CN117551060B - Method for purifying epichlorohydrin containing ether impurities - Google Patents
Method for purifying epichlorohydrin containing ether impurities Download PDFInfo
- Publication number
- CN117551060B CN117551060B CN202410038510.1A CN202410038510A CN117551060B CN 117551060 B CN117551060 B CN 117551060B CN 202410038510 A CN202410038510 A CN 202410038510A CN 117551060 B CN117551060 B CN 117551060B
- Authority
- CN
- China
- Prior art keywords
- tower
- epichlorohydrin
- ether
- azeotropic
- groups
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 240
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 title claims abstract description 173
- 238000000034 method Methods 0.000 title claims abstract description 103
- 239000012535 impurity Substances 0.000 title claims abstract description 89
- WDAXFOBOLVPGLV-UHFFFAOYSA-N ethyl isobutyrate Chemical compound CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 claims abstract description 150
- 239000000463 material Substances 0.000 claims abstract description 128
- 238000011084 recovery Methods 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000005191 phase separation Methods 0.000 claims abstract description 32
- 238000000926 separation method Methods 0.000 claims abstract description 22
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical group COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 claims description 81
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 43
- 239000002699 waste material Substances 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- 238000009835 boiling Methods 0.000 claims description 21
- 238000010992 reflux Methods 0.000 claims description 11
- 238000000746 purification Methods 0.000 abstract description 17
- 238000005265 energy consumption Methods 0.000 abstract description 9
- 238000009833 condensation Methods 0.000 abstract 1
- 230000005494 condensation Effects 0.000 abstract 1
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 32
- 239000000047 product Substances 0.000 description 32
- 239000000203 mixture Substances 0.000 description 28
- 238000004458 analytical method Methods 0.000 description 24
- 229940051269 1,3-dichloro-2-propanol Drugs 0.000 description 17
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 description 17
- SSZWWUDQMAHNAQ-UHFFFAOYSA-N 3-chloropropane-1,2-diol Chemical compound OCC(O)CCl SSZWWUDQMAHNAQ-UHFFFAOYSA-N 0.000 description 17
- 235000011187 glycerol Nutrition 0.000 description 14
- 238000004064 recycling Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 6
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 5
- FOLYKNXDLNPWGC-UHFFFAOYSA-N 1-chloro-3-methoxypropan-2-ol Chemical compound COCC(O)CCl FOLYKNXDLNPWGC-UHFFFAOYSA-N 0.000 description 4
- RZWHKKIXMPLQEM-UHFFFAOYSA-N 1-chloropropan-1-ol Chemical compound CCC(O)Cl RZWHKKIXMPLQEM-UHFFFAOYSA-N 0.000 description 4
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- FASUFOTUSHAIHG-UHFFFAOYSA-N 3-methoxyprop-1-ene Chemical compound COCC=C FASUFOTUSHAIHG-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- 238000003109 Karl Fischer titration Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 boiling point Chemical compound 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/32—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention belongs to the technical field of separation purification and recovery, and particularly relates to a method for purifying epichlorohydrin containing ether impurities, which aims to solve the technical problems that the ether impurities in epichlorohydrin cannot be effectively removed, the flow is complex, the energy consumption is high and the like in the existing purification process. The method comprises the following steps: (1) Ethyl isobutyrate and epichlorohydrin containing ether impurities are sent to an azeotropic de-ether tower for rectification, part of the azeotrope output from the tower top after condensation is mixed with water and sent to an azeotropic recovery tower, and tower bottom materials are sent to a de-weight tower; (2) Rectifying the fed materials by the azeotropic recovery tower, condensing the tower top materials and then feeding the condensed materials into a phase separation tank; (3) The weight removing tower rectifies the fed material, and after the material at the top of the tower is condensed, part of the material is refluxed and part of the material is extracted to obtain the refined epichlorohydrin product with the ether impurities removed. The method is simple and easy to operate, can effectively remove ether impurities-glycidyl methyl ether in the epichlorohydrin, and has simple flow and low energy consumption.
Description
Technical Field
The invention belongs to the technical field of separation purification and recovery, and particularly relates to a method for purifying epichlorohydrin containing ether impurities.
Background
Epichlorohydrin is also known as epichlorohydrin, and is a transparent colorless liquid which is volatile and unstable. It is an important organic chemical raw material and intermediate, and is mainly used for synthesizing epoxy resin, and downstream products of glycerine, chlorohydrin rubber, pesticide and plasticizer, etc..
The industrial production method of epoxy chloropropane mainly comprises chlorohydrin method, glycerol method and hydrogen peroxide method. Among them, the chlorohydrin method has a mature production process, but has the disadvantages of high reaction temperature, more byproducts, serious equipment corrosion, large discharge of three wastes, and the like, and has been listed as a limited industry. The glycerol method is to take crude glycerol or refined glycerol containing a small amount of methanol as a raw material, and obtain epichlorohydrin through chlorination and cyclization, wherein the methanol can participate in the reaction to generate glycidyl methyl ether. The hydrogen peroxide process is to oxidize hydrogen peroxide and 3-chloropropene directly in methanol to prepare epoxy chloropropane with TS-1 molecular sieve as catalyst, and the methanol and 3-chloropropene react side reaction to produce allyl methyl ether and then react with hydrogen peroxide to produce glycidyl methyl ether.
Since glycidyl methyl ether has close physical and chemical properties such as boiling point, polarity and molecular weight as an impurity, if separation is to be performed by conventional methods such as ordinary rectification, a very high theoretical plate number and a very large reflux ratio are required, and the method has the disadvantages of large equipment investment and high energy consumption, and is definitely an uneconomical and inadvisable separation method. The quality of epichlorohydrin products can be influenced by the glycidyl methyl ether with higher content, and even the high-quality index can not be met, so that the products can not be applied to the downstream high-end field.
CN 112778080A reports a method for recovering allyl methyl ether-free 3-chloropropene from epichlorohydrin reaction liquid, and the method provided by the invention can reduce the accumulation of allyl methyl ether in 3-chloropropene by a method consisting of multistage rectification and extractive rectification, and further reduce the residual of glycidyl methyl ether in epichlorohydrin. The method can slow down the proliferation of the glycidyl methyl ether in the reactor to a certain extent in the process of applying the raw materials, but cannot control the content of the byproduct glycidyl methyl ether in the reaction, and has longer process flow and higher process energy consumption.
Therefore, the existing purification process has the problems that the ether-containing impurities in the epichlorohydrin cannot be effectively removed, the process is complex, the energy consumption is high, and the like.
Disclosure of Invention
The invention aims to provide a method for purifying epoxy chloropropane containing ether impurities, which is simple and easy to operate, and can effectively remove the ether impurities in the epoxy chloropropane, and has the advantages of simple flow and low energy consumption.
In order to achieve the purpose of the invention, the following technical scheme is adopted:
a process for purifying epichlorohydrin containing an ether impurity, the ether impurity being glycidyl methyl ether; the method comprises the following steps:
(1) Ethyl isobutyrate is taken as an entrainer, and is sent to an azeotropic de-etherifying tower together with epichlorohydrin containing ether impurities for rectification separation, an azeotrope output from the top of the azeotropic de-etherifying tower is partially refluxed after being condensed by a first tower top condenser, and is mixed with water and pumped to an azeotropic recovery tower after being partially extracted, and a tower bottom material output from the bottom of the azeotropic de-etherifying tower is pumped to a de-duplication tower;
(2) The azeotropic recovery tower carries out rectification separation on the materials sent in the step (1), the tower top materials output from the tower top of the azeotropic recovery tower are condensed by a second tower top condenser and then sent into a phase separation tank, the heavy phase materials output from the phase separation tank are all refluxed to the azeotropic recovery tower, the light phase materials output from the phase separation tank are partially refluxed to the azeotropic recovery tower and partially extracted, and the tower bottom materials output from the tower bottom of the azeotropic recovery tower are pumped to a waste liquid tank as ether-rich waste liquid;
(3) And (3) rectifying and separating the materials fed in the step (1) by a weight removing tower, condensing the tower top materials output from the top of the weight removing tower by a third tower top condenser, partially refluxing to the weight removing tower, partially extracting to obtain refined epichlorohydrin products with ether impurities removed, and feeding the tower bottom materials output from the bottom of the weight removing tower to a waste liquid tank as high-boiling residues.
In the method for purifying the epichlorohydrin containing the ether impurities, preferably, in the step (2), the light phase material output from the phase separation tank is recovered after being extracted and sent to the step (1) to be reused as the entrainer.
The process for purifying epichlorohydrin containing ether impurities according to the invention is preferably carried out in step (1) with a total feed rate of entrainer, calculated as L in terms of ethyl isobutyrate 1 The feed flow of the epichlorohydrin containing the ether impurities is L according to the ether impurities therein 2 L is then 1 /L 2 =30-60。
The method for purifying epichlorohydrin containing ether impurities is preferably carried out in the step (1), wherein the ratio of the fresh feed flow rate of the entrainer to the recycled feed flow rate is (1-10)/100, calculated as ethyl isobutyrate in the entrainer.
The process for purifying epichlorohydrin containing ether impurities of the present invention is preferably carried out in step (1) wherein the feed rate of water in the feed to the azeotropic recovery column is L 3 The feed flow of the azeotrope is L in terms of ethyl isobutyrate therein 4 L is then 3 /L 4 =（0.5-5）/100。
The process of the present invention for purifying epichlorohydrin containing ether impurities, preferably,
the operating conditions of the azeotropic deetheration column include:
The pressure at the top of the tower is 15-40 kPaA; and/or the number of the groups of groups,
the temperature of the tower top is 54-80 ℃; and/or the number of the groups of groups,
the pressure of the tower bottom is 25-55 kPaA; and/or the number of the groups of groups,
the temperature of the tower kettle is 77-99 ℃.
The process of the present invention for purifying epichlorohydrin containing ether impurities, preferably,
the operating conditions of the azeotropic recovery column include:
the pressure at the top of the tower is 20-30 kPaA; and/or the number of the groups of groups,
the temperature of the tower top is 48-57 ℃; and/or the number of the groups of groups,
the pressure of the tower bottom is 30-40 kPaA; and/or the number of the groups of groups,
the temperature of the tower kettle is 67-78 ℃.
The process of the present invention for purifying epichlorohydrin containing ether impurities, preferably,
the operating conditions of the heavy-duty removal tower comprise:
the pressure at the top of the tower is 5-20 kPaA; and/or the number of the groups of groups,
the temperature of the tower top is 40-71 ℃; and/or the number of the groups of groups,
the pressure of the tower bottom is 10-30 kPaA; and/or the number of the groups of groups,
the temperature of the tower kettle is 110-135 ℃.
In the method for purifying the epichlorohydrin containing the ether impurities, preferably, in the step (1), the epichlorohydrin containing the ether impurities is derived from a separation unit of a process for producing the epichlorohydrin by a glycerol method and/or a hydrogen peroxide method.
The process for purifying epichlorohydrin containing ether impurities according to the invention is preferably carried out in step (1) in which the content of ether impurities in the epichlorohydrin is 200-3000 ppm and/or the content of epichlorohydrin is 94-99.5-wt% and/or the water content is < 1000 ppm.
The invention has the beneficial effects that:
the method for purifying the epichlorohydrin containing the ether impurities is simple and easy to operate, can effectively remove the ether impurities-glycidyl methyl ether in the epichlorohydrin, has high removal efficiency, simple flow and low energy consumption, can achieve the removal rate of the ether impurities-glycidyl methyl ether of more than 95 and wt percent, and can effectively remove and purify the epichlorohydrin obtained by a glycerol method and/or a hydrogen peroxide method, thereby extending the application of the method in high-end downstream products;
the method for purifying the epichlorohydrin containing the ether impurities is widely applicable to the process for producing the epichlorohydrin by a glycerol method and/or a hydrogen peroxide method, and the content of the ether impurities, namely glycidyl methyl ether, in the refined epichlorohydrin product obtained by the method is less than 50 ppm, so that the method can meet the application requirements of high-end products in the downstream field of the epichlorohydrin.
Drawings
FIG. 1 is a schematic flow diagram of a process for purifying epichlorohydrin containing ether impurities according to the invention in one embodiment; wherein,
the system comprises an azeotropic de-ether tower 1, an azeotropic recovery tower 2, a de-weight tower 3, a first tower top condenser 11, a second tower top condenser 21, a phase-splitting tank 22, a recycling entrainer pipeline 23 and a third tower top condenser 31.
Detailed Description
The technical scheme and effects of the present invention are further described below with reference to the detailed description/examples and the accompanying drawings. The following embodiments/examples are only for illustrating the contents of the present invention, and the present invention is not limited to the following embodiments or examples. Simple modifications of the invention using the inventive concept are within the scope of the invention as claimed.
The invention provides a method for purifying epichlorohydrin containing ether impurities, wherein the ether impurities are glycidyl methyl ether; as shown in fig. 1, the method includes:
(1) Ethyl isobutyrate is taken as an entrainer and is sent to an azeotropic de-etherifying tower 1 together with epichlorohydrin containing ether impurities for rectification separation, an azeotrope output from the tower top of the azeotropic de-etherifying tower 1 is partially refluxed after being condensed by a first tower top condenser 11, is partially extracted and then is mixed with water and pumped to an azeotropic recovery tower 2, and a tower bottom material output from the tower bottom of the azeotropic de-etherifying tower 1 is pumped to a de-duplication tower 3;
(2) Rectifying and separating the materials sent in the step (1) by the azeotropic recovery tower 2, condensing the tower top materials output from the tower top of the azeotropic recovery tower 2 by a second tower top condenser 21, sending the tower top materials into a phase separation tank 22, fully refluxing the heavy phase materials output from the phase separation tank 22 to the azeotropic recovery tower 2, partially refluxing the light phase materials output from the phase separation tank 22 to the azeotropic recovery tower 2, partially extracting, and pumping the tower bottom materials output from the tower bottom of the azeotropic recovery tower 2 to a waste liquid tank as ether-rich waste liquid;
(3) And (3) rectifying and separating the materials fed in the step (1) by the weight-removing tower, condensing the tower top materials output from the tower top of the weight-removing tower 3 by a third tower top condenser 31, then partially refluxing to the weight-removing tower 3, partially extracting to obtain refined epichlorohydrin products with ether impurities removed, and conveying the tower bottom materials output from the tower bottom of the weight-removing tower 3 to a waste liquid tank as high-boiling substances.
According to the invention, the enrichment of glycidyl methyl ether on the top of the azeotropic de-etherifying tower 1 is realized by utilizing the azeotropic characteristic of ethyl isobutyrate and ether impurities-glycidyl methyl ether, so that the purpose of removing the glycidyl methyl ether is achieved; in order to recycle ethyl isobutyrate in the azeotrope at the top of the azeotropic de-etherifying tower 1, the azeotropic recycling tower 2 utilizes the characteristics of azeotropy of ethyl isobutyrate and water and extremely low solubility with water, and realizes purification and recycling of ethyl isobutyrate by rectification separation of a heterogeneous azeotropic system of ethyl isobutyrate and water; by adopting ethyl isobutyrate and water as double entrainers, the high-efficiency removal of ether impurities in epoxy chloropropane containing ether impurities and the recovery of ethyl isobutyrate in an azeotrope are respectively realized in a double-tower azeotropic rectification mode. The method for purifying the epichlorohydrin containing the ether impurities is simple and easy to operate, can effectively remove the ether impurities in the epichlorohydrin, and has the advantages of high removal efficiency, simple flow, low energy consumption and high removal rate of glycidyl methyl ether up to 95 wt percent.
It will be appreciated by those skilled in the art that the epichlorohydrin containing the ether impurity in the present invention may be derived from any source, and that the ether impurity-glycidyl methyl ether contained therein may be removed by the method of the present invention, thereby obtaining a purified epichlorohydrin product of good quality from which the ether impurity-glycidyl methyl ether is removed. In one embodiment, in the step (1), the epichlorohydrin containing the ether impurities is derived from a separation unit of a process for producing the epichlorohydrin by a glycerol method and/or a hydrogen peroxide method.
Those skilled in the art understand that the process of producing epichlorohydrin by using a glycerol method and/or a hydrogen peroxide method can produce glycidyl methyl ether, and the physical and chemical properties of the glycidyl methyl ether, such as boiling point, polarity, molecular weight and the like, of the epichlorohydrin are close, so that the glycidyl methyl ether cannot be removed economically and effectively by using a traditional rectification method, and the quality of the obtained epichlorohydrin product is affected. The invention can effectively remove the water by adopting an azeotropic method. The chloropropanol by-product generated by the glycerin reaction unit has higher boiling point, but has large volatility difference with epoxy chloropropane, and can be separated by a common rectification mode.
The process for producing epichlorohydrin by the glycerol method also can produce chloropropanol byproducts with higher boiling point, but the chloropropanol byproducts have large volatility difference with epichlorohydrin, and the chloropropanol byproducts and the epichlorohydrin are separated and removed by a common rectification mode in the devolatilization process at the front end. The epichlorohydrin feed containing ether impurities is a material which is subjected to rectification separation in a front-end devolatilization process.
In one embodiment, in step (1), the content of ether impurity-glycidyl methyl ether in the epichlorohydrin containing ether impurity is 200-3000 ppm, such as 500 ppm, 1000 ppm, 1500 ppm, 2000 ppm and 2500 ppm; and/or epichlorohydrin is present in an amount of 94-99.5 wt%, such as 95 wt%, 95.5 wt%, 96 wt%, 96.5 wt%, 97 wt%, 97.5 wt%, 98 wt%, 98.5 wt%, and 99 wt%; and/or a water content of < 1000 ppm
In one embodiment, in the step (2), the light phase material output from the phase separation tank 22 is recovered after being extracted and sent to the step (1) to be reused as an entrainer, so that the ethyl isobutyrate in the light phase material output from the phase separation tank 22 can be recovered, and the raw material waste is reduced.
The process of the present invention for purifying epichlorohydrin containing ether impurities, in one embodiment, in step (1), the total feed rate of the entrainer is L in terms of ethyl isobutyrate therein 1 The feed flow of the epichlorohydrin containing the ether impurities is L according to the ether impurities therein 2 L is then 1 /L 2 =30-60, such as 35, 40, 45, 50, and 55.
It will be appreciated by those skilled in the art that the entrainer of the feed at the beginning of the feed may be referred to as a fresh entrainer; the light phase material output from the phase separation tank 22 in the step (2) is recovered after being extracted and sent to the step (1) to be reused as the entrainer, which can be called as a reuse entrainer, and the entrainer fed at the moment not only comprises fresh entrainer but also comprises reuse entrainer. The total feed rate of the entrainer refers to the total feed rates of fresh entrainer and recycled entrainer fed.
Those skilled in the art will appreciate that in step (1), if the azeotropic agent is not recycled in step (2), the total feed flow of the azeotropic agent refers to the feed flow of fresh azeotropic agent; if the azeotropic agent is recycled in step (2), the total feed flow of the azeotropic agent is the total feed flow of the fresh azeotropic agent and the recycled azeotropic agent, and the feed flow of the fresh azeotropic agent in step (1) needs to be adjusted to maintain the total feed flow of the azeotropic agent.
Those skilled in the art will appreciate that if a material contains a B material, the material will be in terms of flow of material B = actual flow of material x content of B material.
In one embodiment, in the step (1), the ratio of fresh feed flow rate to recycled feed flow rate of the entrainer is (1-10)/100, such as 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt% and 9 wt%, calculated as ethyl isobutyrate in the entrainer, so that the ethyl isobutyrate is largely recycled, and the waste of the entrainer is avoided.
The process of the invention for purifying epichlorohydrin containing ether impurities, in one embodiment, step (1) In the feed to the azeotropic recovery column 2, the feed flow rate of water is denoted as L 3 The feed rate of the azeotrope is denoted as L according to the ethyl isobutyrate therein 4 L is then 3 /L 4 = (0.5-5)/100, such as 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt% and 4.5 wt%.
The process of the present invention for purifying epichlorohydrin containing ether impurities, in one embodiment, the operating conditions of azeotropic deetherization column 1 comprise:
the overhead pressure is 15-40 kPaA, such as 20 kPaA, 25 kPaA, 30 kPaA and 35 kPaA; and/or the number of the groups of groups,
the overhead temperature is 54-80deg.C, such as 60deg.C, 65deg.C, 70deg.C and 75deg.C; and/or the number of the groups of groups,
the pressure in the tower kettle is 25-55 kPaA, such as 30 kPaA, 35 kPaA, 40 kPaA, 45 kPaA and 50 kPaA; and/or the number of the groups of groups,
the temperature of the column bottoms is 77-99 ℃, such as 80 ℃, 85 ℃, 90 ℃ and 95 ℃.
The process of the present invention for purifying epichlorohydrin containing ether impurities, in one embodiment, the operating conditions of azeotropic recovery column 2 comprise:
the overhead pressure is 20-30 kPaA, such as 25 kPaA; and/or the number of the groups of groups,
the overhead temperature is 48-57 ℃, such as 50 ℃ and 55 ℃; and/or the number of the groups of groups,
the pressure in the tower kettle is 30-40 kPaA, such as 35 kPaA; and/or the number of the groups of groups,
the column bottoms temperature is 67-78 ℃, such as 70 ℃ and 75 ℃.
The process of the present invention for purifying epichlorohydrin containing ether impurities, in one embodiment, the operating conditions of the deentrainment column 3 include:
the overhead pressure is 5-20 kPaA, such as 10 kPaA and 15 kPaA; and/or the number of the groups of groups,
the temperature of the tower top is 40-71 ℃, such as 45 ℃, 50 ℃, 55 ℃, 60 ℃ and 65 ℃; and/or the number of the groups of groups,
the pressure in the column bottoms is 10-30 kPaA, such as 15 kPaA, 20 kPaA and 25 kPaA; and/or the number of the groups of groups,
the temperature of the tower bottom is 110-135 ℃, such as 115 ℃, 120 ℃, 125 ℃ and 130 ℃.
The method for purifying the epichlorohydrin containing the ether impurities is simple and easy to operate, can effectively remove the ether impurities-glycidyl methyl ether in the epichlorohydrin, and has the advantages of high removal efficiency, simple flow, low energy consumption, and the removal rate of the ether impurities-glycidyl methyl ether can reach more than 95 and wt percent;
the method for purifying the epichlorohydrin containing the ether impurities is widely applicable to the process for producing the epichlorohydrin by a glycerol method and/or a hydrogen peroxide method, and the content of glycidyl methyl ether in the refined epichlorohydrin product obtained by the method is less than 50 ppm, so that the application requirements of high-end products in the downstream field of the epichlorohydrin can be met.
The method for purifying the epichlorohydrin containing the ether impurities is carried out by using the following system:
the system comprises an azeotropic de-ether tower 1, an azeotropic recovery tower 2 and a de-weight tower 3 which are connected through pipelines;
the azeotropic de-etherer tower 1 is used for feeding an entrainer and epoxy chloropropane containing ether impurities, rectifying the entrainer and the epoxy chloropropane, outputting an azeotrope from the top of the tower and outputting tower kettle materials from the bottom of the tower; the tower top of the azeotropic de-etherifying tower 1 is provided with a first tower top condenser 11 which is used for condensing the azeotrope output from the tower top of the azeotropic de-etherifying tower 1 and outputting the condensed azeotrope for partial reflux and partial feeding to the azeotropic recovery tower 2;
the azeotropic recovery tower 2 is used for feeding partial condensed azeotrope and water from the first tower top condenser 11, rectifying the partial condensed azeotrope and the water, and respectively outputting tower top materials and tower bottom materials which are ether-rich waste liquid; the top of the azeotropic recovery tower 2 is sequentially provided with a second top condenser 21 and a phase separation tank 22, which are used for sequentially condensing and separating phase of the top material from the azeotropic recovery tower 2 and outputting a light phase material and a heavy phase material;
the de-weight tower 3 is used for feeding and rectifying part of tower kettle materials from the azeotropic de-ether tower 1, and respectively outputting tower top materials and tower kettle materials serving as high-boiling substances; the top of the heavy-removal tower 3 is provided with a third tower top condenser 31 for partially refluxing after condensing the tower top material of the heavy-removal tower 3 and partially producing a refined epichlorohydrin product.
In one embodiment, the system further comprises a recycling entrainer pipeline 23, one end of the recycling entrainer pipeline 23 is connected to the light phase material outlet of the phase separation tank 22, and the other end is connected to the entrainer inlet of the azeotropic de-ether tower 1, and the recycling entrainer pipeline is used for conveying the light phase material from the phase separation tank 22 to the azeotropic de-ether tower 1 for recycling.
The present application is further illustrated by the following specific examples and comparative examples.
The sources of the raw materials used in the following examples and comparative examples are as follows:
the raw materials are all conventional in the field, and the purity specifications are analytically pure or chemically pure, and are all commonly and commercially available unless specified;
epichlorohydrin A containing ether impurities 1 The separation procedure from the process of producing epichlorohydrin by the glycerol method is a crude product after removing the solvent and raw materials from the epichlorohydrin reaction liquid; the composition of the composite material comprises: 0.3 wt% glycidyl methyl ether, 99.5 wt% epichlorohydrin, 0.09 wt% water, 0.08 wt% 1, 3-dichloro-2-propanol, and 0.03 wt% 3-chloro-1, 2-propanediol;
epichlorohydrin A containing ether impurities 2 The separation procedure from the process of producing epoxy chloropropane by the hydrogen peroxide method is a crude product after removing the solvent and raw materials from the epoxy chloropropane reaction liquid; the composition of the composite material comprises: 0.15 wt% glycidyl methyl ether, 97.51 wt% epichlorohydrin, 0.09 wt% water, 0.48 wt% 1, 3-dichloro-2-propanol, 1.54 wt% 1-chloro-3-methoxy-2-propanol, and 0.23 wt% 3-chloro-1, 2-propanediol;
Ethyl isobutyrate raw material with purity of 99.9 wt%;
the water comes from public engineering pipe network in industrial park and has PW grade specification.
The test methods used in the following examples and comparative examples are as follows:
glycidyl methyl ether, epichlorohydrin, ethyl isobutyrate, 1, 3-dichloro-2-propanol, 3-chloro-1, 2-propanediol, 1-chloro-3-methoxy-2-propanol were analyzed by GC-7890 chromatograph, respectively, under the following chromatographic conditions: the initial temperature of the column box is 50 ℃, the column box is kept for 2 min, the temperature is programmed to be 250 ℃ at the speed of 10 ℃/min, and the column box is kept for 10 min; the temperature of the gasification chamber is 280 ℃, and the temperature of the detection chamber is 280 ℃; FID detection; sample injection amount is 0.2 microliter; the chromatographic column is as follows: agilent Hp-VOC 60 m.times.0.32 mm.times.1.8 um;
moisture was measured using karl fischer titration.
Example 1 (S1)
Epoxy chloropropane A containing ether impurities 1 A method of performing purification, as shown in fig. 1, the method comprising:
(1) The ethyl isobutyrate raw material with the actual flow rate of 8.95 kg/h (wherein the content of the ethyl isobutyrate is 99.9 wt percent and the flow rate is converted into L according to the ethyl isobutyrate 1 =8.94 kg/h) as an entrainer with an actual flow of epichlorohydrin a containing ether impurities of 99 kg/h 1 (wherein the ether impurity-glycidyl methyl ether content is 0.3. 0.3 wt%, and the flow is converted to L based on the ether impurity-glycidyl methyl ether content) 2 The mixture is carried out in an azeotropic de-etherifying tower 1 together with the mixture which is carried out the (0.297, kg/h) and is rectified and separated, the azeotrope output from the top of the azeotropic de-etherifying tower 1 is partially refluxed after being condensed by a first top condenser 11 of the azeotropic de-etherifying tower 1, and the actual flow is partially 10.5 kg/h (the content of the ethyl isobutyrate is 84.9 wt percent, and the flow is converted into L according to the ethyl isobutyrate 4 After extraction with an actual flow of water of 0.45 kg/h (L) 3 =0.45 kg/h) is pumped to the azeotropic recovery tower 2, and the tower bottom material output from the tower bottom of the azeotropic de-etherer tower 1 is pumped to the de-weight tower 3; wherein,
the operating conditions of azeotropic deetheration column 1 include: the pressure at the top of the tower is 15 KPaA, the temperature at the top of the tower is 54 ℃, the pressure at the bottom of the tower is 25 KPaA, and the temperature at the bottom of the tower is 77 ℃;
(2) Rectifying and separating the materials sent in the step (1) by the azeotropic recovery tower 2, condensing the tower top materials output from the tower top of the azeotropic recovery tower 2 by a second tower top condenser 21, sending the tower top materials into a phase separation tank 22, completely refluxing the heavy phase materials output from the phase separation tank 22 to the azeotropic recovery tower 2, partially refluxing the light phase materials output from the phase separation tank 22 to the azeotropic recovery tower 2, partially extracting, and taking 2.71 kg/h of tower bottom materials output from the tower bottom of the azeotropic recovery tower 2Pumping the extracted actual flow serving as the ether-rich waste liquid to a waste liquid tank; the light phase material output from the phase separation tank 22 is recovered after being extracted at an actual flow rate of 8.22 kg/h (wherein the content of ethyl isobutyrate is 99.85 wt percent, and the flow rate is converted into 8.21 kg/h according to the content of ethyl isobutyrate), and is sent to the step (1) to be recycled as an entrainer, and the actual flow rate of the fresh entrainer in the step (1) is adjusted to ensure that the total feeding flow rate L in the step (1) is calculated according to the content of ethyl isobutyrate 1 Remain unchanged; wherein,
the operating conditions of the azeotropic recovery column 2 include: the pressure at the top of the tower is 20 KPaA, the temperature at the top of the tower is 48 ℃, the pressure at the bottom of the tower is 30 KPaA, and the temperature at the bottom of the tower is 67 ℃;
(3) Rectifying and separating the materials sent in the step (1) by a weight-removing tower 3, condensing the tower top materials output from the tower top of the weight-removing tower 3 by a third tower top condenser 31, then partially refluxing to the weight-removing tower 3, partially extracting at 97.2 kg/h actual flow to obtain refined epichlorohydrin products with ether impurities removed, and sending the tower bottom materials output from the tower bottom of the weight-removing tower 3 at 0.22 kg/h actual flow to a waste liquid tank as high-boiling matters; wherein,
the operating conditions of the de-weight column 3 include: the pressure at the top of the tower is 5 KPaA, the temperature at the top of the tower is 40 ℃, the pressure at the bottom of the tower is 10 KPaA, and the temperature at the bottom of the tower is 110 ℃.
Results:
the materials of each flow are respectively sampled and analyzed, and the analysis results are as follows:
the composition of the azeotrope at the top of the azeotropic deetheration tower 1 comprises: 2.8 wt% of glycidyl methyl ether, 11.5 wt% of epichlorohydrin content, 0.82 wt% of water and 84.9 wt% of ethyl isobutyrate;
the azeotropic de-ethering tower 1 tower kettle material comprises the following components: 0.004 wt% glycidyl methyl ether, 99.86 wt% epichlorohydrin, 0.12 wt% water, 0.09 wt% 1, 3-dichloro-2-propanol, 0.04 wt% 3-chloro-1, 2-propanediol;
The composition of the light phase material at the top of the phase separation tank 22 used as the recycling entrainer comprises: 0.001 wt% of glycidyl methyl ether, 0.05 wt% of epichlorohydrin, 0.1 wt% of water and 99.85 wt% of ethyl isobutyrate;
the composition of the tower kettle material of the azeotropic recovery tower 2 used as the ether-rich waste liquid comprises: 10.78 wt% of glycidyl methyl ether, 44.1 wt% of epichlorohydrin, 19.3 wt% of water and 26.2 wt% of ethyl isobutyrate;
the composition of the refined epichlorohydrin product comprises: 0.004 wt% of glycidyl methyl ether, 99.983 wt% of epichlorohydrin and 0.013 wt% of water;
the tower kettle materials of the heavy component removing tower 3 used as the high-boiling components comprise: 0.004 wt% glycidyl methyl ether, 46.5 wt% epichlorohydrin, 39.2 wt% 1, 3-dichloro-2-propanol, 17.4 wt% 3-chloro-1, 2-propanediol.
Epichlorohydrin A containing ether impurities is fed 1 The analysis results of the materials such as the ether-rich waste liquid, the purified epichlorohydrin product and the high boiling substances are shown in Table 1.
TABLE 1 analysis results of related materials in example 1
From the analysis results of the materials in example 1 and the data in Table 1, the content of glycidyl methyl ether in the refined epichlorohydrin product obtained in example 1 of the present invention was reduced to 0.004 and wt%, and the content of epichlorohydrin was increased to 99.98 and wt%; epichlorohydrin A containing ether impurities relative to the feed 1 In the method, the content of glycidyl methyl ether is 0.3 wt%, the content of epoxy chloropropane is 99.5 wt%, the effective removal of the glycidyl methyl ether and the purification of the epoxy chloropropane are realized, the removal rate of the glycidyl methyl ether can reach 98.6 wt%, the recovery rate of the epoxy chloropropane in the separation process is more than 98.6 wt%, namely the loss rate of the epoxy chloropropane is lower than 1.4 wt%.
Example 2 (S2)
Epichlorohydrin A containing ether impurities was treated in the same manner as in (S1) of example 1 1 Purification was performed, which only differs from example 1 in that:
in the step (1), the light phase material outputted from the phase separation tank 22 is recovered after being extracted at an actual flow rate of 8.28 kg/h, but is not sent to the step (1) to be recycled as an entrainer.
The results were the same as in example 1, but compared to example 1, the consumption of fresh entrainer-ethyl isobutyrate feedstock was increased per hour by 8.27 kg, which corresponds to an increase in consumption of 84.2 kg ethyl isobutyrate feedstock per 1t of purified epichlorohydrin product produced.
Example 3 (S3)
Epichlorohydrin A containing ether impurities was treated in the same manner as in (S1) of example 1 1 Purification was performed, which only differs from example 1 in that:
in the step (1), the entrainer is ethyl isobutyrate raw material with the actual flow rate of 17.54 kg/h (wherein the content of the ethyl isobutyrate is 99.9 wt percent, and the flow rate is converted into 17.52 kg/h according to the ethyl isobutyrate);
In the step (2), the light phase material output from the phase separation tank 22 is recovered after being extracted at an actual flow rate of 17.38 kg/h (wherein the content of ethyl isobutyrate is 99.78 wt percent and the flow rate is converted into 17.34 kg/h according to the content of ethyl isobutyrate), and is sent to the step (1) to be recycled as an entrainer, and the actual flow rate of the fresh entrainer in the step (1) is adjusted to keep the total feeding flow rate of the ethyl isobutyrate in the step (1) unchanged;
in the step (1), the azeotrope output from the top of the azeotropic de-etherifying tower 1 is partially refluxed after being condensed by a first top condenser 11, and is partially extracted at an actual flow rate of 20.0 kg/h (wherein the content of ethyl isobutyrate is 87.6 wt percent, the flow rate is converted into 17.52 kg/h according to the ethyl isobutyrate), and then is mixed with water at an actual flow rate of 0.09 kg/h and pumped to the azeotropic recovery tower 2.
Results:
the materials of each flow are respectively sampled and analyzed, and the analysis results are as follows:
the composition of the azeotrope at the top of the azeotropic deetheration tower 1 comprises: 1.48 wt% of glycidyl methyl ether, 10.4 wt% of epichlorohydrin content, 0.50 wt% of water and 87.6 wt% of ethyl isobutyrate;
the azeotropic de-ethering tower 1 tower kettle material comprises the following components: 0.002 wt% of glycidyl methyl ether, 99.88 wt% of epichlorohydrin, 0.01 wt% of water, 0.08 wt% of 1, 3-dichloro-2-propanol and 0.035 wt% of 3-chloro-1, 2-propanediol;
The composition of the light phase material at the top of the phase separation tank 22 used as the recycling entrainer comprises: 0.002 wt% of glycidyl methyl ether, 0.08 wt% of epichlorohydrin, 0.12 wt% of water and 99.78 wt% of ethyl isobutyrate;
the composition of the tower kettle material of the azeotropic recovery tower 2 used as the ether-rich waste liquid comprises: 10.9 wt% of glycidyl methyl ether, 76.2 wt% of epichlorohydrin, 6.2 wt% of water and 6.59 wt% of ethyl isobutyrate;
the composition of the refined epichlorohydrin product comprises: 0.002 wt% of glycidyl methyl ether, 99.991 wt% of epichlorohydrin and 0.012 wt% of water;
the tower kettle materials of the heavy component removing tower 3 used as the high-boiling components comprise: 0.002 Glycidyl methyl ether, 51.2. 51.2 wt% epichlorohydrin, 34.0. 34.0 wt% 1, 3-dichloro-2-propanol, 14.9. 14.9 wt% 3-chloro-1, 2-propanediol.
Epichlorohydrin A containing ether impurities is fed 1 The analysis results of the materials such as the ether-rich waste liquid, the purified epichlorohydrin product and the high boiling substances are shown in Table 2.
TABLE 2 analysis results of related materials in example 3
From the analysis results of the materials in example 3 and the data in Table 2, it is understood that the content of glycidyl methyl ether in the purified epichlorohydrin product obtained in example 3 of the present invention was reduced to 0.002. 0.002 wt%, and the content of epichlorohydrin was increased to 99.991 wt%; epichlorohydrin A containing ether impurities relative to the feed 1 In the method, the content of glycidyl methyl ether is 0.3 wt%, the content of epoxy chloropropane is 99.5 wt%, the effective removal of the glycidyl methyl ether and the purification of the epoxy chloropropane are realized, the removal rate of the glycidyl methyl ether can reach 99.3 wt%, the recovery rate of the epoxy chloropropane in the separation process is more than 97.7 wt%, namely the loss rate of the epoxy chloropropane is lower than 2.3 wt%.
Example 4 (S4)
Epichlorohydrin A containing ether impurities was treated in the same manner as in (S1) of example 1 1 Purification was performed, which only differs from example 1 in that:
in the step (1), the entrainer is ethyl isobutyrate raw material with the actual flow rate of 13.34 kg/h (wherein the content of the ethyl isobutyrate is 99.9 wt percent, and the flow rate is converted into 13.33 kg/h according to the ethyl isobutyrate);
in the step (1), the light phase material output from the phase separation tank 22 is recovered after being extracted at an actual flow rate of 12.16 kg/h (wherein the content of ethyl isobutyrate is 99.68 wt percent and the flow rate is converted into 12.12 kg/h according to the content of ethyl isobutyrate), and is sent to the step (1) to be recycled as an entrainer, and the actual flow rate of the fresh entrainer in the step (1) is adjusted to keep the total feeding flow rate of the ethyl isobutyrate in the step (1) unchanged;
In the step (1), the azeotrope output from the top of the azeotropic de-etherifying tower 1 is partially refluxed after being condensed by a first top condenser 11, and is partially extracted at an actual flow rate of 15.22 kg/h (wherein the content of ethyl isobutyrate is 87.6 wt percent, and the flow rate is converted into 13.33 kg/h according to the ethyl isobutyrate), and then is mixed with water at an actual flow rate of 0.4 kg/h and pumped to the azeotropic recovery tower 2.
Results:
the materials of each flow are respectively sampled and analyzed, and the analysis results are as follows:
the composition of the azeotrope at the top of the azeotropic deetheration tower 1 comprises: 1.93 wt% of glycidyl methyl ether, 9.8 wt% of epichlorohydrin content, 0.70 wt% of water and 87.6 wt% of ethyl isobutyrate;
the azeotropic de-ethering tower 1 tower kettle material comprises the following components: 0.003 wt% glycidyl methyl ether, 99.87 wt% epichlorohydrin, 0.01 wt% water, 0.08 wt% 1, 3-dichloro-2-propanol, 0.04 wt% 3-chloro-1, 2-propanediol;
the composition of the light phase material at the top of the phase separation tank 22 used as the recycling entrainer comprises: 0.002 wt% of glycidyl methyl ether, 0.09 wt% of epichlorohydrin, 0.23 wt% of water and 99.68 wt% of ethyl isobutyrate;
the composition of the tower kettle material of the azeotropic recovery tower 2 used as the ether-rich waste liquid comprises: 8.5 wt% of glycidyl methyl ether, 42.9 wt% of epichlorohydrin, 13.8 wt% of water and 34.7wt% of ethyl isobutyrate;
The composition of the refined epichlorohydrin product comprises: 0.003 wt% of glycidyl methyl ether, 99.986 wt% of epichlorohydrin and 0.012 wt% of water;
the tower kettle materials of the heavy component removing tower 3 used as the high-boiling components comprise: 0.003 Glycidyl methyl ether, 50.1. 50.1 wt% epichlorohydrin, 32.9. 32.9 wt% 1, 3-dichloro-2-propanol, 17.0. 17.0 wt% 3-chloro-1, 2-propanediol.
Epichlorohydrin A containing ether impurities is fed 1 The analysis results of the materials such as the ether-rich waste liquid, the purified epichlorohydrin product and the high boiling substances are shown in Table 3.
TABLE 3 analysis of the relevant materials in example 4
From the analysis results of the materials in example 4 and the data in Table 3, it is understood that the content of glycidyl methyl ether in the purified epichlorohydrin product obtained in example 4 of the present invention was reduced to 0.003. 0.003 wt%, and the content of epichlorohydrin was increased to 99.986 wt%; epichlorohydrin A containing ether impurities relative to the feed 1 In the method, the content of glycidyl methyl ether is 0.3 wt%, the content of epoxy chloropropane is 99.5 wt%, the effective removal of the glycidyl methyl ether and the purification of the epoxy chloropropane are realized, the removal rate of the glycidyl methyl ether can reach 99.0 wt%, the recovery rate of the epoxy chloropropane in the separation process is more than 98.4 wt%, namely the loss rate of the epoxy chloropropane is lower than 1.6 wt%.
Example 5 (S5)
Epichlorohydrin A containing ether impurities was treated in the same manner as in (S1) of example 1 1 Purification was performed, which only differs from example 1 in that:
in step (1), the operating conditions of the azeotropic deetheration column 1 include: the pressure at the top of the tower is 40 kPaA, and the temperature at the top of the tower is 80 ℃; the column bottom pressure was 50 kPaA and the column bottom temperature was 97 ℃.
In step (2), the operation conditions of the azeotropic recovery column 2 are: the pressure at the top of the tower is 25 kPaA, and the temperature at the top of the tower is 53 ℃; the column bottom pressure was 40 kPaA and the column bottom temperature was 78 ℃.
In the step (3), the operating conditions of the weight removing tower 3 are as follows: the pressure at the top of the tower is 20 kPaA, and the temperature at the top of the tower is 71 ℃; the column bottom pressure was 30 kPaA and the column bottom temperature was 135 ℃.
Results:
the materials of each flow are respectively sampled and analyzed, and the analysis results are as follows:
the composition of the azeotrope at the top of the azeotropic deetheration tower 1 comprises: 2.72 wt% of glycidyl methyl ether, 11.5. 11.5 wt% of epichlorohydrin content, 0.84. 0.84 wt% of water and 85.0. 85.0 wt% of ethyl isobutyrate;
the azeotropic de-ethering tower 1 tower kettle material comprises the following components: 0.005 wt% of glycidyl methyl ether, 99.86 wt% of epichlorohydrin, 0.016 wt% of water, 0.09 wt% of 1, 3-dichloro-2-propanol and 0.04 wt% of 3-chloro-1, 2-propanediol;
the composition of the light phase material at the top of the phase separation tank 22 used as the recycling entrainer comprises: 0.003 wt% of glycidyl methyl ether, 0.06 wt% of epichlorohydrin, 0.17 wt% of water and 99.76 wt% of ethyl isobutyrate;
The composition of the tower kettle material of the azeotropic recovery tower 2 used as the ether-rich waste liquid comprises: 10.4 wt% of glycidyl methyl ether, 44.1 wt% of epichlorohydrin, 19.1 wt% of water, 0.02 wt% of 3-chloro-1, 2-propanediol and 26.3 wt% of ethyl isobutyrate;
the composition of the refined epichlorohydrin product comprises: 0.005 wt% of glycidyl methyl ether, 99.975 wt% of epichlorohydrin, 0.017 wt% of water and 0.001 wt% of 1, 3-dichloro-2-propanol;
the tower kettle materials of the heavy component removing tower 3 used as the high-boiling components comprise: 0.004 Glycidyl methyl ether, 40.5. 40.5 wt% epichlorohydrin, 38.7. 38.7 wt% 1, 3-dichloro-2-propanol, 20.8. 20.8 wt% 3-chloro-1, 2-propanediol.
Epichlorohydrin A containing ether impurities is fed 1 The analysis results of the materials such as the ether-rich waste liquid, the purified epichlorohydrin product and the high boiling substances are shown in Table 4.
TABLE 4 analysis results of related materials in example 5
From the analysis results of the materials in example 5 and the data in Table 4, it is understood that the content of glycidyl methyl ether in the purified epichlorohydrin product obtained in example 5 of the present invention was reduced to 0.005. 0.005 wt%, and the content of epichlorohydrin was increased to 99.975. 99.975 wt%; epichlorohydrin A containing ether impurities relative to the feed 1 In the method, the content of glycidyl methyl ether is 0.3 wt%, the content of epoxy chloropropane is 99.5 wt%, the effective removal of the glycidyl methyl ether and the purification of the epoxy chloropropane are realized, the removal rate of the glycidyl methyl ether can reach 95.7 wt%, the recovery rate of the epoxy chloropropane in the separation process is more than 98.6 wt%, namely the loss rate of the epoxy chloropropane is lower than 1.4 wt%.
Example 6 (S6)
Epichlorohydrin A containing ether impurities was treated in the same manner as in (S1) of example 1 1 Purification was performed, which only differs from example 1 in that:
in step (1), the operating conditions of the azeotropic deetheration column 1 include: the pressure at the top of the column is 37 kPaA, and the temperature at the top of the column is 68 ℃; the pressure in the column bottom was 55 kPaA and the temperature in the column bottom was 99 ℃.
In step (2), the operation conditions of the azeotropic recovery column 2 are: the pressure at the top of the tower is 30 kPaA, and the temperature at the top of the tower is 57 ℃; the column bottom pressure was 35 kPaA and the column bottom temperature was 73 ℃.
In the step (3), the operating conditions of the weight removing tower 3 are as follows: the pressure at the top of the tower is 15 kPaA, and the temperature at the top of the tower is 61 ℃; the column bottom pressure was 20 kPaA and the column bottom temperature was 123 ℃.
Results:
the materials of each flow are respectively sampled and analyzed, and the analysis results are as follows:
the composition of the azeotrope at the top of the azeotropic deetheration tower 1 comprises: 2.68 wt% of glycidyl methyl ether, 14.3 wt% of epichlorohydrin content, 0.80 wt% of water and 82.7 wt% of ethyl isobutyrate;
the azeotropic de-ethering tower 1 tower kettle material comprises the following components: 0.004wt% glycidyl methyl ether, 99.82wt% epichlorohydrin, 0.016wt% water, 0.1wt% 1, 3-dichloro-2-propanol, 0.05wt% 3-chloro-1, 2-propanediol;
the composition of the light phase material at the top of the phase separation tank 22 used as the recycling entrainer comprises: 0.002 wt% of glycidyl methyl ether, 0.06 wt% of epichlorohydrin, 0.15 wt% of water and 99.8 wt% of ethyl isobutyrate;
The composition of the tower kettle material of the azeotropic recovery tower 2 used as the ether-rich waste liquid comprises: 9.6 wt% of glycidyl methyl ether, 50.7. 50.7 wt% of epichlorohydrin, 16.2. 16.2 wt% of water, 0.01. 0.01 wt% of 3-chloro-1, 2-propanediol and 23.7. 23.7 wt% of ethyl isobutyrate;
the composition of the refined epichlorohydrin product comprises: 0.004 wt% of glycidyl methyl ether, 99.987 wt% of epichlorohydrin, 0.017 wt% of water and 0.001 wt% of 1, 3-dichloro-2-propanol;
the tower kettle materials of the heavy component removing tower 3 used as the high-boiling components comprise: 0.003 Glycidyl methyl ether, 29.8 wt% epichlorohydrin, 39.6 wt% 1, 3-dichloro-2-propanol, 30.6 wt% 3-chloro-1, 2-propanediol.
Epichlorohydrin A containing ether impurities is fed 1 The analysis results of the materials such as the ether-rich waste liquid, the purified epichlorohydrin product and the high boiling substances are shown in Table 5.
TABLE 5 analysis of the relevant materials in example 6
From the analysis results of the materials in example 6 and the data in Table 5, it is understood that the content of glycidyl methyl ether in the purified epichlorohydrin product obtained in example 6 of the present invention was reduced to 0.004 and wt%, and the content of epichlorohydrin was increased to 99.987 wt%; epichlorohydrin A containing ether impurities relative to the feed 1 In the method, the content of glycidyl methyl ether is 0.3 wt%, the content of epoxy chloropropane is 99.5 wt%, the effective removal of the glycidyl methyl ether and the purification of the epoxy chloropropane are realized, the removal rate of the glycidyl methyl ether can reach 97.0 wt%, the recovery rate of the epoxy chloropropane in the separation process is more than 98.3 wt%, namely the loss rate of the epoxy chloropropane is lower than 1.7 wt%.
Example 7 (S7)
According to the embodiment1 (S1) method for epoxy chloropropane A containing ether impurities 2 Purification was performed, which only differs from example 1 in that:
in the step (1), the entrainer is ethyl isobutyrate raw material with the actual flow rate of 4.49 kg/h (wherein the content of the ethyl isobutyrate is 99.9 wt percent, and the flow rate is converted into 4.48 kg/h according to the ethyl isobutyrate);
in the step (1), epichlorohydrin A containing ether impurities 2 The actual flow rate of (a) is 99 kg/h (wherein the epichlorohydrin content is 0.15 wt percent, and the flow rate is converted into 0.149 kg/h according to ether impurities-glycidyl methyl ether;
in the step (2), the light phase material output from the phase separation tank 22 is recovered after being extracted at an actual flow rate of 4.13 kg/h (wherein the content of ethyl isobutyrate is 99.85 wt percent and the flow rate is converted into 4.12 kg/h according to the content of ethyl isobutyrate), and is sent to the step (1) to be recycled as an entrainer, and the actual flow rate of the fresh entrainer in the step (1) is adjusted to keep the total feeding flow rate of the ethyl isobutyrate in the step (1) unchanged;
in the step (1), the azeotrope output from the top of the azeotropic de-etherifying tower 1 is partially refluxed after being condensed by a first tower top condenser 11, and is partially pumped to the azeotropic recovery tower 2 after being extracted by an actual flow rate of 5.31 kg/h (wherein the content of ethyl isobutyrate is 82.5wt percent and the flow rate is converted into 4.38 kg/h according to the content of ethyl isobutyrate), and the water is mixed with an actual flow rate of 0.21 kg/h;
In the step (3), after the tower top material output from the tower top of the heavy-duty removing tower 3 is condensed by a third tower top condenser 31, part of the tower top material flows back to the heavy-duty removing tower 3, part of the tower top material is extracted at the actual flow of 95.7 kg/h to obtain a refined epichlorohydrin product with ether impurities removed, and the tower bottom material output from the tower bottom of the heavy-duty removing tower 3 at the actual flow of 2.42 kg/h is used as a high-boiling-point material to be sent to a waste liquid tank.
Results:
the materials of each flow are respectively sampled and analyzed, and the analysis results are as follows:
the composition of the azeotrope at the top of the azeotropic deetheration tower 1 comprises: 2.78 wt% of glycidyl methyl ether, 13.0 wt% of epichlorohydrin content, 1.58 wt% of water and 82.5 wt% of ethyl isobutyrate;
the azeotropic de-ethering tower 1 tower kettle material comprises the following components: 0.001 Glycidyl methyl ether, 97.63 wt% epichlorohydrin, 0.012 wt% water, 0.51 wt% 1, 3-dichloro-2-propanol, 1.62 wt% 1-chloro-3-methoxy-2-propanol, 0.24 wt% 3-chloro-1, 2-propanediol;
the composition of the light phase material at the top of the phase separation tank 22 used as the recycling entrainer comprises: 0.001 wt% of glycidyl methyl ether, 0.06 wt% of epichlorohydrin, 0.15 wt% of water and 99.85 wt% of ethyl isobutyrate;
the composition of the tower kettle material of the azeotropic recovery tower 2 used as the ether-rich waste liquid comprises: 10.5 wt% of glycidyl methyl ether, 49.0 wt% of epichlorohydrin, 20.9 wt% of water and 18.5 wt% of ethyl isobutyrate;
The composition of the refined epichlorohydrin product comprises: 0.001 wt% of glycidyl methyl ether, 99.979 wt% of epichlorohydrin and 0.013 wt% of water;
the tower kettle materials of the heavy component removing tower 3 used as the high-boiling components comprise: 0.001 Glycidyl methyl ether, 4.8 wt% epichlorohydrin, 20.7 wt% 1, 3-dichloro-2-propanol, 64.8 wt% 1-chloro-3-methoxy-2-propanol, 9.7 wt% 3-chloro-1, 2-propanediol.
Epichlorohydrin A containing ether impurities is fed 2 The analysis results of the materials such as the ether-rich waste liquid, the purified epichlorohydrin product and the high boiling substances are shown in Table 6.
TABLE 6 analysis results of related materials in example 7
From the analysis results of the materials in example 7 and the data in Table 6, it is understood that the content of glycidyl methyl ether in the purified epichlorohydrin product obtained in example 7 of the present invention was reduced to 0.001 and wt%, and the content of epichlorohydrin was increased to 99.979 and wt%; epichlorohydrin A containing ether impurities relative to the feed 2 In the method, the content of the glycidyl methyl ether is 0.15 to wt percent, the content of the epichlorohydrin is 97.51 wt percent, and the method realizes the effective removal of the glycidyl methyl ether and the epoxyThe removal rate of the chloropropane to the glycidyl methyl ether can reach 99.3 and wt percent, and the recovery rate of the epichlorohydrin in the separation process is more than 99.1 and wt percent, namely the loss rate of the epichlorohydrin is lower than 0.9 and wt percent.
Claims (7)
1. A process for purifying epichlorohydrin containing an ether impurity, characterized in that the ether impurity is glycidyl methyl ether; the method comprises the following steps:
(1) Ethyl isobutyrate is taken as an entrainer, and is sent to an azeotropic de-etherifying tower together with epichlorohydrin containing ether impurities for rectification separation, an azeotrope output from the top of the azeotropic de-etherifying tower is partially refluxed after being condensed by a first tower top condenser, and is mixed with water and pumped to an azeotropic recovery tower after being partially extracted, and a tower bottom material output from the bottom of the azeotropic de-etherifying tower is pumped to a de-duplication tower;
(2) The azeotropic recovery tower carries out rectification separation on the materials sent in the step (1), the tower top materials output from the tower top of the azeotropic recovery tower are condensed by a second tower top condenser and then sent into a phase separation tank, the heavy phase materials output from the phase separation tank are all refluxed to the azeotropic recovery tower, the light phase materials output from the phase separation tank are partially refluxed to the azeotropic recovery tower and partially extracted, and the tower bottom materials output from the tower bottom of the azeotropic recovery tower are pumped to a waste liquid tank as ether-rich waste liquid;
(3) Rectifying and separating the materials fed in the step (1) by a weight removing tower, condensing the tower top materials output from the top of the weight removing tower by a third tower top condenser, then partially refluxing to the weight removing tower, partially extracting to obtain refined epichlorohydrin products with ether impurities removed, and feeding tower bottom materials output from the bottom of the weight removing tower to a waste liquid tank as high-boiling residues; wherein,
In the step (1), the epichlorohydrin containing ether impurities is derived from a separation unit of a process for producing epichlorohydrin by a glycerol method and/or a hydrogen peroxide method;
in the step (1), the content of ether impurities in the epichlorohydrin containing the ether impurities is 200-3000 ppm, the content of the epichlorohydrin is 94-99.5-wt%, and the water content is less than 1000 ppm;
in the step (2), the light phase material output from the phase separation tank is recovered after being extracted and sent to the step (1) to be reused as an entrainer.
2. The process of claim 1 wherein in step (1) the total feed rate of entrainer is L based on ethyl isobutyrate therein 1 The feed flow of the epichlorohydrin containing the ether impurities is L according to the ether impurities therein 2 L is then 1 /L 2 =30-60。
3. The process of claim 1 wherein in step (1) the ratio of fresh feed rate to recycled feed rate of the entrainer, based on ethyl isobutyrate in the entrainer, is (1-10)/100.
4. The process of claim 1 wherein in step (1) the feed rate of water in the feed to the azeotropic recovery column is L 3 The feed flow of the azeotrope is L in terms of ethyl isobutyrate therein 4 L is then 3 /L 4 =（0.5-5）/100。
5. The process of claim 1, wherein the operating conditions of the azeotropic deethering column comprise:
the pressure at the top of the tower is 15-40 kPaA; and/or the number of the groups of groups,
the temperature of the tower top is 54-80 ℃; and/or the number of the groups of groups,
the pressure of the tower bottom is 25-55 kPaA; and/or the number of the groups of groups,
the temperature of the tower kettle is 77-99 ℃.
6. The process of claim 1 wherein the operating conditions of the azeotropic recovery column comprise:
the pressure at the top of the tower is 20-30 kPaA; and/or the number of the groups of groups,
the temperature of the tower top is 48-57 ℃; and/or the number of the groups of groups,
the pressure of the tower bottom is 30-40 kPaA; and/or the number of the groups of groups,
the temperature of the tower kettle is 67-78 ℃.
7. The method of claim 1, wherein the de-duplication column operating conditions comprise:
the pressure at the top of the tower is 5-20 kPaA; and/or the number of the groups of groups,
the temperature of the tower top is 40-71 ℃; and/or the number of the groups of groups,
the pressure of the tower bottom is 10-30 kPaA; and/or the number of the groups of groups,
the temperature of the tower kettle is 110-135 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410038510.1A CN117551060B (en) | 2024-01-11 | 2024-01-11 | Method for purifying epichlorohydrin containing ether impurities |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410038510.1A CN117551060B (en) | 2024-01-11 | 2024-01-11 | Method for purifying epichlorohydrin containing ether impurities |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117551060A CN117551060A (en) | 2024-02-13 |
| CN117551060B true CN117551060B (en) | 2024-04-09 |
Family
ID=89820815
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410038510.1A Active CN117551060B (en) | 2024-01-11 | 2024-01-11 | Method for purifying epichlorohydrin containing ether impurities |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117551060B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1931848A (en) * | 2006-09-28 | 2007-03-21 | 蓝星化工新材料股份有限公司无锡树脂厂 | Process of recovering epoxy chloropropane from effluent |
| CN108530396A (en) * | 2018-06-12 | 2018-09-14 | 山东凯泰科技股份有限公司 | A kind of chloro propylene epoxidation method prepares the product purification method of epoxychloropropane |
| CN112374676A (en) * | 2020-10-22 | 2021-02-19 | 江苏扬农化工集团有限公司 | Device and method for separating and purifying byproducts in epichlorohydrin wastewater |
| CN115745920A (en) * | 2022-12-08 | 2023-03-07 | 万华化学集团股份有限公司 | Method for recovering effective components in waste liquid in epoxy chloropropane production |
| CN116041140A (en) * | 2023-01-03 | 2023-05-02 | 万华化学集团股份有限公司 | Purification method of 3-chloropropene containing ether impurities |
-
2024
- 2024-01-11 CN CN202410038510.1A patent/CN117551060B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1931848A (en) * | 2006-09-28 | 2007-03-21 | 蓝星化工新材料股份有限公司无锡树脂厂 | Process of recovering epoxy chloropropane from effluent |
| CN108530396A (en) * | 2018-06-12 | 2018-09-14 | 山东凯泰科技股份有限公司 | A kind of chloro propylene epoxidation method prepares the product purification method of epoxychloropropane |
| CN112374676A (en) * | 2020-10-22 | 2021-02-19 | 江苏扬农化工集团有限公司 | Device and method for separating and purifying byproducts in epichlorohydrin wastewater |
| CN115745920A (en) * | 2022-12-08 | 2023-03-07 | 万华化学集团股份有限公司 | Method for recovering effective components in waste liquid in epoxy chloropropane production |
| CN116041140A (en) * | 2023-01-03 | 2023-05-02 | 万华化学集团股份有限公司 | Purification method of 3-chloropropene containing ether impurities |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117551060A (en) | 2024-02-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1162417C (en) | Process for epoxidation of olefins | |
| CN105906584B (en) | The method for removing the aldehydes in propylene oxide reaction mixture | |
| CN100558694C (en) | The Azotropic distillation method of separating acetic acid, methyl acetate and water in the preparation aromatic carboxylic acid process | |
| CN108530396B (en) | Method for refining chloropropene prepared by epoxidation method | |
| CN105622337B (en) | Novel reactive distillation coupling process and device for separating liquid-phase product of ethylene glycol prepared from coal | |
| JP2010523698A (en) | Multi-stage method and apparatus for recovering dichlorohydrin | |
| CN103172596B (en) | Propylene oxide refining method | |
| CN106588599A (en) | Purification method of PODE (polyoxymethylene dimethyl ether) | |
| CN105254532B (en) | A kind of method of three tower variable-pressure rectification separating acetonitrile methyl alcohol-benzene ternary azeotrope | |
| CN106588589A (en) | Purification method for polyoxymethylene dimethyl ether(PODE) | |
| CN112225650B (en) | Refining method for obtaining high-purity methylal by purifying industrial-grade methylal | |
| CN112374676B (en) | Device and method for separating and purifying byproducts in epichlorohydrin wastewater | |
| JP2010523703A (en) | Method and apparatus for azeotropic recovery of dichlorohydrin | |
| CN105218305A (en) | A kind of byproduct recovery process of synthetic gas preparing ethylene glycol | |
| CN106892798B (en) | Process for preparing dichloropropanol | |
| KR20100016455A (en) | Process and apparatus for recovery of dichlorohydrins via codistillation | |
| KR20060120218A (en) | Method for separating trioxane from a mixture containing trioxane, formaldehyde and water | |
| CN117551060B (en) | Method for purifying epichlorohydrin containing ether impurities | |
| CN111875478A (en) | Method for refining methanol recovered by epoxy chloropropane process by hydrogen peroxide method | |
| RU2408569C2 (en) | Method of producing allyl alcohol | |
| CN106588596A (en) | Method for purifying polyoxymethylene dimethyl ether | |
| CN213977489U (en) | Glycerol chlorination unit for epoxy chloropropane production device | |
| CN115141163A (en) | Method for efficiently recovering effective components in waste liquid of 1, 4-butanediol prepared by epoxypropane method | |
| CN109851579A (en) | Epoxyalkane production method | |
| CN112778080A (en) | Method for recovering 3-chloropropene from solution containing 3-chloropropene and methanol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |