CN108659042B - Extraction separation method and extraction rectification equipment of alkyl phosphine dichloride - Google Patents
Extraction separation method and extraction rectification equipment of alkyl phosphine dichloride Download PDFInfo
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- CN108659042B CN108659042B CN201810654386.6A CN201810654386A CN108659042B CN 108659042 B CN108659042 B CN 108659042B CN 201810654386 A CN201810654386 A CN 201810654386A CN 108659042 B CN108659042 B CN 108659042B
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- phosphine dichloride
- alkyl phosphine
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- -1 alkyl phosphine dichloride Chemical compound 0.000 title claims abstract description 92
- 238000000605 extraction Methods 0.000 title claims abstract description 33
- 238000000926 separation method Methods 0.000 title claims abstract description 18
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 76
- 238000011084 recovery Methods 0.000 claims abstract description 43
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 40
- 238000010992 reflux Methods 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 22
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229950011008 tetrachloroethylene Drugs 0.000 claims abstract description 21
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004064 recycling Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- ONRKUGHFZWYUJP-UHFFFAOYSA-N methylphosphane dihydrochloride Chemical group Cl.Cl.PC ONRKUGHFZWYUJP-UHFFFAOYSA-N 0.000 claims description 13
- 238000000895 extractive distillation Methods 0.000 claims description 12
- SWLUDPNYHHFUKX-UHFFFAOYSA-N ethylphosphane dihydrochloride Chemical compound Cl.Cl.CCP SWLUDPNYHHFUKX-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002699 waste material Substances 0.000 abstract description 6
- 238000013461 design Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 150000002903 organophosphorus compounds Chemical class 0.000 description 5
- 238000005086 pumping Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 229910000619 316 stainless steel Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- AFINAILKDBCXMX-PBHICJAKSA-N (2s,3r)-2-amino-3-hydroxy-n-(4-octylphenyl)butanamide Chemical compound CCCCCCCCC1=CC=C(NC(=O)[C@@H](N)[C@@H](C)O)C=C1 AFINAILKDBCXMX-PBHICJAKSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000005515 coenzyme Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229940127089 cytotoxic agent Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JHNJGLVSPIMBLD-UHFFFAOYSA-N dichloro(ethyl)phosphane Chemical compound CCP(Cl)Cl JHNJGLVSPIMBLD-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003958 nerve gas Substances 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003986 organophosphate insecticide Substances 0.000 description 1
- ZFJMTDFOGDGPTF-UHFFFAOYSA-N phosphanium;chloride;hydrochloride Chemical compound P.Cl.Cl ZFJMTDFOGDGPTF-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/52—Halophosphines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0492—Applications, solvents used
-
- 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
- B01D3/146—Multiple effect distillation
-
- 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
- B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
- B01D3/40—Extractive distillation
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention discloses an extraction separation method of alkyl phosphine dichloride, which takes 1,1, 2-trichloroethane or tetrachloroethylene as an extracting agent and can separate the alkyl phosphine dichloride from phosphorus trichloride serving as a raw material. The invention also discloses extraction and rectification equipment of alkyl phosphine dichloride, which comprises a phosphorus trichloride rectification tower, an alkyl phosphine dichloride rectification tower and an extraction and recovery tower, and designs the theoretical plate number, the feeding position, the reflux ratio and the like of each tower, so that the continuous separation of the alkyl phosphine dichloride and the phosphorus trichloride and the recycling of an extracting agent can be realized, the separation efficiency is high, and three wastes are less.
Description
Technical Field
The invention relates to the technical field of rectification separation, in particular to an extraction separation method of alkyl phosphine dichloride and extraction rectification equipment for implementing the method.
Background
With the rapid development of economy in China, the demand of organic phosphorus compounds in agriculture and industrial production is rapidly increasing. The organic phosphorus compound means a compound having a carbon-phosphorus bond or a phosphoric acid derivative having an organic group. The organophosphorus compound is widely applied to nucleic acid, coenzyme, organophosphorus nerve gas, organophosphorus insecticide, organophosphorus bactericide, organophosphorus herbicide, chemotherapeutic agent, plasticizer, antioxidant, surfactant, complexing agent, organophosphorus extractant, flotation agent, flame retardant and the like. The alkyl phosphine dichloride is an important intermediate for synthesizing the organic phosphorus compound, has wide application, can directly or indirectly synthesize hundreds of organic phosphorus compounds by the alkyl phosphine dichloride, has extremely high conversion rate by taking the alkyl phosphine dichloride as a starting material for reaction, and almost quantitatively performs most reactions.
The alkyl phosphine dichloride can be synthesized by phosphorus trichloride and corresponding alkyl, the reaction needs to be carried out at high temperature (about 600 ℃), the per-pass conversion rate of the phosphorus trichloride in the reaction is lower and is about 30 percent, and the boiling points of the phosphorus trichloride and the product alkyl phosphine dichloride are closer, so how to recover the phosphorus trichloride to the maximum extent, realize the recycling of materials, and the obtaining of the high-purity product alkyl phosphine dichloride becomes the key problem of the process.
Disclosure of Invention
The invention aims to provide an extraction and rectification method and equipment for alkyl phosphine dichloride, which select a proper extracting agent, solve the separation problem of raw material mixtures such as phosphorus trichloride and alkyl phosphine dichloride by using an extraction and rectification method, recover unreacted phosphorus trichloride and alkyl phosphine dichloride generated by reaction to the maximum extent and realize the recycling of materials.
In order to achieve the purpose, the invention adopts the following technical scheme:
an extraction separation method of alkyl phosphine dichloride comprises the following steps: adding an extracting agent into a raw material mixture containing phosphorus trichloride and alkyl phosphine dichloride, mixing, sequentially evaporating out the phosphorus trichloride and the alkyl phosphine dichloride, and recycling the extracting agent in the residual liquid for reuse; the extractant is selected from 1,1, 2-trichloroethane or tetrachloroethylene; when the alkyl phosphine dichloride is ethyl phosphine dichloride, the extractant is tetrachloroethylene.
Preferably, the addition amount of the extracting agent is 1-15% of the mass of the raw material mixture.
Preferably, the temperature for distilling out the phosphorus trichloride is 88-91 ℃, and the temperature for distilling out the alkyl phosphine dichloride is 120-125 ℃.
The invention also provides alkyl phosphine dichloride extraction and rectification equipment for realizing the method, which comprises a phosphorus trichloride rectifying tower, an alkyl phosphine dichloride rectifying tower and an extraction and recovery tower; the middle part of the phosphorus trichloride rectifying tower is respectively provided with a raw material mixture feeding port and an extractant feeding port, the top of the phosphorus trichloride rectifying tower is connected with a phosphorus trichloride condenser, a liquid outlet of the condenser is connected with the top of the phosphorus trichloride rectifying tower, and a phosphorus trichloride extraction line is arranged on a connecting pipeline; the bottom of the phosphorus trichloride rectifying tower is connected with a feed inlet of an alkyl phosphine dichloride rectifying tower, the top of the alkyl phosphine dichloride rectifying tower is connected with an alkyl phosphine dichloride condenser, a liquid outlet of the condenser is connected with the top of the alkyl phosphine dichloride rectifying tower, and an alkyl phosphine dichloride extraction line is arranged on a connecting pipeline; the bottom of the alkyl phosphine dichloride rectifying tower is connected with a feed inlet of an extractant recovery tower, the top of the extractant recovery tower is connected with an extractant condenser, a liquid outlet of the condenser is connected with the top of the extractant recovery tower, an extractant recovery pipeline is arranged on the connecting pipeline and is connected with the extractant feed inlet, and a tower bottom liquid extraction line is arranged at the bottom of the extractant recovery tower.
Preferably, a first reboiler is arranged at the bottom of the phosphorus trichloride rectifying tower and is used for circularly heating materials at the bottom of the tower; a second reboiler is arranged at the bottom of the alkyl phosphine dichloride rectifying tower and is used for circularly heating materials at the bottom of the tower; a third reboiler is arranged at the bottom of the extractant recovery tower and is used for circularly heating materials at the bottom of the tower; and an extractant intermediate tank is arranged on the extractant recovery pipeline.
Preferably, the phosphorus trichloride rectifying tower, the alkyl phosphine dichloride rectifying tower and the extracting agent recovery tower are plate towers or packed towers.
Preferably, the theoretical plate number of the phosphorus trichloride rectifying tower is 90-120, the feeding position of the raw material mixture is 60-67 th plate, and the feeding position of the extracting agent is 65-72 th plate; and/or:
the temperature of the top of the phosphorus trichloride rectifying tower is as follows: 74 ℃ -76 ℃, overhead pressure: 0.1KPa to 1.01 KPa; the reflux ratio of the tower top is as follows: 5:1-12: 1; temperature at the bottom of the column: 88 ℃ to 91 ℃, bottom pressure: 15KPa-33.6 KPa.
Preferably, the theoretical plate number of the alkyl phosphine dichloride rectifying tower is 31-48, and the feed inlet is positioned at 18 th-24 th plates; and/or:
when the alkyl phosphine dichloride is methyl phosphine dichloride, the overhead temperature: 81.0 ℃ to 83.5 ℃, and when the alkyl phosphine dichloride is ethyl phosphine dichloride, the overhead temperature: 112.0-113.0 ℃; pressure at the top of the column: 0.1KPa to 1.01 KPa; the reflux ratio of the tower top is as follows: 1:1-1.9: 1; temperature at the bottom of the column: 120-125 ℃, bottom pressure: 3.0KPa to 26.0 KPa;
preferably, the theoretical plate number of the extraction agent recovery tower is 26-35, and the feed inlet is positioned at 16 th-24 th plates; and/or:
when the extractant is tetrachloroethylene, the temperature of the top of the extraction recovery tower is as follows: 121.0 ℃ to 122.0 ℃, and when the extractant is 1,1, 2-trichloroethane, the overhead temperature: 113.5-114.5 ℃; pressure at the top of the column: 0.1KPa to 1.01 KPa; the reflux ratio of the tower top is as follows: 1:1-5: 1; temperature at the bottom of the column: 138 ℃ -145 ℃, bottom pressure: 40KPa-60 KPa.
Compared with the prior art, the invention has the following beneficial effects:
the invention selects proper extracting agent, adopts the method of extraction and rectification to solve the separation problem of alkyl phosphine dichloride and phosphorus trichloride which is a reaction raw material, recovers unreacted phosphorus trichloride and alkyl phosphine dichloride generated by reaction to the maximum extent, realizes the recycling of materials and reduces the amount of three wastes.
In the traditional process, phosphorus oxychloride is used as an extracting agent, so that the equipment is not only highly corrosive, but also is violently decomposed when meeting water, a large amount of heat and dense smoke are generated, even explosion is possible, and the safety risk and the kettle residue treatment difficulty are greatly increased. The invention adopts tetrachloroethylene or 1,1, 2-trichloroethane as an extracting agent, has small corrosion to equipment, does not contain phosphorus in the extracting agent, is not easy to burn, and greatly reduces the safety risk. The kettle residue is easier to treat, residual extracting agent can be recovered to the maximum extent by a water washing and liquid separation method, and the amount of three wastes is reduced. Compared with the traditional process, the method is safer, more economical and more environment-friendly.
The invention realizes the continuous separation of alkyl phosphine dichloride and phosphorus trichloride and the recycling of the extracting agent by the design of the extraction and rectification equipment of alkyl phosphine dichloride, has high separation efficiency and less three wastes.
Drawings
FIG. 1 is a schematic diagram of an extractive distillation apparatus for alkyl phosphine dichloride according to the present invention.
In the drawings: 1 phosphorus trichloride rectifying column, 2 phosphorus trichloride condenser, 3 phosphorus trichloride reboiler, 4 first pipeline pumps, 5 alkyl phosphine dichloride rectifying column, 6 alkyl phosphine dichloride condenser, 7 alkyl phosphine dichloride reboiler, 8 second pipeline pumps, 9 extractant recovery tower, 10 extractant condenser, 11 extractant reboiler, 12 extractant intermediate tank, 13 third pipeline pumps.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1 extraction separation of Methylphosphine dichloride
A set of phi 30mm glass rectifying tower is adopted for the experiment, 316 stainless steel packing is filled in the rectifying tower, and the height of the rectifying tower is 1 m. The composition of the raw material mixture is: 68.5 percent of phosphorus trichloride, 29.7 percent of methyl phosphine dichloride, 0.7 percent of chloroform, 1.1 percent of dichloromethane and tetrachloroethylene as an extracting agent. And (3) performing extractive distillation by adopting a continuous operation method, performing distillation for three times, and respectively obtaining high-purity phosphorus trichloride, methyl phosphine dichloride and tetrachloroethylene at the tower top.
(1) Rectifying to obtain high-purity phosphorus trichloride
The tetrachloroethylene feed inlet is arranged at the upper part, the raw material liquid feed inlet is arranged at the lower part, two peristaltic pumps are adopted for feeding materials simultaneously, and the feed amount of the tetrachloroethylene is controlled to be 10 percent of the raw material mixture. Controlling the reflux ratio of 8:1, the temperature of the tower kettle of 91 ℃, the temperature of the tower top of 76 ℃, continuously extracting phosphorus trichloride with the purity of 95.8 percent from the tower top, and extracting a mixture of methyl phosphine dichloride and tetrachloroethylene from the tower bottom.
(2) Rectifying to obtain high-purity methyl phosphine dichloride
Continuously pumping the mixture of the methyl phosphine dichloride and the tetrachloroethylene into a rectifying tower by a pump, controlling the reflux ratio to be 1.2:1, the temperature of a tower kettle to be 121 ℃, the temperature of a tower top to be 83 ℃, continuously extracting the methyl phosphine dichloride with the purity of 96.3 percent from the tower top, and continuously extracting the mixture of an extracting agent and kettle residues from the tower bottom.
(3) Recovery of the extractant
Continuously pumping the mixture of the extractant and the residue into a rectifying tower by a pump, controlling the reflux ratio to be 3:1, the tower kettle temperature to be 142 ℃, the tower top temperature to be 122 ℃, continuously extracting the extractant from the tower top, wherein the purity is 96.8 percent, and continuously extracting the residue from the tower bottom.
Example 2 extraction separation of Ethyl Phosphorus dichloride
A set of phi 30mm glass rectifying tower is adopted for the experiment, 316 stainless steel packing is filled in the rectifying tower, and the height of the rectifying tower is 1 m. The composition of the raw material mixture is: 67.4% of phosphorus trichloride, 30.7% of ethyl phosphine dichloride, 0.8% of chloroform, 1.3% of dichloromethane and an extracting agent of tetrachloroethylene. And (3) performing extractive distillation by adopting a continuous operation method, performing distillation for three times, and respectively obtaining high-purity phosphorus trichloride, ethyl phosphine dichloride and tetrachloroethylene at the tower top.
(1) Rectifying to obtain high-purity phosphorus trichloride
The tetrachloroethylene feed inlet is arranged at the upper part, the raw material liquid feed inlet is arranged at the lower part, two peristaltic pumps are adopted for feeding materials simultaneously, and the feed amount of the tetrachloroethylene is controlled to be 10 percent of the raw material mixture. Controlling the reflux ratio of 10:1, the temperature of a tower kettle to be 90 ℃, the temperature of a tower top to be 76 ℃, continuously extracting phosphorus trichloride with the purity of 96.1% from the tower top, and extracting a mixture of ethyl phosphine dichloride and tetrachloroethylene from the tower bottom.
(4) Rectifying to obtain high-purity ethyl phosphine dichloride
Continuously pumping the mixture of the ethyl phosphine dichloride and the tetrachloroethylene into a rectifying tower by a pump, controlling the reflux ratio to be 1.5:1, the temperature of a tower kettle to be 122 ℃, the temperature of a tower top to be 82 ℃, continuously extracting the ethyl phosphine dichloride with the purity of 96.9 percent from the tower top, and continuously extracting the mixture of an extracting agent and kettle residues from the tower bottom.
(5) Recovery of the extractant
Continuously pumping the mixture of the extractant and the kettle residue into a rectifying tower by a pump, controlling the reflux ratio to be 3:1, the tower kettle temperature to be 143 ℃, the tower top temperature to be 122 ℃, continuously extracting the extractant from the tower top, wherein the purity is 95.8 percent, and continuously extracting the kettle residue from the tower bottom.
EXAMPLE 3 extractive distillation apparatus for alkyl phosphine dichloride
As shown in figure 1, the equipment for the extractive distillation of alkyl phosphine dichloride comprises a phosphorus trichloride rectifying tower 1, an alkyl phosphine dichloride rectifying tower 5 and an extraction recovery tower 9 which can be a plate tower or a packed tower which can be the same or different.
The theoretical plate number of the phosphorus trichloride rectifying tower 1 is 90-120, the feed inlet of the raw material mixture is positioned at the 60 th-67 th plate, the feed inlet of the extracting agent is positioned at the 65 th-72 th plate, and the temperature of the top of the tower is as follows: 74 ℃ -76 ℃, overhead pressure: 0.1KPa to 1.01 KPa; the reflux ratio of the tower top is as follows: 5:1-12: 1; temperature at the bottom of the column: 88 ℃ to 91 ℃, bottom pressure: 15KPa-33.6 KPa. The top of the phosphorus trichloride rectifying tower 1 is connected with a phosphorus trichloride condenser 2, part of the condensed liquid flows back to the phosphorus trichloride rectifying tower 1 in a reflux ratio of 5:1-12:1, and the rest is extracted through a phosphorus trichloride extraction line; the bottom of the phosphorus trichloride rectifying tower 1 is provided with a first reboiler 3 for circularly heating materials at the bottom of the tower, and a discharge hole at the bottom of the tower is connected with a feed inlet of an alkyl phosphine dichloride rectifying tower 5.
The theoretical plate number of the alkyl phosphine dichloride rectifying tower 5 is 31-48, the feed inlet is positioned at the 18 th-24 th plate, the tower top temperature is as follows: 81.0-83.5 ℃ or 112.0-113.0 ℃, overhead pressure: 0.1KPa to 1.01 KPa; the reflux ratio of the tower top is as follows: 1:1-1.9: 1; temperature at the bottom of the column: 120-125 ℃, bottom pressure: 3.0KPa to 26.0 KPa. The top of the tower is connected with an alkyl phosphine dichloride condenser 6, part of the condensed liquid flows back to a phosphine dichloride rectifying tower 5 with the reflux ratio of 1:1-1.9:1, and the rest is extracted through an alkyl phosphine dichloride extraction line; and a second reboiler 7 is arranged at the bottom of the alkyl phosphine dichloride rectifying tower 5 and used for circularly heating materials at the bottom of the tower, and a discharge hole at the bottom of the tower is connected with a feed inlet of an extracting agent recovery tower 9.
The theoretical plate number of the extractant recovery tower 9 is 26-35, the feed inlet is positioned at 16 th-24 th plates, the tower top temperature is as follows: 121.0 ℃ -122.0 ℃ or 113.5 ℃ -114.5 ℃, overhead pressure: 0.1KPa to 1.01 KPa; the reflux ratio of the tower top is as follows: 1:1-5: 1; temperature at the bottom of the column: 138 ℃ -145 ℃, bottom pressure: 40KPa-60 KPa. The top of the tower is connected with an extractant condenser 10, the condensed liquid enters an extractant intermediate tank 12, and part of the condensed liquid flows back to an extractant recovery tower 9 with a reflux ratio of 1:1-5:1, the rest is connected with an extractant feed inlet of a phosphorus trichloride rectifying tower 1 through an extractant recovery pipeline, a third reboiler 11 is arranged at the bottom of the extractant recovery tower 9 and used for circularly heating materials at the bottom of the tower, and the discharged materials at the bottom of the tower enter a three-waste treatment process through a tower bottom liquid extraction line.
The extraction and rectification method of alkyl phosphine dichloride by combining the equipment comprises the following steps:
the raw material mixture containing phosphorus trichloride and alkyl phosphine dichloride and an extracting agent are conveyed into a phosphorus trichloride rectifying tower 1 from different parts, and the tower top temperature is as follows: 74 ℃ -76 ℃, overhead pressure: 0.1KPa to 1.01KPa, bottom temperature: 88 ℃ to 91 ℃, bottom pressure: 15KPa-33.6 KPa. After phosphorus trichloride is condensed by a condenser 2, part of phosphorus trichloride reflows to enter a phosphorus trichloride rectifying tower 1, and the reflux ratio is as follows: 5:1-12:1, and partially extracting the device. Part heavy component and extractant circulate and heat between 1 tower cauldron of phosphorus trichloride rectifying column and reboiler 3, and part gets into alkyl phosphine dichloride rectifying column 5 through first tubing pump 4, and the top of the tower temperature: 81.0-83.5 ℃ or 112.0-113.0 ℃, overhead pressure: 0.1KPa to 1.01 KPa; temperature at the bottom of the column: 120-125 ℃, bottom pressure: 3.0KPa to 26.0 KPa. After alkyl phosphine dichloride is condensed by a condenser 6, part of the condensed alkyl phosphine dichloride flows back to enter an alkyl phosphine dichloride rectifying tower 5, and the reflux ratio is as follows: 1:1-1.9:1, and partially extracting the device. Part of heavy components and the extractant are circularly heated between a tower kettle 5 of the alkyl phosphine dichloride rectifying tower and a reboiler 7, part of heavy components and the extractant enter an extractant recovery tower 9 through a second pipeline pump 8, and the temperature of the tower top is as follows: 121.0 ℃ -122.0 ℃ or 113.5 ℃ -114.5 ℃, overhead pressure: 0.1KPa to 1.01KPa, bottom temperature: 138 ℃ -145 ℃, bottom pressure: 40KPa-60 KPa. After the extractant is condensed by a condenser 10, part of the extractant reflows to enter an extractant recovery tower 9, and the reflux ratio is as follows: 1:1-5:1, and part of the extracted liquid enters an extracting agent intermediate tank 12 and is conveyed into a phosphorus trichloride rectifying tower 1 by a third pipeline pump 13; part of heavy components are circularly heated between the tower bottom of the extractant recovery tower 9 and the reboiler 11, and part of tower bottom liquid is extracted from the device to carry out three-waste treatment.
EXAMPLE 4 extractive distillation experiment of alkyl phosphine dichloride
1. Table 1 shows examples of the same reaction conditions, different equipment types and parameters, in which the composition of the raw material mixture is: 74.5 percent of phosphorus trichloride, 23.7 percent of methyl phosphine dichloride, 0.7 percent of chloroform, 1.1 percent of dichloromethane, 3 percent of tetrachloroethylene as an extractant, 75 percent of the top temperature of a phosphorus trichloride rectifying tower, 0.51KPa of the top pressure, 90 percent of the bottom temperature of the phosphorus trichloride rectifying tower, 17.2KPa of the bottom pressure of the phosphorus trichloride rectifying tower, and 7:1 of reflux ratio; the tower top temperature of the methyl phosphine dichloride rectifying tower is 82 ℃, the tower top pressure is 0.56KPa, the tower bottom temperature is 123 ℃, the tower bottom pressure is 18.2KPa, and the reflux ratio is 1.5: 1; the temperature at the top of the extractant recovery tower is 121 ℃, the pressure at the top of the extractant recovery tower is 0.77KPa, the temperature at the bottom of the extractant recovery tower is 140 ℃, the pressure at the bottom of the extractant recovery tower is 52KPa, and the reflux ratio is 3: 1.
TABLE 1 examples of extractive rectification of alkyl phosphine dichlorides with different equipment types and parameters
Note: two values in a row of the feeding position of the phosphorus trichloride rectifying tower are as follows in sequence: the feeding position of the raw material mixture and the feeding position of the extracting agent.
2. Table 2 shows examples of different reaction conditions, wherein the phosphorus trichloride rectifying tower, the alkyl phosphine dichloride rectifying tower and the extractant recovery tower are plate towers; the feeding position of the raw material mixture is the 67 th tray of the phosphorus trichloride rectifying tower, the feeding position of the extracting agent is the 72 th tray of the phosphorus trichloride rectifying tower, the feeding position of the alkyl phosphine dichloride rectifying tower is the 19 th tray, and the feeding position of the extracting agent recovery tower is the 19 th tray; the theoretical plate numbers of the phosphorus trichloride rectifying tower, the alkyl phosphine dichloride rectifying tower and the extracting agent recovery tower are respectively 105, 39 and 34.
TABLE 2 examples of extractive rectification of alkyl phosphine dichlorides under different reaction conditions
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. The extraction and separation method of alkyl phosphine dichloride is characterized by comprising the following steps: adding an extracting agent into a raw material mixture containing phosphorus trichloride and alkyl phosphine dichloride, mixing, sequentially evaporating out the phosphorus trichloride and the alkyl phosphine dichloride, and recycling the extracting agent in the residual liquid for reuse; the alkyl phosphine dichloride is methyl phosphine dichloride or ethyl phosphine dichloride, and when the alkyl phosphine dichloride is the methyl phosphine dichloride, the extracting agent is selected from 1,1, 2-trichloroethane or tetrachloroethylene; when the alkyl phosphine dichloride is ethyl phosphine dichloride, the extractant is tetrachloroethylene.
2. The process for the extractive separation of an alkyl phosphine dichloride as claimed in claim 1 wherein: the addition amount of the extracting agent is 1-15% of the mass of the raw material mixture.
3. The process for the extractive separation of an alkyl phosphine dichloride as claimed in claim 1 wherein: the temperature for distilling out the phosphorus trichloride is 88 to 91 ℃, and the temperature for distilling out the alkyl phosphine dichloride is 120 to 125 ℃.
4. An alkyl phosphine dichloride extractive distillation equipment used for the method of any one of claims 1 to 3, which is characterized in that: comprises a phosphorus trichloride rectifying tower (1), an alkyl phosphine dichloride rectifying tower (5) and an extraction recovery tower (9); the middle part of the phosphorus trichloride rectifying tower (1) is respectively provided with a raw material mixture feeding port and an extracting agent feeding port, the top of the phosphorus trichloride rectifying tower (1) is connected with a phosphorus trichloride condenser (2), a liquid outlet of the condenser is connected with the top of the phosphorus trichloride rectifying tower (1), and a phosphorus trichloride extraction line is arranged on a connecting pipeline; the bottom of the phosphorus trichloride rectifying tower (1) is connected with a feed inlet of an alkyl phosphine dichloride rectifying tower (5), the top of the alkyl phosphine dichloride rectifying tower (5) is connected with an alkyl phosphine dichloride condenser (6), a liquid outlet of the condenser is connected with the top of the alkyl phosphine dichloride rectifying tower (5), and an alkyl phosphine dichloride extraction line is arranged on a connecting pipeline; the bottom of the alkyl phosphine dichloride rectifying tower (5) is connected with a feed inlet of an extracting agent recovery tower (9), the top of the extracting agent recovery tower (9) is connected with an extracting agent condenser (10), a liquid outlet of the condenser is connected with the top of the extracting agent recovery tower (9), an extracting agent recovery pipeline is arranged on a connecting pipeline, the recovery pipeline is connected with an extracting agent feed inlet of a phosphorus trichloride rectifying tower (1), and a tower kettle liquid extraction line is arranged at the bottom of the extracting agent recovery tower (9).
5. The alkyl phosphine dichloride extractive distillation apparatus of claim 4, wherein: the tower bottom of the phosphorus trichloride rectifying tower (1) is provided with a first reboiler (3) for circularly heating materials at the tower bottom; a second reboiler (7) is arranged at the bottom of the alkyl phosphine dichloride rectifying tower (5) and is used for circularly heating materials at the bottom of the tower; a third reboiler (11) is arranged at the bottom of the extractant recovery tower (9) and is used for circularly heating materials at the bottom of the tower; an extractant intermediate tank (12) is arranged on the extractant recovery pipeline.
6. The alkyl phosphine dichloride extractive distillation apparatus of claim 4, wherein: the phosphorus trichloride rectifying tower (1), the alkyl phosphine dichloride rectifying tower (5) and the extractant recovery tower (9) are plate towers or packed towers.
7. The alkyl phosphine dichloride extractive distillation apparatus of claim 4, wherein: the theoretical plate number of the phosphorus trichloride rectifying tower (1) is 90-120, the feeding position of the raw material mixture is 60-67 th plates, and the feeding position of the extracting agent is 65-72 th plates; and/or:
the tower top temperature of the phosphorus trichloride rectifying tower (1): 74 ℃ -76 ℃, overhead pressure: 0.1KPa to 1.01 KPa; the reflux ratio of the tower top is as follows: 5:1-12: 1; temperature at the bottom of the column: 88 ℃ to 91 ℃, bottom pressure: 15KPa-33.6 KPa.
8. The alkyl phosphine dichloride extractive distillation apparatus of claim 4, wherein: the theoretical plate number of the alkyl phosphine dichloride rectifying tower (5) is 31-48, and the feed inlet is positioned at the 18 th-24 th plate; and/or:
when the alkyl phosphine dichloride is methyl phosphine dichloride, the tower top temperature of the alkyl phosphine dichloride rectifying tower (5) is 81.0-83.5 ℃, and when the alkyl phosphine dichloride is ethyl phosphine dichloride, the tower top temperature is 112.0-113.0 ℃; pressure at the top of the column: 0.1KPa to 1.01 KPa; the reflux ratio of the tower top is as follows: 1:1-1.9: 1; temperature at the bottom of the column: 120-125 ℃, bottom pressure: 3.0KPa to 26.0 KPa.
9. The alkyl phosphine dichloride extractive distillation apparatus of claim 4, wherein: the theoretical plate number of the extractant recovery tower (9) is 26-35, and the feed inlet is positioned at the 16 th-24 th plate; and/or:
when the extractant is tetrachloroethylene, the tower top temperature of the extractant recovery tower (9) is 121.0-122.0 ℃; when the extractant is 1,1, 2-trichloroethane, the tower top temperature is 113.5-114.5 ℃; pressure at the top of the column: 0.1KPa to 1.01 KPa; the reflux ratio of the tower top is as follows: 1:1-5: 1; temperature at the bottom of the column: 138 ℃ -145 ℃, bottom pressure: 40KPa-60 KPa.
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| CN109970790B (en) * | 2019-04-29 | 2021-12-03 | 利尔化学股份有限公司 | Extraction separation method and rectification device of methyl phosphine dichloride |
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| CN116251535B (en) * | 2023-02-14 | 2023-09-26 | 贵州威顿晶磷电子材料股份有限公司 | Low-emission manufacturing device and manufacturing method for electronic grade triethyl phosphate |
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