CN112645330B - Device and process for recycling carbonyl sulfide in tail gas of chlorination process - Google Patents

Device and process for recycling carbonyl sulfide in tail gas of chlorination process Download PDF

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CN112645330B
CN112645330B CN202011493424.8A CN202011493424A CN112645330B CN 112645330 B CN112645330 B CN 112645330B CN 202011493424 A CN202011493424 A CN 202011493424A CN 112645330 B CN112645330 B CN 112645330B
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condenser
tail gas
tower
low
stage
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CN112645330A (en
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顾川川
孔敏
杨森
陈杰
赵志明
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Zhejiang Titan Design & Engineering Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/70—Compounds containing carbon and sulfur, e.g. thiophosgene
    • C01B32/77—Carbon oxysulfide
    • 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
    • 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
    • B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
    • B01D3/322—Reboiler specifications
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
    • B01D5/0033—Other features
    • B01D5/0036—Multiple-effect condensation; Fractional condensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
    • B01D5/0057—Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes
    • B01D5/006—Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes with evaporation or distillation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
    • B01D5/0078—Condensation of vapours; Recovering volatile solvents by condensation characterised by auxiliary systems or arrangements
    • B01D5/009—Collecting, removing and/or treatment of the condensate

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a device and a process for recycling carbonyl sulfide in tail gas of a chlorination process, and belongs to the technical field of tail gas recycling. The device comprises a tail gas compressor, a first-stage condenser, a first-stage gas-liquid separator, a second-stage condenser, a second-stage gas-liquid separator, a feeding condenser, a low-temperature rectifying tower, a tower top condenser, a tower bottom reboiler, a carbon oxysulfide product buffer tank and a carbon oxysulfide filling pump. The process is that the tail gas is compressed by a tail gas compressor and then is sent to a first-stage condenser, a first-stage gas-liquid separator, a second-stage condenser and a second-stage gas-liquid separator for condensation and separation, and then is sent to a feeding condenser for condensation and then is rectified and separated by a low-temperature rectifying tower, hydrogen chloride is separated from the top of the tower, carbon oxysulfide is separated from the bottom of the tower, the carbon oxysulfide enters a carbon oxysulfide product buffer tank for temporary storage, and is output by a carbon oxysulfide filling pump. The invention has high integration degree of equipment, reduces the discharge of three wastes and the waste of raw materials, and reduces the separation difficulty.

Description

Device and process for recycling carbonyl sulfide in tail gas of chlorination process
Technical Field
The invention belongs to the technical field of tail gas recycling, and particularly relates to a device and a process for recycling carbonyl sulfide in tail gas of a chlorination process.
Background
Chlorination is a reaction of introducing chlorine atoms into molecules of a compound, is an important unit reaction in pharmaceutical and chemical industry, and has application in various fields such as bulk drugs, agriculture, light industry, rubber and the like. The tail gas of the chlorination process often contains byproducts of hydrogen chloride, organic solvents and other byproducts, and has complex components and difficult recovery.
Solid phosgene is an important intermediate for pharmaceutical synthesis and pesticide manufacture. The method has application in the synthesis of fine chemicals such as chloroformate, acyl chloride and the like, medicaments such as azlocillin, antihypertensive and the like, carbamate pesticides, herbicides, pesticides and the like. Compared with chlorinating agents such as phosphorus oxychloride, phosgene and the like, the high-stability aqueous solution has relatively strong stability and is more beneficial to chemical production. In the chlorination of solid phosgene, when the chlorinated substance contains mercapto groups, hydrogen chloride and carbon oxysulfide are often by-produced. Carbon oxysulfide is an important raw material for pesticides, medicines and other chemical products, and particularly occupies an important position in the production process of thiocarbamate pesticides; in recent years, it has been found that high purity carbonyl sulfide can be used as an etching gas for integrated circuit fabrication to replace fluoride etching gas which is difficult to degrade and has a greenhouse effect.
At present, common treatment modes of the solid phosgene chlorination tail gas are as follows: firstly, recovering hydrogen chloride in tail gas through water absorption, then, treating the residual tail gas by liquid alkali to enable carbon oxysulfide in the residual tail gas to react into sodium carbonate and sodium hydrosulfide, oxidizing the sodium hydrosulfide into sodium thiosulfate by hydrogen peroxide, and additionally, treating solid waste obtained after concentrating wastewater. The treatment method not only wastes valuable carbon oxysulfide byproducts, but also generates a large amount of solid waste and wastewater, thereby increasing the waste treatment cost.
Along with the gradual development of the application of the carbonyl sulfide, the application value of the carbonyl sulfide is further improved, and the recovered carbonyl sulfide as a byproduct of the chlorination mercapto of the solid phosgene has objective economic return, can reduce the generation of waste water and waste residues, and reduces consumption and emission.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a device and a process for recycling carbonyl sulfide in the tail gas of the chlorination process, which can be efficiently, reliably, safely and integrally used for obtaining high-quality and high-purity byproducts and reducing the emission of waste water and waste residues.
The integrated recovery device for the carbonyl sulfide in the chlorination process tail gas comprises an organic solvent recovery module, a low-temperature rectification module and a byproduct buffer module, and is characterized in that the organic solvent recovery module comprises a tail gas compressor, a primary condenser, a primary gas-liquid separator, a secondary condenser and a secondary gas-liquid separator, and the tail gas compressor is sequentially connected with the primary condenser, the primary gas-liquid separator, the secondary condenser and the secondary gas-liquid separator; the low-temperature rectification module comprises a feeding condenser, a low-temperature rectification tower, a tower top condenser and a tower bottom reboiler, wherein the feeding condenser is connected with the low-temperature rectification tower, the tower top condenser is arranged above the low-temperature rectification tower, the tower bottom reboiler is arranged below the low-temperature rectification tower, and the feeding condenser is connected with the secondary gas-liquid separator through a pipeline;
the byproduct buffer module comprises a carbon oxysulfide product buffer tank and a carbon oxysulfide filling pump, and the carbon oxysulfide product buffer tank is connected with the low-temperature rectifying tower through a pipeline.
The recycling device of the carbonyl sulfide in the tail gas of the chlorination process is characterized in that an upper outlet of the top of the low-temperature rectifying tower is connected with an upper inlet of a top condenser, a lower outlet of the top condenser is divided into two branches, and the lower inlet of the top of the low-temperature rectifying tower and an outlet for recycling hydrogen chloride are respectively connected.
The recycling device of the carbonyl sulfide in the tail gas of the chlorination process is characterized in that an exhaust valve is arranged on the carbonyl sulfide product buffer tank.
The recycling device of the carbonyl sulfide in the chlorination process tail gas is characterized in that an upper inlet of the bottom of the low-temperature rectifying tower is connected with an upper outlet of a tower bottom reboiler, a lower outlet of the bottom of the tower is divided into two branches, and the lower inlet of the tower bottom reboiler is connected with an upper inlet of a carbonyl sulfide product buffer tank.
The recycling device of the carbonyl sulfide in the tail gas of the chlorination process is characterized in that the primary gas-liquid separator and the secondary gas-liquid separator are provided with outlets for recycling organic solvents.
The process of the recycling device of the carbonyl sulfide in the chlorination process tail gas is characterized by comprising the following steps of:
1) After the recycled chlorinated tail gas is pressurized by a tail gas compressor, condensing by a first-stage condenser and a first-stage gas-liquid separator, condensing by a second-stage condenser and a second-stage gas-liquid separator, and effectively condensing and recycling the liquid-phase organic solvent; gaseous hydrogen chloride and carbonyl sulfide enter a low-temperature rectifying tower;
2) Condensing the gas phase mixture by a feed condenser, then feeding the condensed gas phase mixture into a low-temperature rectifying tower for rectifying and separating, separating byproduct hydrogen chloride from the top of the tower for dehydration and absorption, and obtaining a carbon oxysulfide byproduct deoxidized carbon sulfide product buffer tank from the bottom of the tower;
3) The high-purity carbonyl sulfide enters a carbonyl sulfide product buffer tank for temporary storage, and is filled and discharged by a carbonyl sulfide filling pump periodically.
The process is characterized in that the liquid-phase organic solvent is one or a mixture of more of toluene, ethanol, ethyl acetate, methanol, methylene dichloride and acetone.
The process is characterized in that the refrigerant medium adopted by the primary condenser and the secondary condenser is circulating water, low-temperature water, circulating water, frozen ethylene glycol or low-temperature water and frozen ethylene glycol.
The process is characterized in that the refrigerant medium adopted by the feeding condenser is frozen glycol or cryogenic medium; the refrigerant medium adopted by the tower top condenser is frozen glycol or cryogenic medium; the heat medium adopted by the tower bottom reboiler is hot water, high-temperature glycol or steam.
The process is characterized in that the temperature of the heating medium is 25-145 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1) Aiming at the problems that the existing common tail gas treatment process for destroying the carbon oxysulfide in the chlorinated tail gas by using alkali and hydrogen peroxide to reach the exhaust emission standard wastes a large amount of byproduct carbon oxysulfide, increases the consumption of raw materials and discharges three wastes, by adopting the technology, different material recovery sequences in the tail gas are reasonably arranged, and a proper recovery mode is selected, so that the aim of recovering a large amount of byproduct carbon oxysulfide with high purity is fulfilled, and the organic solvent and the other byproduct hydrochloric acid used in the chlorination process are also recovered.
2) The device has high integration degree, can realize device modularization, can select different refrigerants and compression pressures according to different tail gas working conditions, and improves the application range of the device.
3) According to the invention, the carbon oxysulfide in the chlorination tail gas which needs to be treated originally is recovered, so that the three-waste emission and raw material waste are reduced, and the byproduct value of the chlorination process is increased; the condensation recovery module is adopted to effectively trap the organic solvent, so that the subsequent tail gas components are reduced, and the separation difficulty is reduced.
4) According to the invention, by adopting a low-temperature rectification technology, water is not introduced in the separation of hydrogen chloride, so that the generation of impurities caused by the water separation of the carbonyl sulfide is avoided, and the yield and purity of the carbonyl sulfide are increased; the buffer of temporary storage and filling modules makes the device suitable for different working conditions such as intermittent production, continuous production and the like.
Drawings
FIG. 1 is a process flow diagram of a carbon oxysulfide recovery device in a tail gas of a chlorination process.
In the figure: 1-an organic solvent recovery module, 2-a cryogenic rectification module; 3-a byproduct caching module; 4-an exhaust gas compressor; 5-a first-stage condenser; 6-a first-stage gas-liquid separator; 7-a two-stage condenser; 8-a secondary gas-liquid separator; 9-a feed condenser; 10-a low-temperature rectifying tower; 11-an overhead condenser; 12-an overhead condenser; 13-a bottoms reboiler; a 14-carbonyl sulfide product buffer tank; 15-carbon oxysulfide filling pump.
Detailed Description
The invention is further described below with reference to the drawings of the specification, but the scope of the invention is not limited thereto.
As shown in fig. 1, a recycling device for carbonyl sulfide in tail gas of an integrated chlorination process is divided into an organic solvent recycling module 1, a low-temperature rectification module 2 and a byproduct buffer module 3, and comprises a tail gas compressor 4, a primary condenser 5, a primary gas-liquid separation 6, a secondary condenser 7, a secondary gas-liquid separator 8, a feed condenser 9, a low-temperature rectification tower 10, a tower top condenser 11, a tower bottom reboiler 12, a carbonyl sulfide product buffer 13 and a carbonyl sulfide filling pump 14.
The outlet of the tail gas compressor 4 is connected with the outlet of the first-stage condenser 5, the first-stage condenser 5 is connected with the first-stage gas-liquid separator 6, the upper outlet of the first-stage gas-liquid separator 6 is connected with the inlet of the second-stage condenser 7, and the second-stage condenser 7 is connected with the second-stage gas-liquid separator 8; the inlet of the feed condenser 9 is connected with the outlet of the secondary gas-liquid separator 8, the outlet of the feed condenser 9 is connected with the low-temperature rectifying tower 10, the upper outlet of the top of the low-temperature rectifying tower 10 is connected with the upper inlet of the top condenser 11, and the lower outlet of the top condenser 11 is divided into two branches which are respectively connected with the lower inlet of the top of the low-temperature rectifying tower 10 and the outlet for recycling hydrogen chloride. The upper inlet of the bottom of the low-temperature rectifying tower 11 is connected with the upper outlet of the bottom reboiler 12, and the lower outlet of the bottom is connected with the lower inlet of the bottom reboiler 12. The lower outlet of the bottom of the low-temperature rectifying tower 11 is divided into two branches, and the branches are respectively connected with the lower inlet of the bottom reboiler 12 and the upper inlet of the carbonyl sulfide product buffer tank 13. The carbon oxysulfide filling pump 14 is connected with the carbon oxysulfide product buffer tank 13, and an exhaust valve is arranged on the carbon oxysulfide product buffer tank 13.
After the recycled chloridized tail gas is pressurized by a tail gas compressor 4, condensing by a first-stage condenser 5, then performing gas-liquid separation by a first-stage gas-liquid separator 6, and then condensing by a second-stage condenser 7 and a second-stage gas-liquid separator 8, and performing gas-liquid separation, the liquid-phase organic solvent is effectively condensed and recycled; the gaseous hydrogen chloride and carbon oxysulfide enter the feed condenser 9. The gas phase mixture enters a low-temperature rectifying tower 10 for rectifying and separating after being condensed by a feed condenser 9, the byproduct hydrogen chloride is separated from the top of the tower for dehydration and absorption, and the carbon oxysulfide byproduct carbon sulfide removal product buffer tank 13 is obtained from the bottom of the tower. The high-purity carbonyl sulfide enters a carbonyl sulfide product buffer tank 13 for temporary storage, and is filled and discharged by a carbonyl sulfide filling pump 14 at regular intervals.
Example 1
The invention is adopted to recycle the carbonyl sulfide in the toluene-containing chlorination tail gas. The total flow of the tail gas to be recovered is 100kg/h, wherein the mass fraction of the carbonyl sulfide is 0.60, the mass fraction of the hydrogen chloride is 0.38, and the mass fraction of the toluene is 0.02. The outlet pressure of the tail gas compressor 4 is 2MPa, the refrigerant of the primary condenser 5 is circulating water, the refrigerant of the secondary condenser 7 is low-temperature water, the refrigerant of the feeding condenser 9 is-30 ℃ of cryogenic calcium chloride, the heating medium of the tower bottom reboiler 12 is 75 ℃ of hot water, and the cooling medium of the tower top condenser 11 is-30 ℃ of cryogenic calcium chloride. The flow rate of the recovered carbonyl sulfide is 48.87kg/h, the mass fraction is 0.992, and the recovery rate is 80.80%
Example 2
The invention is adopted to recycle the carbonyl sulfide in the ethanol-containing chlorination tail gas. The total flow of the tail gas to be recovered is 100kg/h, wherein the mass fraction of the carbonyl sulfide is 0.55, the mass fraction of the hydrogen chloride is 0.40, and the mass fraction of the toluene is 0.05. The outlet pressure of the tail gas compressor 4 is 2MPa, the refrigerant of the primary condenser 5 is circulating water, the refrigerant of the secondary condenser 7 is chilled glycol at-15 ℃, the refrigerant of the feed condenser 9 is cryogenic calcium chloride at-30 ℃, the heating medium of the tower bottom reboiler 12 is hot water at 75 ℃, and the cooling medium of the tower top condenser 11 is cryogenic calcium chloride at-30 ℃. The flow rate of the recovered carbonyl sulfide is 45.58kg/h, the mass fraction is 0.993, and the recovery rate is 82.29%.
Example 3
The invention is adopted to recycle the carbonyl sulfide in the chloride tail gas containing methylene dichloride. The total flow of the tail gas to be recovered is 100kg/h, wherein the mass fraction of the carbonyl sulfide is 0.58, the mass fraction of the hydrogen chloride is 0.39, and the mass fraction of the toluene is 0.03. The outlet pressure of the tail gas compressor 4 is 2MPa, the refrigerant of the primary condenser 5 is low-temperature water, the refrigerant of the secondary condenser 7 is chilled glycol at-15 ℃, the refrigerant of the feed condenser 9 is cryogenic calcium chloride at-30 ℃, the heating medium of the tower bottom reboiler 12 is hot water at 75 ℃, and the cooling medium of the tower top condenser 11 is cryogenic calcium chloride at-30 ℃. The flow rate of the recovered carbonyl sulfide is 50.11kg/h, the mass fraction is 0.991, and the recovery rate is 85.62%.
Example 4
The invention is adopted to recycle the carbonyl sulfide in the chloridized tail gas containing the ethyl acetate. The total flow of the tail gas to be recovered is 100kg/h, wherein the mass fraction of the carbonyl sulfide is 0.65, the mass fraction of the hydrogen chloride is 0.32, and the mass fraction of the toluene is 0.03. The outlet pressure of the tail gas compressor 4 is 2MPa, the refrigerant of the primary condenser 5 is circulating water, the refrigerant of the secondary condenser 7 is low-temperature water, the refrigerant of the feeding condenser 9 is frozen glycol at-15 ℃, the heating medium of the tower bottom reboiler 12 is high-temperature glycol at 105 ℃, and the cooling medium of the tower top condenser 11 is cryogenic calcium chloride at-30 ℃. The flow rate of the recovered carbonyl sulfide is 51.25kg/h, the mass fraction is 0.994, and the recovery rate is 78.37%.
Example 5
The invention is adopted to recycle the carbonyl sulfide in the chloride tail gas containing methylene dichloride. The total flow of the tail gas to be recovered is 100kg/h, wherein the mass fraction of the carbonyl sulfide is 0.59, the mass fraction of the hydrogen chloride is 0.39, and the mass fraction of the toluene is 0.02. The outlet pressure of the tail gas compressor 4 is 2MPa, the refrigerant of the primary condenser 5 is low-temperature water, the refrigerant of the secondary condenser 7 is chilled glycol at-15 ℃, the refrigerant of the feed condenser 9 is cryogenic calcium chloride at-30 ℃, the heating medium of the tower bottom reboiler 12 is hot water at 40 ℃, and the cooling medium of the tower top condenser 11 is cryogenic calcium chloride at-30 ℃. The flow rate of the recovered carbonyl sulfide is 52.37kg/h, the mass fraction is 0.989, and the recovery rate is 87.79%.
Example 6
The invention is adopted to recycle the carbonyl sulfide in the chloridized tail gas containing methanol. The total flow of the tail gas to be recovered is 100kg/h, wherein the mass fraction of the carbonyl sulfide is 0.56, the mass fraction of the hydrogen chloride is 0.41, and the mass fraction of the toluene is 0.03. The outlet pressure of the tail gas compressor 4 is 2MPa, the refrigerant of the primary condenser 5 is circulating water, the refrigerant of the secondary condenser 7 is low-temperature water, the refrigerant of the feed condenser 9 is chilled glycol at-15 ℃, the heating medium of the tower bottom reboiler 12 is 145 ℃ steam, and the cooling medium of the tower top condenser 11 is-30 ℃ cryogenic calcium chloride. The flow rate of the recovered carbonyl sulfide is 43.29kg/h, the mass fraction is 0.995, and the recovery rate is 76.92%.
Example 7
The invention is adopted to recycle the carbonyl sulfide in the chlorinated tail gas containing acetone. The total flow of the tail gas to be recovered is 100kg/h, wherein the mass fraction of the carbonyl sulfide is 0.58, the mass fraction of the hydrogen chloride is 0.37, and the mass fraction of the toluene is 0.05. The outlet pressure of the tail gas compressor 4 is 2MPa, the refrigerant of the primary condenser 5 is circulating water, the refrigerant of the secondary condenser 7 is chilled glycol at-15 ℃, the refrigerant of the feed condenser 9 is cryogenic calcium chloride at-30 ℃, the heating medium of the tower bottom reboiler 12 is hot water at 25 ℃, and the cooling medium of the tower top condenser 11 is cryogenic calcium chloride at-30 ℃. The flow rate of the recovered carbonyl sulfide is 50.93kg/h, the mass fraction is 0.987, and the recovery rate is 86.67%.
Example 8
The invention is adopted to recycle the carbonyl sulfide in the ethanol-containing chlorination tail gas. The total flow of the tail gas to be recovered is 100kg/h, wherein the mass fraction of the carbonyl sulfide is 0.57, the mass fraction of the hydrogen chloride is 0.39, and the mass fraction of the toluene is 0.04. The outlet pressure of the tail gas compressor 4 is 2MPa, the refrigerant of the primary condenser 5 is circulating water, the refrigerant of the secondary condenser 7 is low-temperature water, the refrigerant of the feeding condenser 9 is frozen glycol at-15 ℃, the heating medium of the tower bottom reboiler 12 is hot water at 25 ℃, and the cooling medium of the tower top condenser 11 is cryogenic calcium chloride at-30 ℃. The flow rate of the recovered carbonyl sulfide is 50.93kg/h, the mass fraction is 0.986, and the recovery rate is 88.10%.
Example 9
The invention is adopted to recycle the carbonyl sulfide in the chloridized tail gas containing the ethyl acetate. The total flow of the tail gas to be recovered is 100kg/h, wherein the mass fraction of the carbonyl sulfide is 0.56, the mass fraction of the hydrogen chloride is 0.41, and the mass fraction of the toluene is 0.03. The outlet pressure of the tail gas compressor 4 is 2MPa, the refrigerant of the primary condenser 5 is circulating water, the refrigerant of the secondary condenser 7 is low-temperature water, the refrigerant of the feed condenser 9 is chilled glycol at-15 ℃, the heating medium of the tower bottom reboiler 12 is 145 ℃ steam, and the cooling medium of the tower top condenser 11 is-30 ℃ cryogenic calcium chloride. The flow rate of the recovered carbonyl sulfide is 43.96kg/h, the mass fraction is 0.995, and the recovery rate is 78.11%.
Example 10
The invention is adopted to recycle the carbonyl sulfide in the chloridized tail gas containing methanol. The total flow of the tail gas to be recovered is 100kg/h, wherein the mass fraction of the carbonyl sulfide is 0.60, the mass fraction of the hydrogen chloride is 0.35, and the mass fraction of the toluene is 0.05. The outlet pressure of the tail gas compressor 4 is 2MPa, the refrigerant of the primary condenser 5 is circulating water, the refrigerant of the secondary condenser 7 is low-temperature water, the refrigerant of the feeding condenser 9 is frozen glycol at-15 ℃, the heating medium of the tower bottom reboiler 12 is hot water at 25 ℃, and the cooling medium of the tower top condenser 11 is cryogenic calcium chloride at-30 ℃. The flow rate of the recovered carbonyl sulfide is 52.35kg/h, the mass fraction is 0.988, and the recovery rate is 86.20%.
Example 11
The invention is adopted to recycle the carbonyl sulfide in the toluene-containing chlorination tail gas. The total flow of the tail gas to be recovered is 100kg/h, wherein the mass fraction of the carbonyl sulfide is 0.61, the mass fraction of the hydrogen chloride is 0.36, and the mass fraction of the toluene is 0.03. The outlet pressure of the tail gas compressor 4 is 2MPa, the refrigerant of the primary condenser 5 is circulating water, the refrigerant of the secondary condenser 7 is low-temperature water, the refrigerant of the feed condenser 6 is chilled glycol at-15 ℃, the heating medium of the tower bottom reboiler 12 is 145 ℃ steam, and the cooling medium of the tower top condenser 11 is-30 ℃ cryogenic calcium chloride. The flow rate of the recovered carbonyl sulfide is 47.62kg/h, the mass fraction is 0.994, and the recovery rate is 77.60%.

Claims (10)

1. An integrated recovery device of carbon oxysulfide in the tail gas of a chlorination process comprises an organic solvent recovery module (1), a low-temperature rectification module (2) and a byproduct buffer module (3), and is characterized in that,
The organic solvent recovery module (1) comprises a tail gas compressor (4), a first-stage condenser (5), a first-stage gas-liquid separator (6), a second-stage condenser (7) and a second-stage gas-liquid separator (8), wherein the tail gas compressor (4) is sequentially connected with the first-stage condenser (5), the first-stage gas-liquid separator (6), the second-stage condenser (7) and the second-stage gas-liquid separator (8);
The low-temperature rectification module (2) comprises a feeding condenser (9), a low-temperature rectification tower (10), a tower top condenser (11) and a tower bottom reboiler (12), wherein the feeding condenser (9) is connected with the low-temperature rectification tower (10), the tower top condenser (11) is arranged above the low-temperature rectification tower (10), the tower bottom reboiler (12) is arranged below the low-temperature rectification tower (10), and the feeding condenser (9) is connected with the secondary gas-liquid separator (8) through a pipeline;
The byproduct buffer module (3) comprises an oxygen carbon sulfide product buffer tank (13) and an oxygen carbon sulfide filling pump (14), and the oxygen carbon sulfide product buffer tank (13) is connected with the low-temperature rectifying tower (10) through a pipeline.
2. The device for recycling carbonyl sulfide in tail gas of integrated chlorination process as claimed in claim 1, wherein the upper outlet of the top of the low temperature rectifying tower (10) is connected with the upper inlet of the top condenser (11), the lower outlet of the top condenser (11) is divided into two branches, and the two branches are respectively connected with the lower inlet of the top of the low temperature rectifying tower (10) and the outlet for recycling hydrogen chloride.
3. An integrated recovery unit for carbon oxysulfide from tail gas of chlorination process as claimed in claim 1, wherein said carbon oxysulfide product buffer tank (13) is provided with an exhaust valve.
4. The device for recycling carbonyl sulfide in integrated chlorination process tail gas according to claim 1, wherein an upper inlet of a bottom of the low-temperature rectifying tower (10) is connected with an upper outlet of a bottom reboiler (12), and a lower outlet of the bottom is divided into two branches and is respectively connected with a lower inlet of the bottom reboiler (12) and an upper inlet of a carbonyl sulfide product buffer tank (13).
5. An integrated recovery plant for carbon oxysulfide from the tail gas of a chlorination process according to claim 1, characterised in that said primary gas-liquid separator (6) and said secondary gas-liquid separator (8) are provided with outlets for recovering the organic solvent.
6. A process for the recovery of carbon oxysulfide from the tail gas of an integrated chlorination process as set forth in claim 1, comprising the steps of:
1) After the recycled chloridized tail gas is pressurized by a tail gas compressor (4), condensing by a first-stage condenser (5) and a first-stage gas-liquid separator (6), condensing by a second-stage condenser (7) and a second-stage gas-liquid separator (8), and effectively condensing and recycling the liquid-phase organic solvent; the gaseous hydrogen chloride and the carbonyl sulfide enter a low-temperature rectifying tower (10);
2) The gas phase mixture enters a low-temperature rectifying tower (10) for rectifying and separating after being condensed by a feed condenser (9), byproduct hydrogen chloride is separated from the top of the tower for dehydration and absorption, and a carbon oxysulfide byproduct deoxidized carbon sulfide product buffer tank (13) is obtained at the bottom of the tower;
3) The high-purity carbonyl sulfide enters a carbonyl sulfide product buffer tank (13) for temporary storage, and is filled and discharged by a carbonyl sulfide filling pump (14) periodically.
7. The process of claim 6, wherein the liquid organic solvent is one or more of toluene, ethanol, methylene chloride, ethyl acetate, methanol, and acetone.
8. The process of an integrated recovery unit for carbonyl sulfide in a tail gas of a chlorination process as claimed in claim 6, wherein the refrigerant medium adopted by the primary condenser (5) and the secondary condenser (7) is circulating water+low temperature water, circulating water+chilled ethylene glycol or low temperature water+chilled ethylene glycol.
9. The process of an integrated recovery unit for carbon oxysulfide from the tail gas of a chlorination process according to claim 6, wherein the refrigerant medium used in said feed condenser (9) is chilled glycol or a cryogenic medium; the refrigerant medium adopted by the tower top condenser (11) is frozen glycol or cryogenic medium; the heat medium adopted by the tower bottom reboiler (12) is hot water, high-temperature glycol or steam.
10. A process for an integrated carbon oxysulfide recovery device from a tail gas of a chlorination process as set forth in claim 9, the method is characterized in that the temperature of the heating medium is 25-145 ℃.
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