CN112221312A - Method and device for separating and recovering tail gas in thionyl chloride production process - Google Patents
Method and device for separating and recovering tail gas in thionyl chloride production process Download PDFInfo
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- CN112221312A CN112221312A CN202011027951.XA CN202011027951A CN112221312A CN 112221312 A CN112221312 A CN 112221312A CN 202011027951 A CN202011027951 A CN 202011027951A CN 112221312 A CN112221312 A CN 112221312A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/002—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by condensation
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Abstract
The invention relates to a device and a method for separating and recovering tail gas in a thionyl chloride production process, which are characterized in that: (1) after the tail gas generated in the thionyl chloride production process is subjected to cryogenic cooling in a first-stage cryogenic device, allowing a liquid phase to flow into a liquid accumulation tank, and allowing a gas phase to enter a second-stage cryogenic device, wherein the first-stage cryogenic temperature is-12 to-17 ℃; (2) the secondary cryogenic temperature is-22 to-28 ℃, the liquid phase flows into the liquid accumulation tank, and the gas phase enters the tertiary cryogenic device; (3) the secondary cryogenic temperature is-35 to-39 ℃, the liquid phase flows into a liquid accumulation tank, and the gas phase enters a primary spray absorption tower; (4) after being absorbed by the first-stage spray absorption tower, unabsorbed gas enters the second-stage spray absorption tower, and after being absorbed by the second-stage spray absorption tower, the unabsorbed gas is directly discharged outside. The invention has the advantages that: adopts a three-stage deep cooling process to separate SO in the tail gas2、Cl2So that the sulfur dioxide and the chlorine in the whole set are basically and completely utilized, and the three wastes are greatly reduced.
Description
Technical Field
The invention belongs to the technical field of chemical production, and relates to a method and a device for separating and recovering tail gas in a thionyl chloride production process.
Background
The thionyl chloride is colorless or light yellow liquid with pungent smell at normal temperature and normal pressure, a small amount of decomposition is carried out above the boiling point (78.8 ℃), the decomposition rate is high at 140 ℃, the decomposition is completed at 500 ℃, the decomposition products comprise sulfur dioxide, chlorine, sulfur dichloride and sulfur monochloride, and the thionyl chloride is an important organic synthetic chlorinating agent, such as chlorination of alcohol hydroxyl, chlorination of carboxylic acid, chlorination of anhydride, and chlorine replacement of organic sulfonic acid or nitro compound. The acyl chloride can be used for ring-closing reaction and Beckmann transposition, is an important chemical intermediate, and is widely applied to the traditional industries such as agriculture, medicine, dye and the like. In addition, the application range of thionyl chloride is also expanding continuously, and the thionyl chloride is widely applied to food additive industries such as preparation of sucralose and new energy industries such as production of lithium ion batteries.
The production method of thionyl chloride mainly comprises three methods, namely a chlorosulfonic acid method, a phosphorus oxychloride co-production method and a sulfur dioxide gas phase method, and the method is mainly adopted by national thionyl chloride production enterprises for production because of the advantages of advanced process, cheap and easily-obtained raw materials, high product yield, stable quality, less three-waste emission and the like of the sulfur dioxide gas phase method. The tail gas in the process of producing the thionyl chloride by the sulfur dioxide gas phase method mainly comes from the induced draft and the evacuation of a synthesis kettle, a catalytic converter, a crude product receiver, a heavy product removal tower, a light product removal tower and a cracker, and the generated tail gas mainly comprises sulfur dioxide, thionyl chloride, sulfur dichloride and chlorine gas.
The traditional thionyl chloride tail gas treatment method is that the tail gas is directly introduced into a water absorption device without being treated, thionyl chloride and sulfur dichloride in the tail gas react with water to generate acid gases such as hydrogen chloride and sulfur dioxide, the hydrogen chloride is absorbed by the water to prepare hydrochloric acid, and the sulfur dioxide which is not completely absorbed by the water is introduced into a sodium hydroxide solution spraying absorption device to be absorbed to prepare sodium sulfite solution. The traditional tail gas treatment method has the defects of more hydrochloric acid and sodium sulfite as byproducts and low value, and has high alkali liquor absorption cost because the tail gas is not recycled, and a small amount of sulfur dioxide in the tail gas is still discharged into the atmosphere, so that the unit consumption is increased, and the environmental protection pressure is also increased.
Disclosure of Invention
The invention aims to solve the problems of the conventional thionyl chloride tail gas treatment, and provides a device and a method for separating tail gas in a thionyl chloride production process, which can effectively separate sulfur dioxide and chlorine gas to recycle the sulfur dioxide and the chlorine gas to a production system, thereby achieving the purposes of improving yield and reducing cost.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the utility model provides a thionyl chloride production process tail gas separation recovery unit which characterized in that includes: the system comprises a primary cryogenic device, a secondary cryogenic device, a tertiary cryogenic device, a primary spray absorption tower and a secondary spray absorption tower which are sequentially connected through pipelines; the first-stage cryogenic device, the second-stage cryogenic device and the third-stage cryogenic device are respectively connected with the liquid accumulation tank through pipelines, and the liquid accumulation tank is connected with the synthesis kettle through a pipeline.
Further, the deep cooling device is a fixed tube-plate heat exchanger.
Furthermore, the inner lining of the spray absorption tower is made of polytetrafluoroethylene, and polypropylene corrugated plate regular packing is arranged in the inner lining of the spray absorption tower.
Further, the spray absorption tower is internally provided with polypropylene corrugated plate regular packing with the model number of Y250.
A method for separating and recovering tail gas in a thionyl chloride production process is characterized by comprising the following steps:
(1) after tail gas (68-80 percent of sulfur dioxide and 20-32 percent of chlorine gas) generated in the production process of thionyl chloride is subjected to cryogenic cooling in a primary cryogenic device, liquid-phase sulfur dioxide flows into a liquid accumulation tank, uncooled gas phase (4-7.5 percent of sulfur dioxide and 92.5-96 percent of chlorine gas) enters a secondary cryogenic device, and the temperature of the primary cryogenic device is controlled to be-12 to-17 ℃;
(2) controlling the temperature of the secondary cryogenic device to be-22 to-28 ℃, enabling liquid-phase sulfur dioxide after cryogenic cooling to flow into a liquid accumulation tank, and enabling gas phase (the content of sulfur dioxide is less than 1 percent and chlorine is 99 percent) which is not cooled to enter the tertiary cryogenic device;
(3) controlling the temperature of a secondary cryogenic device to be-35 to-39 ℃, enabling liquid-phase sulfur dioxide after cryogenic cooling to flow into a liquid accumulation tank, and enabling uncooled gas phase (3.8-7% of sulfur dioxide and 93-96.2% of chlorine) to enter a primary spray absorption tower;
(4) after being absorbed by the first-stage spray absorption tower, unabsorbed gas (80-89 percent of sulfur dioxide and 11-20 percent of chlorine) enters the second-stage spray absorption tower, and after being absorbed by the second-stage spray absorption tower, the unabsorbed gas (26-43 percent of sulfur dioxide and 57-74 percent of chlorine) is directly discharged into the atmosphere; wherein the first-stage spraying absorption tower adopts pure water absorption, the second-stage spraying absorption tower adopts hydrogen peroxide with the concentration of 20-30% for absorption, hydrochloric acid (the concentration is 15-22%) obtained in the first-stage spraying absorption tower can be recycled, sulfuric acid solution (the concentration is controlled to be 12-16%) obtained in the second-stage spraying absorption tower can be recycled, and sulfur dioxide and chlorine liquid in the liquid accumulation tank are directly pumped back to the synthesis kettle for use.
The invention has the advantages that:
1. the recovery method reduces the consumption of the sulfur dioxide and ensures that the conversion rate can reach more than 99.0 percent because the sulfur dioxide is recovered and reused;
2. adopts a three-stage deep cooling process to separate SO in the tail gas2、Cl2So that the sulfur dioxide and the chlorine in the whole set are basically and completely utilized, and the three wastes are greatly reduced;
3. the traditional sulfur dioxide tail gas adopts water absorption and alkali absorption treatment processes, the liquid alkali consumption is large, the value of a byproduct sodium sulfite is low, the tail gas is incompletely absorbed, a small amount of sulfur dioxide is still discharged into the atmosphere, and the process is undoubtedly a great restriction factor under the current environmental protection pressure3）。
Drawings
FIG. 1 is a basic flow chart of the separation, recovery and treatment of tail gas from thionyl chloride production process according to the present invention.
Detailed Description
The invention is further illustrated with reference to fig. 1:
the utility model provides a thionyl chloride production process tail gas separation recovery unit, includes: the system comprises a primary cryogenic device, a secondary cryogenic device, a tertiary cryogenic device, a primary spray absorption tower and a secondary spray absorption tower which are sequentially connected through pipelines; the primary cryogenic device, the secondary cryogenic device and the tertiary cryogenic device are respectively connected with the effusion tank through pipelines, and the effusion tank is connected with the synthesis kettle through a pipeline; the first-stage cryogenic device, the second-stage cryogenic device and the third-stage cryogenic device are fixed tube-plate heat exchangers; the absorption tower sprays is the inside lining polytetrafluoroethylene material, and the regular packing of polypropylene buckled plate that changes of built-in Y250, and the position that wherein one-level cryogenic device, second grade cryogenic device, tertiary cryogenic device set up is higher than the position of ponding jar to form pressure differential and make liquid can the unimpeded transport, reduce the consumption and the possible leakage of the energy that the pump sending brought.
Example 1
A method for separating and recovering tail gas in a thionyl chloride production process comprises the following specific implementation steps:
(1) noncondensable gas (sulfur dioxide is 78 percent and chlorine is 22 percent) discharged by a thionyl chloride crude product condenser, a crude product receiver, a sulfur preparation kettle and a rectifying device is introduced from the shell pass of a primary cryogenic device (a fixed tube plate heat exchanger), after heat exchange is carried out on-13 ℃ frozen brine flowing through the tube pass, 98 percent of the sulfur dioxide gas is condensed and flows into a liquid accumulation tank, and the residual tail gas enters the shell pass of a secondary cryogenic device;
(2) after the heat exchange of the residual tail gas (sulfur dioxide is 78 percent and chlorine is 22 percent) through the-25 ℃ frozen brine flowing through the tube pass of the secondary cryogenic device, 98 percent of sulfur dioxide gas is condensed and flows into a liquid accumulation tank, and the residual tail gas enters the shell pass of the tertiary cryogenic device;
(3) after the heat exchange of the residual tail gas is carried out by the frozen brine with the temperature of-35 ℃ flowing through the tube pass of the three-stage cryogenic device, 98 percent of chlorine gas is condensed and flows into the liquid accumulation tank, the residual tail gas enters the spraying absorption device, and liquid sulfur dioxide in the liquid accumulation tank directly returns to the catalyst for use;
(4) introducing tail gas from a three-stage cryogenic device from the lower part of a first-stage spray absorption tower, simultaneously starting a circulating pump at the bottom of the tower to circulate, controlling the temperature at the bottom of the tower to be 20 ℃, simultaneously sampling every 6 hours to perform primary analysis, analyzing whether the content of hydrochloric acid reaches 15-22%, if so, starting to discharge hydrochloric acid at the bottom of the tower, and simultaneously starting a pure water valve to supplement water to the first-stage spray absorption tower;
(5) introducing tail gas from the primary spray absorption device from the lower part of the secondary spray absorption tower, simultaneously starting a circulating pump at the bottom of the tower to circulate, controlling the temperature at the bottom of the tower to be 20 ℃, simultaneously sampling every 6 hours to perform primary analysis, analyzing whether the concentration of sulfuric acid at the bottom of the tower reaches 12-16%, if so, discharging sulfuric acid solution at the bottom of the tower, simultaneously starting a hydrogen peroxide valve, supplementing hydrogen peroxide to the secondary spray absorption tower, and directly discharging the tail gas from the secondary spray tower into the atmosphere.
Claims (5)
1. The utility model provides a thionyl chloride production process tail gas separation recovery unit which characterized in that: the system comprises a primary cryogenic device, a secondary cryogenic device, a tertiary cryogenic device, a primary spray absorption tower and a secondary spray absorption tower which are sequentially connected through pipelines; the first-stage cryogenic device, the second-stage cryogenic device and the third-stage cryogenic device are respectively connected with the liquid accumulation tank through pipelines, and the liquid accumulation tank is connected with the synthesis kettle through a pipeline.
2. The device for separating and recovering the tail gas in the thionyl chloride production process according to claim 1, characterized in that: the deep cooling device is a fixed tube-plate heat exchanger.
3. The device for separating and recovering the tail gas in the thionyl chloride production process according to claim 1, characterized in that: the inner lining of the spraying absorption tower is made of polytetrafluoroethylene, and regular packing of polypropylene corrugated plates is arranged in the inner lining of the spraying absorption tower.
4. The device for separating and recovering the tail gas in the thionyl chloride production process according to claim 3, characterized in that: the spray absorption tower is internally provided with polypropylene corrugated plate regular packing with the model number of Y250.
5. A method for separating and recovering tail gas in a thionyl chloride production process is characterized by comprising the following steps:
(1) after the tail gas generated in the production process of thionyl chloride is subjected to cryogenic cooling in a primary cryogenic device, liquid-phase sulfur dioxide flows into a liquid accumulation tank, uncooled gas phase enters a secondary cryogenic device, and the temperature of the primary cryogenic device is controlled to be-12 to-17 ℃;
(2) controlling the temperature of the secondary cryogenic device to be-22 to-28 ℃, enabling liquid-phase sulfur dioxide after cryogenic cooling to flow into the liquid accumulation tank, and enabling uncooled gas phase to enter the tertiary cryogenic device;
(3) controlling the temperature of the secondary cryogenic device to be-35 to-39 ℃, enabling liquid-phase sulfur dioxide after cryogenic cooling to flow into the liquid accumulation tank, and enabling uncooled gas phase to enter the primary spray absorption tower;
(4) after being absorbed by the primary spray absorption tower, unabsorbed gas enters the secondary spray absorption tower, and after being absorbed by the secondary spray absorption tower, the unabsorbed gas is directly discharged into the atmosphere; wherein the first-stage spraying absorption tower adopts pure water absorption, the second-stage spraying absorption tower adopts hydrogen peroxide with the concentration of 20-30% for absorption, hydrochloric acid obtained in the first-stage spraying absorption tower can be recycled, sulfuric acid solution obtained in the second-stage spraying absorption tower can be recycled, and sulfur dioxide and chlorine gas in the liquid accumulation tank are directly pumped back to the synthesis kettle for use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202011027951.XA CN112221312A (en) | 2020-09-26 | 2020-09-26 | Method and device for separating and recovering tail gas in thionyl chloride production process |
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| CN202011027951.XA CN112221312A (en) | 2020-09-26 | 2020-09-26 | Method and device for separating and recovering tail gas in thionyl chloride production process |
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| CN112221312A true CN112221312A (en) | 2021-01-15 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113694676A (en) * | 2021-07-23 | 2021-11-26 | 河北光兴半导体技术有限公司 | Waste gas treatment equipment and glass production system |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107930366A (en) * | 2017-11-30 | 2018-04-20 | 山东凯盛新材料股份有限公司 | The technique that thionyl chloride integrates treating tail gas |
| CN207941383U (en) * | 2017-11-30 | 2018-10-09 | 成武县晨晖环保科技有限公司 | Chloracetyl chloride tail gas by-product sulfuric acid apparatus |
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2020
- 2020-09-26 CN CN202011027951.XA patent/CN112221312A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107930366A (en) * | 2017-11-30 | 2018-04-20 | 山东凯盛新材料股份有限公司 | The technique that thionyl chloride integrates treating tail gas |
| CN207941383U (en) * | 2017-11-30 | 2018-10-09 | 成武县晨晖环保科技有限公司 | Chloracetyl chloride tail gas by-product sulfuric acid apparatus |
Non-Patent Citations (3)
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| 华东化工学院等合编: "《基本有机化工工艺学》", 31 January 1981, 化学工业出版社 * |
| 汪多仁主编: "《溶剂与专用化学品生产配方的合成工艺》", 30 June 2001, 科学技术文献出版社 * |
| 陈滨等合编: "《石油化工手册 第1分册 原料资源篇》", 30 November 1988, 化学工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113694676A (en) * | 2021-07-23 | 2021-11-26 | 河北光兴半导体技术有限公司 | Waste gas treatment equipment and glass production system |
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Effective date of registration: 20210203 Address after: 233200 Jianhe Road, salt chemical industrial park, Dingyuan County, Chuzhou City, Anhui Province Applicant after: Anhui Jinxuan Technology Co.,Ltd. Address before: No. 127, East Street, Lai'an county, Chuzhou City, Anhui Province Applicant before: ANHUI JINGHE INDUSTRIAL Co.,Ltd. |
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