrainer, which comprises the following specific operation steps: adding an alkane entrainer which is azeotroped with water into the dichloropropanol hydrochloric acid aqueous solution, heating to ensure that the system is azeotroped, separating the hydrochloric acid solution from the alkane entrainer in the distilled component through a rectification cooling process, distilling the component which is not distilled under normal pressure to obtain high-purity dichloropropanol, and recycling the alkane entrainer. The method has simple operation, avoids the complex operation of multiple extractions, and has high separation efficiency and lower cost; all materials can be recycled, the utilization rate of raw materials is high, and the environmental pollution is reduced.
Description
Technical Field
The invention belongs to the field of fine chemicals, and particularly relates to a method for separating dichloropropanol from a dichloropropanol hydrochloric acid solution by using an alkane entrainer.
Background
Epichlorohydrin, namely 3-chloro-1, 2-epoxypropane, is an important organic chemical raw material and a synthetic intermediate, can be used as a solvent for cellulose ester, resin and cellulose ether, is also a raw material for producing surfactants, medicines, pesticides, coatings, adhesives, ion exchange resins, plasticizers, glycerol derivatives and glycidyl derivatives, and is widely applied to the industries of chemical industry, light industry, medicines, electronics and the like.
The prior production method of epoxy chloropropane mainly comprises 3 methods: propylene high-temperature chlorination process using propylene as a raw material, propylene acetate process, and glycerin chlorination process using glycerin as a raw material. The intermediates of all three processes form an azeotrope of dichloropropanol-water-hydrogen chloride. When the mixed aqueous solution of dichloropropanol and hydrogen chloride is used for saponification with calcium hydroxide and sodium hydroxide to prepare epoxy chloropropane, the hydrogen chloride in the azeotrope can be subjected to neutralization reaction with alkali liquor, so that the alkali consumption in the saponification process is high, a large amount of chloride is generated, and the sewage pollution is serious. The above problems are effectively solved if the dichloropropanol in the dichloropropanol-water-hydrogen chloride azeotrope can be separated. The current method for separating the dichloropropanol-water-hydrogen chloride azeotrope mainly uses alkane organic solvent for extraction separation. CN200610161842.0 of jiangsu yangxianghi chemical group ltd discloses a method for extracting and separating dichloropropanol from dichloropropanol hydrochloric acid solution, which uses halogenated hydrocarbons, aromatic ethers, phosphate esters and alkane organic solvents as extracting agents to separate and purify dichloropropanol. A process for preparing epoxy chloropropane from the hydrochloric acid aqueous solution of dichloropropanol is disclosed in CN200910046282.8 of Shanghai Cl-alkali chemical company, which includes extracting and purifying dichloropropanol with the organic solvent of alkane such as alcohol, arene or ether. The extraction and separation of the alkane organic solvent generally needs multi-stage extraction, multi-stage extraction equipment is added, the operation procedures are relatively complicated, the resource waste and the environmental pollution are caused, and the production cost is greatly increased.
The patent CN 107935818A of our company discloses a method for separating dichloropropanol from a dichloropropanol-water-hydrogen chloride azeotrope, ammonia water is used for adjusting the pH value, the mixture is kept stand for layering, and the lower organic phase is subjected to reduced pressure distillation to obtain a pure dichloropropanol product; the upper aqueous phase is cooled and crystallized to obtain ammonium chloride crystals and mother liquor thereof, both of which can be used as raw materials of organic phosphorus products, but in the neutralization treatment process of the method, a large amount of ammonia water needs to be continuously added, the operation is repeated, and the overall process cost is high.
Disclosure of Invention
In order to solve the problems of relatively complicated operation procedures, resource waste and environmental pollution in the prior art, the invention provides a method for separating dichloropropanol from dichloropropanol hydrochloric acid solution by using an alkane entrainer.
A method for separating dichloropropanol from dichloropropanol hydrochloric acid solution by using an alkane entrainer comprises the following operation steps:
(1) placing a dichloropropanol hydrochloric acid solution and an alkane entrainer azeotroped with water into a reaction kettle, wherein the reaction kettle is sequentially connected with a rectifying device, a condensing device and a water dividing device;
(2) heating the reaction kettle to carry out azeotropic distillation on the solution in the reaction kettle, transferring the distillation component into a water separator through a condensing device, standing for layering, and separating the hydrochloric acid solution from the alkane entrainer;
(3) and distilling the undistilled components in the reaction kettle under normal pressure to obtain the dichloropropanol.
Preferably, the alkane organic solvent azeotroped with water in the step (1) may be any one of cyclohexane, n-hexane and n-heptane.
Preferably, the dichloropropanol hydrochloric acid solution in the step (1) is generated in the process of preparing the epichlorohydrin by a glycerol chlorination method, and the mass ratio of the dichloropropanol to the hydrochloric acid solution is 25-35: 62-78.
Preferably, the mass ratio of the alkane azeotropic agent azeotropic with water in the step (1) to the dichloropropanol hydrochloric acid solution is 0.5-4: 1.
Preferably, the mass ratio of the alkane azeotropic agent azeotropic with water in the step (1) to the dichloropropanol hydrochloric acid solution is 1-4: 1.
Preferably, the packing material of the rectification device in the step (1) is more than one of raschig rings, spiral rings, ceramic rings, saddles, coke breeze, quartz, glass springs and insulated magnetic beads, and the packing material stacking mode is random stacking.
Preferably, the azeotropic distillation temperature in the step (2) is 62-70 ℃, and the azeotropic distillation time is 4-12 h.
Preferably, the atmospheric distillation temperature in the step (3) is 70-100 ℃.
The dichloropropanol hydrochloric acid solution is a ternary mixed system containing dichloropropanol, hydrogen chloride and water, the content of the dichloropropanol is high, the separation and extraction of the high-purity dichloropropanol by direct methods such as extraction and distillation are difficult, the recovery rate is low, the cost is high, cyclohexane, n-hexane, n-heptane and the like are selected to act with water to generate azeotropic low-boiling-point alkane water-carrying agents with low solubility in water, the azeotropic low-boiling-point alkane water-carrying agents are added into the dichloropropanol hydrochloric acid solution to form a new alkane-hydrochloric acid azeotropic system, the hydrochloric acid is separated by an azeotropic distillation, condensation and water separation device without introducing other organic impurities, and the separated organic solvent can be recycled as the system water-carrying agent.
Has the advantages that:
(1) the method has the advantages that the low-boiling-point alkane organic solvent which is azeotropic with water and the dichloropropanol hydrochloric acid solution are selected to form a new azeotropic system, the purity of the separated dichloropropanol is high, the recovery rate is high, the residual quantity of the organic solvent in the separated hydrochloric acid solution is small, the use and safety performance of the product are not affected, and the problems of high consumption of the organic solvent after multiple extraction, high residual quantity of the organic solvent and high energy consumption in the traditional method are effectively solved.
(2) The method has simple operation, the alkane organic solvent can be recycled, the cost is lower, and no environmental pollution is caused.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
In the embodiment of the invention, the dichloropropanol hydrochloric acid solution is generated in the process of producing epichlorohydrin by a glycerol chlorination method, and the mass fractions of the dichloropropanol and the hydrochloric acid solution are respectively as follows: 35% of dichloropropanol and 65% of hydrochloric acid solution.
Example 1
(1) Adding 200 g of cyclohexane and 200 g of dichloropropanol hydrochloric acid solution into a three-neck flask, wherein the upper part of the three-neck flask is sequentially connected with a rectifying column, a condenser, a water separator and a tail gas absorption device, the filler of the rectifying column is a glass spring, and the filler stacking mode is random stacking; heating the three-neck flask by an oil bath to enable an azeotropic system to flow back, wherein the temperature is about 70 ℃, the azeotropic distillation time of the system is 7 hours, the distillation component is separated by a water separator to obtain 125 g of hydrochloric acid solution with the mass fraction of 23%, the recovery rate is 96.15%, and the organic solvent residue is 10 ppm;
(2) the mixture of dichloropropanol and cyclohexane is distilled and separated at the normal pressure of 82 +/-1 ℃ to obtain 67.48 g of dichloropropanol, the recovery rate is 96.4 percent, and the purity is 99.2 percent;
(3) 198 g of cyclohexane separated and recovered in the steps (1) and (2) is combined, the recovery rate is 99 percent, and the recovered cyclohexane can be recycled.
Example 2
(1) 200 g of normal hexane and 200 g of dichloropropanol hydrochloric acid solution are placed in a three-mouth flask, the upper part of the three-mouth flask is sequentially connected with a rectifying column, a condenser, a water separator and a tail gas absorption device, and the packing of the rectifying column is Raschig ring and spiral ring; heating the three-neck flask by an oil bath to enable an azeotropic system to flow back, wherein the temperature is about 62 ℃, the azeotropic distillation time of the system is 8 hours, the distillation component is separated by a water separator to obtain 122 g of hydrochloric acid solution with the mass fraction of 24%, the recovery rate is 93.85%, and the residual amount of the organic solvent is 25 ppm;
(2) the mixture of dichloropropanol and n-hexane is distilled and separated at the normal pressure of 70 +/-1 ℃ to obtain 67.27 g of dichloropropanol, the recovery rate is 96.1 percent, and the purity is 99.1 percent;
(3) and (3) combining the steps (1) and (2) to separate and recover 196 g of n-hexane, wherein the recovery rate is 98%, and the recovered n-hexane can be recycled.
Example 3
(1) Adding 400 g of cyclohexane and 200 g of dichloropropanol hydrochloric acid solution into a three-neck flask, placing the three-neck flask into an oil bath pot, sequentially connecting the upper part of the three-neck flask with a rectifying column, a condenser, a water separator and a tail gas absorption device, wherein the filler of the rectifying column is saddle-shaped, and the filler accumulation mode is random; heating the three-neck flask by an oil bath to enable an azeotropic system to flow back, wherein the temperature is about 70 ℃, the azeotropic distillation time of the system is 5 hours, the distillation component is separated by a water separator to obtain 120 g of hydrochloric acid solution with the mass fraction of 24.1%, the recovery rate is 92.3%, and the organic solvent residue is 20 ppm;
(2) the mixture of dichloropropanol and cyclohexane is distilled and separated at the normal pressure of 82 +/-1 ℃ to obtain 67.9 g of dichloropropanol, the recovery rate is 97.0 percent, and the purity is 99.3 percent;
(3) 392 g of cyclohexane separated and recovered in the step (1) and the step (2) are combined, the recovery rate is 98 percent, and the recovered cyclohexane can be recycled.
Example 4
(1) Adding 800 g of n-heptane and 200 g of dichloropropanol hydrochloric acid solution into a three-neck flask, wherein the upper part of the three-neck flask is sequentially connected with a rectifying column, a condenser, a water separator and a tail gas absorption device, the filler of the rectifying column is insulating magnetic beads, and the filler accumulation mode is random stacking; heating the three-neck flask by an oil bath to enable an azeotropic system to flow back, wherein the temperature is about 62 ℃, the azeotropic distillation time of the system is 8 hours, and the distillation component is separated by a water separator to obtain 116g of hydrochloric acid solution with the mass fraction of 24.2%, the recovery rate is 89.23%, and the organic solvent residue is 40 ppm;
(2) distilling and separating the mixture of dichloropropanol and n-heptane at the normal pressure of 99 +/-1 ℃ to obtain 68.25g of dichloropropanol, wherein the recovery rate is 97.5 percent, and the purity is 99.5 percent;
(3) and (3) combining the n-heptane separated and recovered in the steps (1) and (2) to obtain 776 g, wherein the recovery rate is 97%, and the recovered n-hexane can be recycled.
Example 5
(1) Adding 100 g of cyclohexane and 200 g of dichloropropanol hydrochloric acid solution into a three-neck flask, wherein the upper part of the three-neck flask is sequentially connected with a rectifying column, a condenser, a water separator and a tail gas absorption device, the filler of the rectifying column is a glass spring, and the filler stacking mode is random stacking; heating the three-neck flask by using an oil bath to enable an azeotropic system to flow back, wherein the temperature is about 70 ℃, the azeotropic distillation time of the system is 12 hours, the distilled components are separated by a water separator to obtain 122 g of hydrochloric acid solution with the mass fraction of 23.26%, the recovery rate is 93.85%, and the organic solvent residue is 10 ppm;
(2) distilling and separating the mixture of dichloropropanol and cyclohexane at the normal pressure of 82 +/-1 ℃ to obtain 57.89 g of dichloropropanol, wherein the recovery rate is 82.7 percent, and the purity is 89.7 percent;
(3) 96 g of cyclohexane separated and recovered in the steps (1) and (2) are combined, the recovery rate is 96%, and the recovered cyclohexane can be recycled.
The components in the above examples were analyzed by Gas Chromatography (GC) under the following test conditions: OV-1730 m.times.0.32 mm.times.0.25 μm capillary chromatography column; temperature of the column box: keeping the temperature at 90 ℃ for 2 min, the heating rate at 25 ℃/min, the final temperature at 220 ℃ and keeping the temperature for 5 min; the gasification temperature: 250 ℃; detector temperature: 250 ℃; carrier gas: 1.0 ml/min; shunting: 60: 1; hydrogen gas: 30 ml/min; air: 400 ml/min, 1 μ L of sample size.
Claims (4)
1. A method for separating dichloropropanol from dichloropropanol hydrochloric acid solution by using an alkane entrainer is characterized by comprising the following steps:
(1) placing a dichloropropanol hydrochloric acid solution and an alkane azeotropic agent azeotroped with water into a reaction kettle, wherein the reaction kettle is sequentially connected with a rectifying device, a condensing device and a water dividing device, and the alkane organic solvent azeotroped with water is one of cyclohexane, normal hexane and normal heptane;
(2) heating the reaction kettle to carry out azeotropic distillation on the solution in the reaction kettle, transferring the distillation component into a water separator through a condensing device, standing for layering, and separating the hydrochloric acid solution from the alkane entrainer;
(3) distilling the undistilled components in the reaction kettle under normal pressure to obtain dichloropropanol;
the mass ratio of the alkane azeotropic agent azeotropic with water to the dichloropropanol hydrochloric acid solution in the step (1) is 1-4: 1
The dichloropropanol hydrochloric acid solution is generated in the process of preparing the epichlorohydrin by a glycerol chlorination method, and the mass fractions of the dichloropropanol and the hydrochloric acid solution are as follows: 35% of dichloropropanol and 65% of hydrochloric acid solution.
2. The method according to claim 1, wherein the packing material in the rectifying device in step (1) is one or more of raschig rings, spiral rings, porcelain rings, saddle rings, coke breeze, quartz, glass springs and insulated magnetic beads; the filling material is piled up in a scattered mode.
3. The method according to claim 1, wherein the temperature of the azeotropic distillation in the step (2) is 62-70 ℃ and the time of the azeotropic distillation is 4-12 h.
4. The method according to claim 1, wherein the atmospheric distillation temperature in the step (3) is 70 to 100 ℃.
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| CN111362778B (en) * | 2020-03-16 | 2022-04-15 | 山东凯泰科技股份有限公司 | Gas-phase desorption separation process of glycerol distillate |
| CN112645798A (en) * | 2020-12-10 | 2021-04-13 | 山东泰和水处理科技股份有限公司 | Method for separating dichloropropanol hydrochloric acid azeotropic liquid |
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| CN1275558A (en) * | 1999-05-26 | 2000-12-06 | 中国石化集团齐鲁石油化工公司 | Extraction separating method for dichloropropand |
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| CN107935818A (en) * | 2017-12-01 | 2018-04-20 | 山东泰和水处理科技股份有限公司 | A kind of method of separating dichloropropanol in water hydrogen chloride azeotropic mixture from dichlorohydrin |
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| CN1275558A (en) * | 1999-05-26 | 2000-12-06 | 中国石化集团齐鲁石油化工公司 | Extraction separating method for dichloropropand |
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| CN102391072A (en) * | 2011-09-23 | 2012-03-28 | 中国天辰工程有限公司 | Method for separating oil-phase dichloropropanol from mixed aqueous solution of dichloropropanol and chlorine hydride |
| CN107935818A (en) * | 2017-12-01 | 2018-04-20 | 山东泰和水处理科技股份有限公司 | A kind of method of separating dichloropropanol in water hydrogen chloride azeotropic mixture from dichlorohydrin |
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