CN114621057A - Production method of dichloropropanol - Google Patents
Production method of dichloropropanol Download PDFInfo
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- CN114621057A CN114621057A CN202210454221.0A CN202210454221A CN114621057A CN 114621057 A CN114621057 A CN 114621057A CN 202210454221 A CN202210454221 A CN 202210454221A CN 114621057 A CN114621057 A CN 114621057A
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- 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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- 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
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
- C07C29/124—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids of halides
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- 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
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Abstract
The invention relates to a production method of dichloropropanol, which comprises a chloropropene hydrolysis step and an allyl alcohol chlorination step. The dichloropropanol production method overcomes the technical defects of long process flow, short service life of the catalyst, high investment cost and the like in the prior art, produces the dichloropropanol product with the purity of over 98 percent, and is easy to operate and control and easy to realize large-scale popularization and application.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of chemical industry, and particularly relates to a production method of dichloropropanol.
[ background of the invention ]
The dichloropropanol is an important organic synthesis intermediate and an important raw material for producing the epichlorohydrin. The industrial production method of dichloropropanol mainly comprises a propylene high-temperature chlorination method, a propylene acetate method and a glycerol chlorination method.
The propylene high-temperature chlorination method mainly comprises the steps of preparing chloropropene through propylene high-temperature chlorination and synthesizing dichloropropanol through chloropropene hypochlorination, and is a traditional classical method for industrially producing epichlorohydrin. However, the concentration of dichloropropanol is about 4% lower, the concentration difficulty is high, the energy consumption is high, the amount of wastewater generated by directly cyclizing and preparing epoxy chloropropane is large, the method belongs to the technology of 'two high' and tends to be eliminated gradually.
The process of the acetate propylene ester method mainly comprises the steps of synthesizing the acetate propylene ester by propylene, oxygen and acetic acid under the catalytic action of noble metal, hydrolyzing the acetate propylene ester and synthesizing dichloropropanol by allyl alcohol chlorination. The disadvantages of this method are long process flow, short catalyst life and high investment cost.
The glycerol chlorination method is characterized in that glycerol and hydrogen chloride gas react to generate dichloropropanol under the action of a catalyst, and the method is a main production method of epoxy chloropropane at present. However, the production capacity of epichlorohydrin by the glycerol method accounts for 90% of the domestic epichlorohydrin market, and the supply of raw material glycerol is short due to the result of the production capacity. The raw material crude glycerin for producing the epoxy chloropropane by the glycerin method comes from the international market, and as the domestic glycerin method production device is one year ahead, foreign merchants and guests can live in the peculiar goods and the price is increased, in the near future, the domestic epoxy chloropropane market is limited by the supply of the crude glycerin in western countries, and the glycerin method epoxy chloropropane process cannot be continuously developed.
Therefore, in order to solve the drawbacks of the prior art, it is necessary to develop a new route for producing dichloropropanol. The present inventors have completed the present invention through a large number of experiments and studies.
[ summary of the invention ]
[ problem to be solved ]
The invention aims to provide a method for producing dichloropropanol.
[ solution ]
The invention is realized by the following technical scheme.
The invention relates to a method for producing dichloropropanol.
The production method comprises the following steps:
A. hydrolysis of chloropropenes
Chloropropene from the outside enters a hydrolysis reactor 1 from the bottom of the hydrolysis reactor 1 through a pipeline, simultaneously water also enters the hydrolysis reactor 1 from the lower part of the hydrolysis reactor 1, and when the water and the chloropropene pass through the hydrolysis reactor 1 filled with a hydrolysis catalyst from bottom to top, the water and the chloropropene undergo hydrolysis reaction to obtain hydrolysis reaction liquid;
the hydrolysis reaction liquid is conveyed from the top of a hydrolysis reactor 1 to the middle of a phase separator 2 through a pipeline for separation, unreacted chloropropene is discharged from the top of the phase separator 2 and returned to the hydrolysis reaction kettle 1 for reuse, a low-concentration allyl alcohol solution is discharged from the bottom of the phase separator 2 and conveyed to an allyl alcohol tower 3 through a pipeline for rectification to obtain water and a high-concentration allyl alcohol solution, the water is discharged from the bottom of the allyl alcohol tower 3 and returned to the hydrolysis reactor 1 for reuse, and the high-concentration allyl alcohol solution is discharged from the top of the allyl alcohol tower 3;
B. chlorination of allyl alcohol
B, the high-concentration allyl alcohol solution obtained in the step A enters the falling film absorption tower 4 from the top through a pipeline, meanwhile, hydrogen chloride gas from the outside enters the falling film absorption tower 4 from the lower part of the falling film absorption tower through a pipeline, and a high-concentration allyl alcohol solution containing high-concentration hydrogen chloride is obtained at the bottom of the falling film absorption tower 4; the solution is sent to the reactor from the top of the chlorination reactor 5 through a pipeline, meanwhile, chlorine from the outside is sent to the reactor from the lower part of the chlorination reactor 5 through a pipeline, the chlorine and the chlorine react in the chlorination reactor 5 to generate allyl alcohol chlorination products, the products are sent to the tower from the middle part of a hydrogen chloride desorption tower 6 through a pipeline, desorbed HCl gas is discharged from the top of the hydrogen chloride desorption tower 6 and returns to a falling film absorption tower 4 for reuse, the bottom product is a mixed solution of dichloropropanol and water, and the mixed solution is purified to obtain a high-purity dichloropropanol product.
According to a preferred embodiment of the invention, in step a, the chloropropene content is above 99.3% by weight; the weight ratio of chloropropene to water is 1: 1 to 5.
According to another preferred embodiment of the present invention, in step a, the hydrolysis catalyst is selected from a styrenic or acrylic acid-based acidic resin.
According to another preferred embodiment of the invention, in the step A, the hydrolysis reaction is carried out at a temperature of 60-150 ℃, a pressure of 0.1-1.5 MPa and a volume space velocity of chloropropene of 0.25-1.0 h-1Under the conditions of (1).
According to another preferred embodiment of the present invention, in step a, the low concentration allyl alcohol solution is rectified in the allyl alcohol tower 3 under the conditions of the tower bottom temperature of 103 to 105 ℃, the tower top temperature of 90.9 to 91.2 ℃ and the normal pressure, so as to obtain a high concentration allyl alcohol solution with an allyl alcohol concentration of 68 to 72% by weight.
According to another preferred embodiment of the present invention, in step a, the hydrolysis reactor 1 is a reactor having a support plate and a distribution plate at the bottom and a filter plate structure at the top; the phase separator 2 is a phase separator having a hollow structure; the allyl alcohol column 3 is a column having a tray structure.
According to another preferred embodiment of the present invention, in step B, the high-concentration allyl alcohol solution containing a high concentration of hydrogen chloride has a hydrogen chloride content of 15 to 25% by weight.
According to another preferred embodiment of the present invention, in the step B, the chlorination reaction is performed between the high-concentration allyl alcohol solution containing high-concentration hydrogen chloride and hydrogen chloride in the chlorination reactor 5 at a temperature of 0 to 10 ℃ and a pressure of 0.1 to 0.3MPa for 0.5 to 2.0 hours.
According to another preferred embodiment of the invention, in step B, the purity of the dichloropropanol product is more than 98% by weight.
According to another preferred embodiment of the present invention, in step B, the falling film absorption tower 4 is a tower having a round block structure; the chlorination reactor 5 is a reactor with a stirring structure; the hydrogen chloride desorption column 6 is a column having a packed structure.
The present invention will be described in more detail below.
The invention relates to a method for producing dichloropropanol. The specific steps of the production method are shown in attached figures 1 and 2.
The production method comprises the following steps:
A. hydrolysis of chloropropenes
Chloropropene from the outside enters a hydrolysis reactor 1 from the bottom of the hydrolysis reactor 1 through a pipeline, simultaneously water also enters the hydrolysis reactor 1 from the lower part of the hydrolysis reactor 1, and when the water and the chloropropene pass through the hydrolysis reactor 1 filled with a hydrolysis catalyst from bottom to top, the water and the chloropropene undergo hydrolysis reaction to obtain hydrolysis reaction liquid;
the content of chloropropene used in the invention is more than 99.3 percent by weight; the chloropropenes are currently marketed, for example, by the Shandong Zhengji chemical company Limited under the trade name 3-chloropropene or by the Zhou Dang Xing chemical company Limited under the trade name chloropropene.
In this step, the weight ratio of chloropropene to water is 1: 1 to 5. If the weight ratio of chloropropene to water is more than 1: 1, hydrolysis is not easy to carry out; if the weight ratio of chloropropene to water is less than 1: 5, the increase of the water amount has little influence on the reaction conversion rate, and increases the energy consumption instead, which is uneconomical. Therefore, the weight ratio of chloropropene to water is controlled to be 1: 1 to 5 are suitable, preferably 1: 2-4, more preferably 1: 2.5 to 3.5.
The hydrolysis catalyst used in the present invention is selected from styrenic or acrylic acid-based acidic resins, which are currently marketed products, such as those sold under the trade name D001 strong acid cation exchange resin or YKCHWD-1 catalyzed resin by Techno Technology, Inc.; acrylic acid resins are currently marketed, for example, by Tianjingbaohong resin technology ltd under the trade name D113 resin.
According to the invention, the hydrolysis reaction is carried out at the temperature of 60-150 ℃, the pressure of 0.1-1.5 MPa and the volume space velocity of chloropropene of 0.25-1.0 h-1Under the conditions of (1).
In the invention, when the hydrolysis reaction pressure and the chloropropene volume space velocity are in the range, if the hydrolysis reaction temperature is lower than 60 ℃, the hydrolysis reaction is difficult to be carried out completely; if the hydrolysis reaction temperature is higher than 150 ℃, chloropropene is volatile and is not beneficial to the hydrolysis reaction. Therefore, the hydrolysis reaction temperature is suitably 60 to 150 ℃, preferably 80 to 140 ℃, more preferably 90 to 120 ℃.
When the hydrolysis reaction temperature and the volume space velocity of chloropropene are in the range, if the hydrolysis reaction pressure is lower than 0.1MPa, the chloropropene is easy to volatilize; if the hydrolysis reaction pressure is higher than 1.5MPa, the influence on the reaction result is not great, and the equipment investment is increased, so that the method is uneconomical. Therefore, it is appropriate that the hydrolysis reaction pressure is 0.1 to 1.5MPa, preferably 0.2 to 1.2MPa, more preferably 0.4 to 1.0 MPa.
When the hydrolysis reaction temperature and the hydrolysis reaction pressure are in the range, if the volume space velocity of chloropropene is less than 0.25h-1Side reactions are increased, and the product yield is low; if the volume space velocity of chloropropene is more than 1.0h-1The reaction time is insufficient, resulting in a low conversion of the raw materials. Therefore, the volume space velocity of chloropropene is 0.25-1.0 h-1Is contained, preferably for 0.30 to 0.80h-1More preferably 0.40 to 0.60h-1。
The hydrolysis reaction liquid is conveyed from the top of a hydrolysis reactor 1 to the middle of a phase separator 2 through a pipeline for separation, unreacted chloropropene is discharged from the top of the phase separator 2 and returned to the hydrolysis reaction kettle 1 for reuse, a low-concentration allyl alcohol solution is discharged from the bottom of the phase separator 2 and conveyed to an allyl alcohol tower 3 through a pipeline for rectification to obtain water and a high-concentration allyl alcohol solution, the water is discharged from the bottom of the allyl alcohol tower 3 and returned to the hydrolysis reactor 1 for reuse, and the high-concentration allyl alcohol solution is discharged from the top of the allyl alcohol tower 3;
according to the invention, a low-concentration allyl alcohol solution is rectified in an allyl alcohol tower 3 under the conditions of a tower bottom temperature of 103-105 ℃, a tower top temperature of 90.9-91.2 ℃ and normal pressure to obtain a high-concentration allyl alcohol solution with an allyl alcohol concentration of 68-72% by weight. The allyl alcohol concentration was analyzed according to the gas chromatography internal standard method.
In this step, the hydrolysis reactor 1 is a reactor with a bottom provided with a support plate and a distribution plate and a top provided with a filter plate structure. The filter plate structure is used for filtering and removing the catalyst and preventing the catalyst from losing, and the filter plate is a plate provided with a filter medium with the aperture of 0.5-1.0 mm;
the phase separator 2 is a phase separator with a hollow structure, and realizes phase separation by utilizing the immiscible principle of substances; the allyl alcohol column 3 is a column having a tray structure which is a valve float plate or bubble tray.
The hydrolysis reactor 1, the phase separator 2 and the allyl alcohol column 3 used in the present invention are products currently marketed, for example, the hydrolysis reactor 1 sold under the trade name of packed bed reactor by Shandong pharmaceutical industry Co., Ltd, the phase separator 2 sold under the trade name of separator by Shandong Hencoku machinery Co., Ltd, the allyl alcohol column 3 sold under the trade name of rectification column by Wuxi Carnation chemical Equipment Co., Ltd;
B. chlorination of allyl alcohol
The high-concentration allyl alcohol solution obtained in the step A enters the falling film absorption tower 4 from the top through a pipeline, meanwhile, hydrogen chloride gas from outside enters the falling film absorption tower 4 from the lower part through a pipeline, and a high-concentration allyl alcohol solution containing high-concentration hydrogen chloride is obtained at the bottom of the falling film absorption tower 4; the solution is sent into the chlorination reactor 5 from the top of the reactor through a pipeline, meanwhile, chlorine from the outside is sent into the reactor from the lower part of the chlorination reactor 5 through a pipeline, the chlorine and the chlorine react in the chlorination reactor 5 to generate allyl alcohol chlorination products, the products are sent into the hydrogen chloride desorption tower 6 from the middle part of the tower through a pipeline, the desorbed HCl gas is discharged from the top of the hydrogen chloride desorption tower 6 and returns to the falling film absorption tower 4 for reuse, the bottom product of the tower is a mixed solution of dichloropropanol and water, and the mixed solution is purified to obtain a high-purity dichloropropanol product.
According to the present invention, the hydrogen chloride content of the highly concentrated allyl alcohol solution containing a high concentration of hydrogen chloride is 15 to 25% by weight. If the hydrogen chloride content of the high-concentration allyl alcohol solution is lower than 15%, allyl alcohol chlorination side reactions are more; if the hydrogen chloride content of the high-concentration allyl alcohol solution is higher than 25%, the reaction result is not greatly influenced by the increased content; therefore, it is appropriate that the hydrogen chloride content of the high-concentration allyl alcohol solution is 15 to 25%, preferably 18 to 22%;
according to the invention, a chlorination reaction is carried out in a chlorination reactor 5 for 0.5-2.0 h at a temperature of 0-10 ℃ and a pressure of 0.1-0.3 MPa between a high-concentration allyl alcohol solution containing high-concentration hydrogen chloride and hydrogen chloride.
When the chlorination reaction pressure and the chlorination reaction time are in the range, if the chlorination reaction temperature is lower than 0 ℃, the chlorination reaction is difficult to carry out; if the chlorination reaction temperature is higher than 10 ℃, the side reaction products are too much. Therefore, the chlorination reaction temperature is suitably 0 to 10 ℃, preferably 1 to 8 ℃, more preferably 2 to 6 ℃.
When the chlorination reaction temperature and the chlorination reaction time are in the range, if the chlorination reaction pressure is lower than 0.1MPa, the chlorination reaction is not easy to carry out; if the chlorination reaction pressure is higher than 0.3MPa, the influence on the reaction result is not great, and the equipment investment is increased, so that the method is not economical. Therefore, it is reasonable that the chlorination reaction pressure is 0.1 to 0.3MPa, preferably 0.15 to 0.25MPa, and more preferably 0.18 to 0.23 MPa.
When the chlorination reaction temperature and the chlorination reaction pressure are in the range, if the chlorination reaction time is shorter than 0.5h, the chlorination reaction is insufficient, and the conversion rate of raw materials is low; if the chlorination reaction time is longer than 2.0 hours, the side reaction products are too much, which affects the product yield. Therefore, the chlorination reaction time is suitably 0.5 to 2.0 hours, preferably 0.8 to 1.8 hours, more preferably 1.0 to 1.5 hours.
The bottom product discharged from the bottom of the hydrogen chloride-desorbing tower 6 is a mixed liquid of dichloropropanol, water and a small amount of hydrogen chloride. The mixed solution is subjected to conventional extraction, rectification and purification methods to obtain a high-purity dichloropropanol product, and the purity of the dichloropropanol product is over 98 percent by weight according to analysis of a gas chromatography normalization method.
The falling film absorber 4 used in the present invention is a tower having a round block structure, such as a falling film absorber sold under the trade name round block hole type graphite falling film absorber by Shandong Xinbo ao anticorrosive equipment Co., Ltd; the chlorination reactor 5 is a reactor having a stirring structure, such as a reactor sold under the trade name chlorination reactor by Shandong Chengming chemical engineering Co., Ltd; the hydrogen chloride desorption column 6 is a column having a packed structure, such as a column sold under the trade name of a graphite packed column by Shandong Xinbo-ao anticorrosive equipment Co.
[ advantageous effects ]
The invention has the beneficial effects that: the dichloropropanol production method overcomes the technical defects of long process flow, short service life of the catalyst, high investment cost and the like in the prior art, produces the dichloropropanol product with the purity of over 98 percent, and is easy to operate and control and easy to realize large-scale popularization and application.
[ description of the drawings ]
FIG. 1 is a flow diagram of the hydrolysis process of the dichloropropanol production process of the invention;
FIG. 2 is a flow diagram of the chlorination process of the dichloropropanol production process of the invention;
in the figure:
1-a hydrolysis reactor; 2-a phase splitter; a 3-allylic alcohol column; 4-a falling film absorption tower; 5-a chlorination reactor; 6-hydrogen chloride desorption tower.
[ detailed description ] embodiments
The invention will be better understood from the following examples.
Example 1: the invention relates to a method for producing dichloropropanol
The implementation steps of this example are as follows:
A. hydrolysis of chloropropenes
Chloropropene with the content of 99.3 percent from the outside enters the hydrolysis reactor 1 from the bottom of the hydrolysis reactor 1 sold by the pharmaceutical equipment Limited company of Shandong under the trade name of a packed bed reactor through a pipeline, and simultaneously water also enters the hydrolysis reactor 1 from the lower part of the hydrolysis reactor 1, wherein the weight ratio of the chloropropene to the water is 1: 3; water and chloropropene are filled with water from bottom to topWhen the hydrolysis reactor 1 of the styrene series acidic resin hydrolysis catalyst sold by Tianjin Kaishu resin science and technology Limited company under the trade name of D001 strong acid cation exchange resin is used, the temperature, the pressure and the volume space velocity of chloropropene are respectively 1.0h, and the temperature is 120 ℃, the pressure is 1.0MPa-1Carrying out hydrolysis reaction under the condition of (1) to obtain a hydrolysis reaction liquid;
the hydrolysis reaction liquid is conveyed from the top of the hydrolysis reactor 1 to the middle of a phase separator 2 sold by Shandong Hengke mechanical Co., Ltd under the trade name of a separator for separation, unreacted chloropropene is discharged from the top of the phase separator 2 and returned to the hydrolysis reaction kettle 1 for reuse, and the low concentration allyl alcohol solution is discharged from the bottom of the phase separator 2, and is conveyed to an allyl alcohol tower 3 sold by Wuxi Carxian petrochemical equipment Limited company under the trade name of a rectifying tower through a pipeline for rectification under the conditions of the tower bottom temperature of 103-105 ℃, the tower top temperature of 90.9-91.2 ℃ and normal pressure to obtain water and high concentration allyl alcohol solution, and the water and the high concentration allyl alcohol solution are analyzed according to the method described in the specification of the application, the allyl alcohol concentration of the solution is 71 percent by weight, water is discharged from the bottom of an allyl alcohol tower 3 and returned to the hydrolysis reactor 1 for reuse, and high-concentration allyl alcohol solution is discharged from the top of the allyl alcohol tower 3;
B. chlorination of allyl alcohol
The high-concentration allyl alcohol solution obtained in the step A enters the falling film absorption tower 4 from the top through a pipeline, meanwhile, hydrogen chloride gas from outside enters the falling film absorption tower 4 from the lower part through a pipeline, and a high-concentration allyl alcohol solution containing high-concentration hydrogen chloride is obtained at the bottom of the falling film absorption tower 4, and the hydrogen chloride content of the high-concentration allyl alcohol solution is 22% by weight according to the analysis of the method described in the specification of the application; the solution is sent into a chlorination reactor 5 from the top of the reactor through a pipeline, meanwhile, chlorine gas from the outside is sent into the reactor from the lower part of the chlorination reactor 5 through a pipeline, the chlorine gas and the chlorine gas are subjected to chlorination reaction for 2.0 hours under the conditions of 8 ℃ and 0.2MPa pressure in the chlorination reactor 5 to generate allyl alcohol chlorination products, the allyl alcohol chlorination products are sent into a tower from the middle part of a hydrogen chloride desorption tower 6 through a pipeline, desorbed HCl gas is discharged from the top of the hydrogen chloride desorption tower 6 and returned to a falling film absorption tower 4 for reuse, the tower bottom products are mixed liquid of dichloropropanol and water, the mixed liquid is subjected to conventional extraction and rectification purification, and the purity of the dichloropropanol products is 98.1 percent by weight according to the analysis method described in the specification.
Example 2: the invention relates to a method for producing dichloropropanol
The implementation steps of this embodiment are as follows:
A. hydrolysis of chloropropenes
Chloropropene with the content of 99.6 percent from the outside enters the hydrolysis reactor 1 from the bottom of the hydrolysis reactor 1 sold by the pharmaceutical equipment Limited company of Shandong under the trade name of a packed bed reactor, and simultaneously water also enters the hydrolysis reactor 1 from the lower part of the hydrolysis reactor 1, wherein the weight ratio of the chloropropene to the water is 1: 1; when water and chloropropene pass through a hydrolysis reactor 1 containing an acrylic acid resin hydrolysis catalyst sold under the trade name D113 resin by Tianjin Boehong resin science and technology Limited at 60 deg.C under 0.1MPa and at a chloropropene volume space velocity of 0.50h-1Carrying out hydrolysis reaction under the condition of (1) to obtain a hydrolysis reaction liquid;
the hydrolysis reaction liquid is conveyed from the top of the hydrolysis reactor 1 to the middle of a phase separator 2 sold by Shandong Hengke mechanical Co., Ltd under the trade name of a separator for separation, unreacted chloropropene is discharged from the top of the phase separator 2 and returned to the hydrolysis reaction kettle 1 for reuse, and the low concentration allyl alcohol solution is discharged from the bottom of the phase separator 2, and is conveyed to an allyl alcohol tower 3 sold by Wuxi Carxian petrochemical equipment Limited company under the trade name of a rectifying tower through a pipeline for rectification under the conditions of the tower bottom temperature of 103-105 ℃, the tower top temperature of 90.9-91.2 ℃ and normal pressure to obtain water and high concentration allyl alcohol solution, and the water and the high concentration allyl alcohol solution are analyzed according to the method described in the specification of the application, the allyl alcohol concentration of the solution is 68 percent by weight, water is discharged from the bottom of an allyl alcohol tower 3 and returned to the hydrolysis reactor 1 for reuse, and high-concentration allyl alcohol solution is discharged from the top of the allyl alcohol tower 3;
B. chlorination of allyl alcohol
The high-concentration allyl alcohol solution obtained in the step A enters the falling film absorption tower 4 from the top through a pipeline, meanwhile, hydrogen chloride gas from outside enters the falling film absorption tower 4 from the lower part through a pipeline, and a high-concentration allyl alcohol solution containing high-concentration hydrogen chloride is obtained at the bottom of the falling film absorption tower 4, and the hydrogen chloride content of the high-concentration allyl alcohol solution is 15% by weight according to the analysis of the method described in the specification of the application; the solution is sent into a chlorination reactor 5 from the top of the reactor through a pipeline, meanwhile, chlorine from the outside is sent into the reactor from the lower part of the chlorination reactor 5 through a pipeline, the chlorine and the chlorine are subjected to chlorination reaction for 1.0h under the conditions of 0 ℃ and 0.1MPa in the chlorination reactor 5 to generate allyl alcohol chlorination products, the allyl alcohol chlorination products are sent into a hydrogen chloride desorption tower 6 from the middle of the tower through a pipeline, desorbed HCl gas is discharged from the top of the hydrogen chloride desorption tower 6 and returned to a falling film absorption tower 4 for reuse, the bottom products are mixed liquid of dichloropropanol and water, the mixed liquid is extracted, rectified and purified, and the purity of the dichloropropanol products is 99.2% by weight according to the analysis method described in the specification.
Example 3: the invention relates to a method for producing dichloropropanol
The implementation steps of this example are as follows:
A. hydrolysis of chloropropenes
Chloropropene with the content of 99.4 percent from the outside enters the hydrolysis reactor 1 from the bottom of the hydrolysis reactor 1 sold by eastern China pharmaceutical industry Co., Ltd under the trade name of a packed bed reactor through a pipeline, and simultaneously water also enters the hydrolysis reactor 1 from the lower part of the hydrolysis reactor 1, wherein the weight ratio of the chloropropene to the water is 1: 5; when water and chloropropene pass through a hydrolysis reactor 1 containing an acrylic acid resin hydrolysis catalyst sold under the trade name D113 resin by Tianjin Boehong resin science and technology Limited, they are heated at a temperature of 150 ℃, a pressure of 1.5MPa and a volume space velocity of chloropropene of 0.25h-1Carrying out hydrolysis reaction under the condition of (1) to obtain a hydrolysis reaction liquid;
the hydrolysis reaction liquid is conveyed from the top of the hydrolysis reactor 1 to the middle of a phase separator 2 sold by Shandong Hengke mechanical Co., Ltd under the trade name of a separator for separation, unreacted chloropropene is discharged from the top of the phase separator 2 and returned to the hydrolysis reaction kettle 1 for reuse, and the low concentration allyl alcohol solution is discharged from the bottom of the phase separator 2, and is conveyed to an allyl alcohol tower 3 sold by Wuxi Carxian petrochemical equipment Limited company under the trade name of a rectifying tower through a pipeline for rectification under the conditions of the tower bottom temperature of 103-105 ℃, the tower top temperature of 90.9-91.2 ℃ and normal pressure to obtain water and high concentration allyl alcohol solution, and the water and the high concentration allyl alcohol solution are analyzed according to the method described in the specification of the application, the allyl alcohol concentration of the solution is 68 percent by weight, water is discharged from the bottom of an allyl alcohol tower 3 and returned to the hydrolysis reactor 1 for reuse, and high-concentration allyl alcohol solution is discharged from the top of the allyl alcohol tower 3;
B. chlorination of allyl alcohol
The high-concentration allyl alcohol solution obtained in the step A enters the falling film absorption tower 4 from the top through a pipeline, meanwhile, hydrogen chloride gas from outside enters the falling film absorption tower 4 from the lower part through a pipeline, and a high-concentration allyl alcohol solution containing high-concentration hydrogen chloride is obtained at the bottom of the falling film absorption tower 4, and the content of the hydrogen chloride is 18% by weight according to the analysis of the method described in the specification of the application; the solution is sent into a chlorination reactor 5 from the top of the reactor through a pipeline, meanwhile, chlorine from the outside is sent into the reactor from the lower part of the chlorination reactor 5 through a pipeline, the chlorine and the chlorine are subjected to chlorination reaction for 1.5 hours in the chlorination reactor 5 under the conditions of 10 ℃ and 0.3MPa to generate allyl alcohol chlorination products, the allyl alcohol chlorination products are sent into a hydrogen chloride desorption tower 6 from the middle of the tower through a pipeline, desorbed HCl gas is discharged from the top of the hydrogen chloride desorption tower 6 and returned to a falling film absorption tower 4 for reuse, the bottom products are mixed liquid of dichloropropanol and water, the mixed liquid is extracted, rectified and purified, and the purity of the dichloropropanol products is 98.5 percent by weight according to the analysis method described in the specification.
Example 4: the invention relates to a method for producing dichloropropanol
The implementation steps of this embodiment are as follows:
A. hydrolysis of chloropropenes
Chloropropene with the content of 99.5 percent from the outside enters the hydrolysis reactor 1 from the bottom of the hydrolysis reactor 1 sold by eastern China pharmaceutical industry Co., Ltd under the trade name of a packed bed reactor through a pipeline, and simultaneously water also enters the hydrolysis reactor 1 from the lower part of the hydrolysis reactor 1, wherein the weight ratio of the chloropropene to the water is 1: 4; water and chloropropene are filled with water from bottom to topWhen the catalyst is used in a hydrolysis reactor 1 of styrene acid resin hydrolysis catalyst sold by Tianjin Kaishu resin science and technology Limited company under the trade name YKCHWD-1 catalytic resin, the catalyst is heated at 90 ℃, the pressure of 0.5MPa and the volume space velocity of chloropropene of 0.75h-1Carrying out hydrolysis reaction under the condition of (1) to obtain a hydrolysis reaction liquid;
the hydrolysis reaction liquid is conveyed from the top of the hydrolysis reactor 1 to the middle of a phase separator 2 sold by Shandong Hengke mechanical Co., Ltd under the trade name of a separator for separation, unreacted chloropropene is discharged from the top of the phase separator 2 and returned to the hydrolysis reaction kettle 1 for reuse, and the low concentration allyl alcohol solution is discharged from the bottom of the phase separator 2, and is conveyed to an allyl alcohol tower 3 sold by Wuxi Carxian petrochemical equipment Limited company under the trade name of a rectifying tower through a pipeline for rectification under the conditions of the tower bottom temperature of 103-105 ℃, the tower top temperature of 90.9-91.2 ℃ and normal pressure to obtain water and high concentration allyl alcohol solution, and the water and the high concentration allyl alcohol solution are analyzed according to the method described in the specification of the application, the allyl alcohol concentration of the solution is 72 percent by weight, water is discharged from the bottom of an allyl alcohol tower 3 and returned to the hydrolysis reactor 1 for reuse, and high-concentration allyl alcohol solution is discharged from the top of the allyl alcohol tower 3;
B. chlorination of allyl alcohol
The high-concentration allyl alcohol solution obtained in the step A enters the falling film absorption tower 4 from the top through a pipeline, meanwhile, hydrogen chloride gas from outside enters the falling film absorption tower 4 from the lower part through a pipeline, and a high-concentration allyl alcohol solution containing high-concentration hydrogen chloride is obtained at the bottom of the falling film absorption tower 4, and the content of the hydrogen chloride is 25% by weight according to the analysis and determination of the method described in the specification of the application; the solution is sent into a chlorination reactor 5 from the top of the reactor through a pipeline, meanwhile, chlorine from the outside is sent into the reactor from the lower part of the chlorination reactor 5 through a pipeline, the chlorine and the chlorine are subjected to chlorination reaction for 0.5h under the conditions of 5 ℃ and 0.2MPa in the chlorination reactor 5 to generate allyl alcohol chlorination products, the allyl alcohol chlorination products are sent into a hydrogen chloride desorption tower 6 from the middle of the tower through a pipeline, desorbed HCl gas is discharged from the top of the hydrogen chloride desorption tower 6 and returned to a falling film absorption tower 4 for reuse, the bottom products are mixed liquid of dichloropropanol and water, the mixed liquid is extracted, rectified and purified, and the purity of the dichloropropanol products is 98.8% by weight according to the analysis method described in the specification.
Claims (10)
1. The production method of dichloropropanol is characterized by comprising the following steps:
A. hydrolysis of chloropropenes
Chloropropene from outside enters a hydrolysis reactor (1) from the bottom of the hydrolysis reactor (1) through a pipeline, simultaneously water also enters the hydrolysis reactor (1) from the lower part of the hydrolysis reactor (1), and when the water and the chloropropene pass through the hydrolysis reactor (1) filled with a hydrolysis catalyst from bottom to top, the water and the chloropropene undergo hydrolysis reaction to obtain hydrolysis reaction liquid;
the hydrolysis reaction liquid is conveyed from the top of the hydrolysis reactor (1) to the middle of the phase separator (2) through a pipeline for separation, unreacted chloropropene is discharged from the top of the phase separator (2) and returned to the hydrolysis reaction kettle (1) for reuse, while low-concentration allyl alcohol solution is discharged from the bottom of the phase separator (2), the low-concentration allyl alcohol solution is conveyed to an allyl alcohol tower (3) through a pipeline for rectification to obtain water and high-concentration allyl alcohol solution, the water is discharged from the bottom of the allyl alcohol tower (3) and returned to the hydrolysis reactor (1) for reuse, and the high-concentration allyl alcohol solution is discharged from the top of the allyl alcohol tower (3);
B. chlorination of allyl alcohol
The high-concentration allyl alcohol solution obtained in the step A enters the falling film absorption tower (4) from the top through a pipeline, meanwhile, hydrogen chloride gas from outside enters the falling film absorption tower (4) from the lower part through a pipeline, and a high-concentration allyl alcohol solution containing high-concentration hydrogen chloride is obtained at the bottom of the falling film absorption tower (4); the solution is sent to a chlorination reactor (5) from the top of the reactor through a pipeline, meanwhile, chlorine from the outside is sent to the reactor from the lower part of the chlorination reactor (5) through a pipeline, the chlorine and the chlorine are subjected to chlorination reaction in the chlorination reactor (5) to generate allyl alcohol chlorination products, the products are sent to a tower from the middle part of a hydrogen chloride desorption tower (6) through a pipeline, desorbed HCl gas is discharged from the top of the hydrogen chloride desorption tower (6) and returns to a falling film absorption tower (4) for reuse, the bottom products are mixed liquid of dichloropropanol and water, and the mixed liquid is purified to obtain a high-purity dichloropropanol product.
2. The production process according to claim 1, characterized in that in step a, the chloropropene content is 99.3% by weight or more; the weight ratio of chloropropene to water is 1: 1 to 5.
3. The method of claim 1, wherein in step A, the hydrolysis catalyst is selected from styrene-based or acrylic acid-based acidic resins.
4. The production method according to claim 1, wherein in the step A, the hydrolysis reaction is carried out at a temperature of 60-150 ℃, a pressure of 0.1-1.5 MPa and a volume space velocity of chloropropene of 0.25-1.0 h-1Under the conditions of (1).
5. The production process according to claim 1, wherein in the step A, the low concentration allyl alcohol solution is rectified in the allyl alcohol column (3) under the conditions of a column bottom temperature of 103 to 105 ℃, a column top temperature of 90.9 to 91.2 ℃ and normal pressure to obtain a high concentration allyl alcohol solution having an allyl alcohol concentration of 68 to 72% by weight.
6. The production process according to claim 1, characterized in that in step a, the hydrolysis reactor (1) is a reactor having a support plate and distribution plate at the bottom and a filter plate structure at the top; the phase separator (2) is a phase separator with a hollow structure; the allyl alcohol column (3) is a column having a tray structure.
7. The production process according to claim 1, wherein in the step B, the hydrogen chloride content of the highly concentrated allyl alcohol solution containing highly concentrated hydrogen chloride is 15 to 25% by weight.
8. The production process according to claim 1, wherein in the step B, the chlorination reaction is carried out in the chlorination reactor (5) at a temperature of 0 to 10 ℃ and a pressure of 0.1 to 0.3MPa for 0.5 to 2.0 hours by reacting a highly concentrated allyl alcohol solution containing a highly concentrated hydrogen chloride with hydrogen chloride.
9. The process according to claim 1, wherein in step B, the purity of the dichloropropanol product is 98% by weight or more.
10. The production process according to claim 1, characterized in that in step B, the falling film absorption column (4) is a column having a round block structure; the chlorination reactor (5) is a reactor with a stirring structure; the hydrogen chloride desorption column (6) is a column with a packing structure.
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| CN114702464A (en) * | 2022-04-27 | 2022-07-05 | 宁波环洋新材料股份有限公司 | Closed cycle production method for preparing epichlorohydrin by adopting allyl alcohol method |
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