CN114749121B - System and process for preparing epichlorohydrin by glycerol method - Google Patents
System and process for preparing epichlorohydrin by glycerol method Download PDFInfo
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- CN114749121B CN114749121B CN202210541401.2A CN202210541401A CN114749121B CN 114749121 B CN114749121 B CN 114749121B CN 202210541401 A CN202210541401 A CN 202210541401A CN 114749121 B CN114749121 B CN 114749121B
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- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
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- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/24—Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
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- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
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Abstract
The invention discloses a system and a process for preparing epichlorohydrin by a glycerol method, wherein the system comprises a glycerol chlorination system and a dichloropropanol cyclization system, and the glycerol chlorination system comprises glycerol chlorination reaction equipment, glycerol chlorination separation equipment and a dichloropropanol storage tank which are sequentially communicated; the dichloropropanol cyclization system comprises a dichloropropanol cyclization reaction device, a dichloropropanol cyclization separation device and an epichlorohydrin storage tank which are sequentially connected and communicated; the dichloropropanol cyclization reaction equipment is communicated with a dichloropropanol storage tank. The invention can avoid the combination of a plurality of reactors in the glycerol chlorination process and save a multi-stage rectifying tower in the dichloropropanol cyclization, thereby achieving the purposes of reducing equipment investment, saving energy and reducing consumption.
Description
Technical Field
The invention relates to the technical field of chemical production, in particular to a system and a process for preparing epichlorohydrin by a glycerol method.
Background
Epichlorohydrin, also known as epichlorohydrin, having the formula C3H5OCl, molecular weight: 92.85, boiling point: 116.1 ℃, melting point-25 ℃, freezing point: 57.2 ℃, is an unstable and volatile oily colorless liquid, can be mixed and dissolved with various organic solvents such as ethanol, carbon tetrachloride and the like, and is an important fine chemical product and organic chemical raw material.
The epoxy chloropropane has wide application, can prepare epoxy resin with strong chemical medium corrosion resistance, high caking property, low shrinkage, excellent dielectric property and high impact strength, and is widely applied to the industries of adhesives, coatings, casting materials, reinforcing materials, electronic laminated products and the like.
The traditional method for synthesizing epichlorohydrin comprises a propylene high-temperature chlorination method and a propylene acetate method, wherein the two methods are that firstly intermediate dichloropropanol is synthesized, and then epichlorohydrin is synthesized. The propylene high-temperature chlorination method is mainly divided into the following three units: firstly, propylene is chloridized at high temperature to prepare chloropropene, secondly, dichloropropanol is prepared, thirdly, epoxy chloropropane is obtained by saponification, although the process is mature and the operation is stable, the defects of the process comprise large chlorine consumption, a plurality of byproducts, serious corrosion to equipment and waste water treatment cost and environmental pollution caused by a large amount of chlorine-containing waste water; the acetate propylene ester process is mainly divided into the following four units: the method comprises the steps of synthesizing allyl acetate, hydrolyzing the allyl acetate, synthesizing dichloropropanol by chlorination of allyl alcohol and allyl alcohol, and saponifying to obtain epoxy chloropropane. The glycerol is used as a raw material to prepare the epichlorohydrin for a long time, small tests are already completed in a laboratory in the middle of 20 th century, but because the glycerol is expensive and industrialization is not realized all the time, and along with the rapid increase of the yield of the glycerol in recent years, the glycerol method for further producing the epichlorohydrin is used for synthesizing the dichloropropanol by reacting the glycerol with hydrogen chloride gas and enters the visual field of people again, and the process has the advantages of avoiding the harsh reaction conditions of a propylene high-temperature chlorination method and waste water which is difficult to treat, not only avoiding the whole process flow to be complicated like an acetic propylene ester method, and being very beneficial to industrial production.
However, in the existing process for preparing epichlorohydrin by using a glycerol method, in the glycerol chlorination process, because the chlorination reaction conversion rate is continuously reduced, the conversion from glycerol to dichloropropanol can be completed only by cascade connection of a plurality of reactors, a large amount of equipment cost is consumed, and the operation process is more complicated, for example, in the patent with the patent application number of CN202010346652.6, the reactors are required to be stirred tank reactors, bubbling reactors, external circulation reactors and other types, and the number of the reactors is 1-5; in the cyclization process, alkali is added into dichloropropanol for cyclization to generate epoxy chloropropane, and then the product and unreacted raw materials are separated by rectification, for example, in the patent with the patent application number of CN202010346652.6, a pre-reactor is firstly arranged, then cyclization reactions are carried out by serially connecting cyclization towers, and finally separation of the product is realized by using a second rectifying tower, and the multistage reactor and the multistage rectifying tower are serially connected, so that the process operation difficulty is increased, and public works such as water vapor and the like are additionally consumed.
Therefore, it is an urgent need to solve the problems of the art to provide a simplified and efficient system and process for preparing epichlorohydrin by using a glycerol method.
Disclosure of Invention
In view of the above, the invention provides a system and a process for preparing epichlorohydrin by a glycerol method, which can avoid the combination of a plurality of reactors in the glycerol chlorination process and omit a multi-stage rectifying tower in the dichloropropanol cyclization, thereby achieving the purposes of reducing equipment investment, saving energy and reducing consumption.
In order to achieve the purpose, the invention adopts the following technical scheme:
a system for preparing epoxy chloropropane by a glycerol method comprises:
the glycerol chlorination system comprises glycerol chlorination reaction equipment, glycerol chlorination separation equipment and a dichloropropanol storage tank which are sequentially connected and communicated;
the system comprises a dichloropropanol cyclization system, a dichloropropanol cyclization reaction device, a dichloropropanol cyclization separation device and an epichlorohydrin storage tank, wherein the dichloropropanol cyclization reaction device, the dichloropropanol cyclization separation device and the epichlorohydrin storage tank are sequentially communicated; the dichloropropanol cyclization reaction equipment is communicated with the dichloropropanol storage tank.
Further, the glycerol chlorination reaction equipment comprises a hydrochloric acid storage tank, a HCL gas storage tank, a glycerol storage tank, a tubular reactor and a tower type bubbling reactor, wherein the hydrochloric acid storage tank is communicated with the tubular reactor through a hydrochloric acid raw material pump and a raw material preheater; the HCL gas storage tank is communicated with the tubular reactor through the raw material preheater, and is communicated with the tower type bubbling reactor; the glycerol storage tank is communicated with the tubular reactor through a glycerol raw material pump and the raw material preheater; the tower type bubbling reactor is communicated with the tubular reactor.
Further, the glycerol chlorination separation equipment comprises a first rectifying tower, a first rectifying tower total condenser and a first rectifying tower reboiler, wherein the tower type bubble reactor is communicated with the first rectifying tower through a first rectifying tower feed pump and a first dichloropropanol preheater, and the bottom of the first rectifying tower is communicated with the tower type bubble reactor through a circulating liquid cooler and a material circulating pump; the top of the first rectifying tower is communicated with the dichloropropanol storage tank through a full condenser of the first rectifying tower, and the dichloropropanol storage tank is communicated with the tower kettle of the first rectifying tower through a reflux pump of the first rectifying tower; the bottom of the first rectifying tower is communicated with a first rectifying tower reboiler, and the first rectifying tower reboiler is communicated with the first rectifying tower kettle.
Further, the dichloropropanol cyclization reaction equipment comprises a dichloropropanol cyclization reactor and a crude epichlorohydrin storage tank, wherein the dichloropropanol storage tank is communicated with the dichloropropanol cyclization reactor through a dichloropropanol feeding pump and a second dichloropropanol preheater; the bottom of the dichloropropanol cyclization reactor is connected with a pipeline for introducing saturated steam; discharging waste water from the bottom of the dichloropropanol cyclization reactor through a waste water cooler and a waste water pump; and the crude epoxy chloropropane storage tank is communicated with the top of the dichloropropanol cyclization reactor through a crude epoxy chloropropane cooler.
Further, the dichloropropanol cyclization separation equipment comprises a second rectifying tower, a second rectifying tower total condenser and a second rectifying tower reboiler, wherein the crude epoxy chloropropane storage tank is communicated with the second rectifying tower through a second rectifying tower feed pump and a second rectifying tower preheater; the top of the second rectifying tower is communicated with the epoxy chloropropane storage tank through a second rectifying tower complete condenser, and the epoxy chloropropane storage tank is communicated with the tower kettle of the second rectifying tower through a second rectifying tower reflux pump; the bottom of the second rectifying tower is communicated with a reboiler of the second rectifying tower, and the reboiler of the second rectifying tower is communicated with the kettle of the second rectifying tower; and discharging the organic waste liquid from the bottom of the second rectifying tower through an organic waste liquid pump and an organic waste liquid cooler.
A process for preparing epichlorohydrin by a glycerol method comprises the following steps:
1) mixing glycerol and HCI gas according to a molar ratio of 1: 2, continuously pressing the mixture into a tubular reactor for chlorination reaction, and converting glycerol;
2) and (2) allowing the material at the outlet of the tubular reactor to enter a tower type bubbling reactor for further reaction, continuously discharging generated water, dichloropropanol and HCI, and introducing HC1 gas into the tower type bubbling reactor in the process, wherein the ratio of the introduced HC1 gas to glycerol is 1: 1;
3) sending the crude dichloropropanol product generated in the step 2) to a first rectifying tower for rectifying to obtain high-purity dichloropropanol serving as a raw material in a cyclization reaction stage;
4) and (2) loading a catalyst into a catalyst bed layer of a dichloropropanol cyclization reactor, conveying the dichloropropanol into the dichloropropanol cyclization reactor for cyclization reaction, introducing saturated steam into the bottom of the dichloropropanol cyclization reactor in the process, separating out epoxy chloropropane, condensing the epoxy chloropropane, conveying the epoxy chloropropane to a second rectifying tower for further purification, wherein the bottom liquid of the second rectifying tower contains unreacted dichloropropanol, and refluxing to the dichloropropanol cyclization reactor for cyclization reaction again.
Further, in the step 1), the operating temperature of the tubular reactor is 60-140 ℃, a catalyst is added into the tubular reactor, and the using amount of the catalyst accounts for 1-3% of the glycerol amount; the catalyst is butyric acid or valeric acid.
Further, in the step 2), the operation temperature of the tower type bubble reactor is 100-140 ℃.
Further, in the step 3), the first rectifying tower is a decompression tower, the vacuum degree is-0.015 MPa-0.025 MPa, and the reflux ratio is 0.5-3.5.
Further, in the step 4), the operating temperature of the dichloropropanol cyclization reactor is 90-130 ℃, the cyclization reaction time is 10-30 min, the cyclization reaction pressure is 30-50 kPa, the second rectification tower is an atmospheric tower, and the reflux ratio is 1-4.
Therefore, compared with the prior art, the system and the process for preparing the epichlorohydrin by the glycerol method provided by the invention have the advantages that 1) a glycerol chlorination process is realized, and a tubular reactor and a tower type bubbling reactor are coupled, so that the defects of series connection of multistage reactors, large equipment investment and gradual reduction of reaction conversion rate are overcome; 2) the bottom of the dichloropropanol cyclization reactor is filled with steam to blow out the primary product epichlorohydrin, and the reactor is endowed with a separation function, namely reactive distillation is used, so that the cascade connection of multistage distillation columns is avoided, and the equipment investment and energy consumption are saved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a schematic diagram of a process flow of a system for preparing epichlorohydrin by a glycerol method according to the present invention;
FIG. 2 is a schematic diagram of a glycerol chlorination system provided by the present invention;
FIG. 3 is a schematic structural diagram of a dichloropropanol cyclization system provided by the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The technical scheme of the invention is further explained by taking the annual production of 5 ten thousand tons of epoxy chloropropane as an example.
As shown in fig. 1-3, the embodiment of the invention discloses a system for preparing epichlorohydrin by a glycerol method, which comprises a glycerol chlorination system and a dichloropropanol cyclization system, wherein the glycerol chlorination system comprises a glycerol chlorination reaction device, a glycerol chlorination separation device and a dichloropropanol storage tank which are sequentially communicated; the dichloropropanol cyclization system comprises a dichloropropanol cyclization reaction device, a dichloropropanol cyclization separation device and an epichlorohydrin storage tank which are sequentially communicated; the dichloropropanol cyclization reaction equipment is communicated with a dichloropropanol storage tank.
The glycerol chlorination reaction equipment comprises a hydrochloric acid storage tank 1, a HCL gas storage tank 2, a glycerol storage tank 3, a tubular reactor 4 and a tower type bubbling reactor 5, wherein the hydrochloric acid storage tank 1 is communicated with the tubular reactor 4 through a hydrochloric acid raw material pump 6 and a raw material preheater 7; the HCL gas storage tank 2 is communicated with the tubular reactor 4 through a raw material preheater 7, and the HCL gas storage tank 2 is communicated with the tower type bubbling reactor 5; the glycerol storage tank 3 is communicated with the tubular reactor 4 through a glycerol raw material pump 8 and a raw material preheater 7; the tower type bubbling reactor 5 is communicated with the tubular reactor 4;
the glycerol chlorination separation equipment comprises a first rectifying tower 9, a first rectifying tower total condenser 10 and a first rectifying tower reboiler 11, wherein the tower type bubble reactor 5 is communicated with the first rectifying tower 9 through a first rectifying tower feed pump 12 and a first dichloropropanol preheater 13, and the bottom of the first rectifying tower 9 is communicated with the tower type bubble reactor 5 through a circulating liquid cooler 14 and a material circulating pump 15; the top of the first rectifying tower 9 is communicated with a dichloropropanol storage tank 16 through a first rectifying tower total condenser 10, and the dichloropropanol storage tank 16 is communicated with the tower bottom of the first rectifying tower 9 through a first rectifying tower reflux pump 17; the bottom of the first rectifying tower 9 is communicated with a first rectifying tower reboiler 11, and the first rectifying tower reboiler 11 is communicated with the first rectifying tower 9;
the dichloropropanol cyclization reaction equipment comprises a dichloropropanol cyclization reactor 18 and a crude epichlorohydrin storage tank 19, wherein the dichloropropanol storage tank 16 is communicated with the dichloropropanol cyclization reactor 18 through a dichloropropanol feeding pump 20 and a second dichloropropanol preheater 21; the bottom of the dichloropropanol cyclization reactor 18 is connected with a pipeline for introducing saturated steam; the bottom of the dichloropropanol cyclization reactor 18 discharges waste water through a waste water cooler 22 and a waste water pump 23; the crude epoxy chloropropane storage tank 19 is communicated with the top of the dichloropropanol cyclization reactor 18 through a crude epoxy chloropropane cooler 24.
The dichloropropanol cyclization separation equipment comprises a second rectifying tower 25, a second rectifying tower total condenser 26 and a second rectifying tower reboiler 27, wherein the crude epichlorohydrin storage tank 19 is communicated with the second rectifying tower 25 through a second rectifying tower feed pump 28 and a second rectifying tower preheater 29; the top of the second rectifying tower 25 is communicated with an epichlorohydrin storage tank 30 through a second rectifying tower complete condenser 26, and the epichlorohydrin storage tank 30 is communicated with the tower kettle of the second rectifying tower 25 through a second rectifying tower reflux pump 31; the bottom of the second rectifying tower 25 is communicated with a second rectifying tower reboiler 27, and the second rectifying tower reboiler 27 is communicated with the bottom of the second rectifying tower 25; the organic waste liquid is discharged from the bottom of the second rectifying tower 25 through an organic waste liquid pump 32 and an organic waste liquid cooler 33.
It is worth mentioning that the connections between the above components are all connected by pipes.
The embodiment of the invention also discloses a process for preparing epichlorohydrin by using a glycerol method, which comprises the following steps:
1) mixing glycerol and HCI gas according to a molar ratio of 1: 2, continuously pressing the mixture into a tubular reactor 4 for chlorination reaction, converting glycerol, wherein the conversion rate can be close to 100 percent, the interior of the tubular reactor 4 is provided with a filler or a proper internal member so as to ensure that reactants have good mixing effect in the flowing process, and the filler used by a general filler tower or the internal member used by a static mixer can be used;
in the step, the operation temperature of the tubular reactor 4 is 60-140 ℃, a catalyst is added into the tubular reactor 4, and the using amount of the catalyst accounts for 1-3% of the glycerol amount; the catalyst is butyric acid or valeric acid.
2) And (2) feeding the material (containing 3-chloro-1, 2-propanediol) at the outlet of the tubular reactor 4 into a tower type bubble reactor 5 for further reaction, continuously discharging the generated water, dichloropropanol and HCI, and introducing HC1 gas into the tower type bubble reactor 5 in the process, wherein the ratio of the introduced HC1 gas to the glycerol is 1: 1, both the conversion of glycerol is increased by excess HC1 and the H formed is carried away by the gas 2 O, driving the reaction to proceed;
the tubular reactor 4 in the step 1) is coupled with the tower type bubbling reactor 5 in the step 2), so that the defects of series connection of multistage reactors, large equipment investment and gradual reduction of reaction conversion rate are avoided.
In this step, the operating temperature of the tower bubble reactor 5 is 100 to 140 ℃.
3) Sending the dichloropropanol crude product (containing water, glycerol, a small amount of 3-chloro-1 and 2-propylene glycol) generated in the step 2) to a first rectifying tower 9 for rectification operation to obtain high-purity dichloropropanol as a raw material in a cyclization reaction stage;
in this step, the first rectifying tower 9 is a vacuum tower, the vacuum degree is-0.015 MPa to 0.025MPa, and the reflux ratio is 0.5 to 3.5.
4) The method comprises the following steps of putting a catalyst into a catalyst bed layer of a dichloropropanol cyclization reactor 18, preheating dichloropropanol, conveying the dichloropropanol into the dichloropropanol cyclization reactor 18 through a pump for cyclization reaction, and introducing saturated steam into the bottom of the dichloropropanol cyclization reactor 18 in the process to separate epoxy chloropropane, so that the reactor is endowed with a separation function, namely reactive distillation is used, the cascade connection of multistage rectifying towers is avoided, and the equipment investment and energy consumption are saved; and the epoxy chloropropane is condensed and then sent to a second rectifying tower 25 for further purification, the residue of the second rectifying tower 25 contains unreacted dichloropropanol, and the unreacted dichloropropanol flows back to the dichloropropanol cyclization reactor 18 for cyclization reaction again, so that the conversion rate is improved.
In the step, the operating temperature of the dichloropropanol cyclization reactor 18 is 90-130 ℃, the cyclization reaction time is 10-30 min, the cyclization reaction pressure is 30-50 kPa, the second rectifying tower 25 is an atmospheric tower, the reflux ratio is 1-4, the yield of the epoxy chloropropane can reach 96%, and the purity can reach 99.7%.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A glycerine method preparation epoxy chloropropane system which characterized in that includes:
the glycerol chlorination system comprises glycerol chlorination reaction equipment, glycerol chlorination separation equipment and a dichloropropanol storage tank which are sequentially communicated; the glycerol chlorination reaction equipment comprises a hydrochloric acid storage tank, a HCL gas storage tank, a glycerol storage tank, a tubular reactor and a tower type bubbling reactor, wherein the hydrochloric acid storage tank is communicated with the tubular reactor through a hydrochloric acid raw material pump and a raw material preheater; the HCL gas storage tank is communicated with the tubular reactor through the raw material preheater, and is communicated with the tower type bubbling reactor; the glycerol storage tank is communicated with the tubular reactor through a glycerol raw material pump and the raw material preheater; the tower type bubbling reactor is communicated with the tubular reactor;
the system comprises a dichloropropanol cyclization system, a dichloropropanol cyclization reaction device, a dichloropropanol cyclization separation device and an epichlorohydrin storage tank, wherein the dichloropropanol cyclization reaction device, the dichloropropanol cyclization separation device and the epichlorohydrin storage tank are sequentially communicated; the dichloropropanol cyclization reaction equipment is communicated with the dichloropropanol storage tank; the dichloropropanol cyclization reaction equipment comprises a dichloropropanol cyclization reactor and a crude epichlorohydrin storage tank, wherein the dichloropropanol storage tank is communicated with the dichloropropanol cyclization reactor through a dichloropropanol feeding pump and a second dichloropropanol preheater; the bottom of the dichloropropanol cyclization reactor is connected with a pipeline for introducing saturated steam; discharging waste water from the bottom of the dichloropropanol cyclization reactor through a waste water cooler and a waste water pump; and the crude epoxy chloropropane storage tank is communicated with the top of the dichloropropanol cyclization reactor through a crude epoxy chloropropane cooler.
2. The system for preparing epoxy chloropropane by a glycerol process according to claim 1, characterized in that the glycerol chlorination separation equipment comprises a first rectifying tower, a first rectifying tower total condenser and a first rectifying tower reboiler, the tower type bubble reactor is connected and communicated with the first rectifying tower through a first rectifying tower feeding pump and a first dichloropropanol preheater, and simultaneously the bottom of the first rectifying tower is connected and communicated with the tower type bubble reactor through a circulating liquid cooler and a material circulating pump; the top of the first rectifying tower is communicated with the dichloropropanol storage tank through a full condenser of the first rectifying tower, and the dichloropropanol storage tank is communicated with the tower kettle of the first rectifying tower through a reflux pump of the first rectifying tower; the bottom of the first rectifying tower is communicated with the first rectifying tower reboiler, and the first rectifying tower reboiler is communicated with the first rectifying tower kettle.
3. The system for preparing the epichlorohydrin by the glycerol process according to claim 1, wherein the dichloropropanol cyclization and separation equipment comprises a second rectifying tower, a second rectifying tower total condenser and a second rectifying tower reboiler, and the crude epichlorohydrin storage tank is communicated with the second rectifying tower through a second rectifying tower feed pump and a second rectifying tower preheater; the top of the second rectifying tower is communicated with the epoxy chloropropane storage tank through the second rectifying tower total condenser, and the epoxy chloropropane storage tank is communicated with the tower kettle of the second rectifying tower through a second rectifying tower reflux pump; the bottom of the second rectifying tower is communicated with a reboiler of the second rectifying tower, and the reboiler of the second rectifying tower is communicated with the kettle of the second rectifying tower; and discharging the organic waste liquid from the bottom of the second rectifying tower through an organic waste liquid pump and an organic waste liquid cooler.
4. The process for preparing epichlorohydrin by the glycerol method according to any one of claims 1 to 3, which comprises the following steps:
1) mixing glycerol and HCI gas according to a molar ratio of 1: 2, continuously pressing the mixture into a tubular reactor for chlorination reaction, and converting glycerol;
2) and (2) allowing the material at the outlet of the tubular reactor to enter a tower type bubbling reactor for further reaction, continuously discharging generated water, dichloropropanol and HCI, and introducing HC1 gas into the tower type bubbling reactor in the process, wherein the ratio of the introduced HC1 gas to glycerol is 1: 1;
3) sending the dichloropropanol crude product generated in the step 2) to a first rectifying tower for rectifying operation to obtain high-purity dichloropropanol serving as a raw material in a cyclization reaction stage;
4) and (2) loading a catalyst into a catalyst bed layer of a dichloropropanol cyclization reactor, conveying the dichloropropanol into the dichloropropanol cyclization reactor for cyclization reaction, introducing saturated steam into the bottom of the dichloropropanol cyclization reactor in the process, separating out epoxy chloropropane, condensing the epoxy chloropropane, conveying the epoxy chloropropane to a second rectifying tower for further purification, wherein the bottom liquid of the second rectifying tower contains unreacted dichloropropanol, and refluxing to the dichloropropanol cyclization reactor for cyclization reaction again.
5. The process according to claim 4, wherein in the step 1), the operation temperature of the tubular reactor is 60-140 ℃, a catalyst is added into the tubular reactor, and the catalyst accounts for 1-3% of the glycerol; the catalyst is butyric acid or valeric acid.
6. The process according to claim 4, wherein in step 2), the operating temperature of the column bubble reactor is 100 to 140 ℃.
7. The process of claim 4, wherein in the step 3), the first rectifying tower is a vacuum tower, the vacuum degree is-0.015 MPa to 0.025MPa, and the reflux ratio is 0.5 to 3.5.
8. The process as claimed in claim 4, wherein in the step 4), the operating temperature of the dichloropropanol cyclization reactor is 90-130 ℃, the cyclization reaction time is 10-30 min, the cyclization reaction pressure is 30-50 kPa, the second rectifying tower is an atmospheric tower, and the reflux ratio is 1-4.
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| CN101007751A (en) * | 2007-01-26 | 2007-08-01 | 江苏工业学院 | Preparation method of dichloro propanol from glycerin |
| CN101157670A (en) * | 2007-11-13 | 2008-04-09 | 武汉理工大学 | Method for synthesizing epichlorohydrin |
| KR20080038284A (en) * | 2008-03-05 | 2008-05-06 | 이수화학 주식회사 | Process for preparing of epichlorohydrine |
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