CN110092707B - Method for removing hydrogen fluoride in tetrafluoroethylene production process - Google Patents
Method for removing hydrogen fluoride in tetrafluoroethylene production process Download PDFInfo
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- CN110092707B CN110092707B CN201810089225.7A CN201810089225A CN110092707B CN 110092707 B CN110092707 B CN 110092707B CN 201810089225 A CN201810089225 A CN 201810089225A CN 110092707 B CN110092707 B CN 110092707B
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- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
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- C01B7/0706—Purification ; Separation of hydrogen chloride
- C01B7/0731—Purification ; Separation of hydrogen chloride by extraction
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Abstract
The invention provides a method for removing hydrogen fluoride in the production process of tetrafluoroethylene, which comprises the following steps: 1) defluorination by extraction reaction, 2) clarification and layering, wherein the upper layer is defluorination agent after extraction reaction and enters a regeneration tower, and the lower layer is hydrochloric acid without hydrogen fluoride and enters an acid tank; 3) and (3) regenerating a defluorination agent: the regeneration tower adopts defluorinating agent from the clarifying and layering tank to mix with circulating alkali liquor from the regeneration tower kettle, and simultaneously, fresh alkali liquor is intermittently supplemented to the mixer. The method for removing the hydrogen fluoride effectively reduces the content of the hydrogen fluoride in the cracking product. The defluorinating agent has low consumption and low cost while achieving good defluorinating effect. The process is simple to operate and can be industrially automated.
Description
Technical Field
The invention relates to the field of organic chemistry, in particular to a method for purifying tetrafluoroethylene.
Background
The production of tetrafluoroethylene belongs to a high-temperature cracking process, the existing fluorine chemical industry mainly adopts superheated steam to crack difluorochloromethane (F22) to produce tetrafluoroethylene, and a small amount of hydrogen fluoride can be produced in the production process, wherein the content of the hydrogen fluoride is about 0.5 percent (mass percentage). As a byproduct of tetrafluoroethylene monomer production, hydrogen fluoride has low content, high treatment cost and great technical difficulty, and how to remove hydrogen fluoride is not reported.
Presence of hydrogen fluoride:
1. the corrosion of the equipment is aggravated, the accidents are frequent, the operating rate of the device is reduced, and the safety accidents are frequent.
2. The hydrochloric acid enters into byproduct hydrochloric acid to influence the quality of the hydrochloric acid, so that the hydrochloric acid is difficult to sell, and the expansion of the hydrochloric acid is a difficult problem in the fluorine chemical industry.
3. The polytetrafluoroethylene high-end resin can enter a subsequent system along with materials to influence the quality of tetrafluoroethylene, the quality of domestic polytetrafluoroethylene high-end resin products is generally lower than that of domestic polytetrafluoroethylene high-end resin products, and the reason is related to the fact that tetrafluoroethylene monomers contain hydrogen fluoride. The tetrafluoroethylene monomer contains a small amount of hydrogen fluoride, which can affect the quality of tetrafluoroethylene polymerization products and the quality of byproduct hydrochloric acid, so that the content of fluorine ions exceeds the standard, and the sale is affected.
In view of the improvement of product quality and safety, there is a strong need in the art for a practical and efficient treatment technique for efficiently removing hydrogen fluoride generated during the production of tetrafluoroethylene.
Disclosure of Invention
Aiming at the defects in the field, the invention aims to provide a method for removing hydrogen fluoride in the production process of tetrafluoroethylene. The defluorinating agent selected by the invention has the advantages of good defluorinating effect, low consumption, high recycling rate, easily available raw materials, stable property and easy layering, is obtained through numerous experimental verifications, and has high reliability.
The technical scheme for realizing the purpose of the invention is as follows:
a method for removing hydrogen fluoride in a tetrafluoroethylene production process comprises the following steps:
1) and (3) defluorination by extraction reaction: enabling pyrolysis gas containing tetrafluoroethylene, water vapor and hydrogen fluoride and a defluorinating agent to flow into a defluorinating device in parallel, and enabling the defluorinated pyrolysis gas to enter a subsequent system; the defluorination agent is selected from one or a mixture of a plurality of siloxanes such as tetrabutoxy silane, tetra-sec-butoxy silane, tetraethoxy silane and the like;
2) clarifying and layering: allowing the defluorinated mixed liquid to enter a clarifying layering tank, standing for 30-40 min for layering, allowing the defluorinating agent subjected to extraction reaction to enter a regeneration tower at the upper layer, and allowing hydrochloric acid containing no hydrogen fluoride to enter an acid tank at the lower layer;
3) and (3) regenerating a defluorination agent: the regeneration tower adopts defluorinating agent from the clarification layering tank to mix with circulating alkali liquor from the regeneration tower kettle, the mixed liquid is regenerated in the regeneration tower and continuously flows to the tower kettle from the tower top, layering is completed in the tower kettle, the upper layer liquid is conveyed to the defluorinating device for recycling, the lower layer liquid is used for separating sodium fluoride, the rest part is self-circulated in the regeneration tower, and the discharge amount of the sodium fluoride waste liquid is 1-5% (volume ratio) of the circulating liquid amount.
Further, in the step 1), the temperature of the pyrolysis gas is 135-150 ℃, and the mass ratio of the pyrolysis gas to the liquid to gas of the defluorinating agent is 6-8: 1; the retention time of the materials in the defluorinating device is 2-3 min.
The defluorination agent can be achieved by using one or more of tetrabutoxy silane, tetra-sec-butoxy silane and tetraethoxy silane, and the mass ratio of the tetrabutoxy silane, the tetra-sec-butoxy silane and the tetraethoxy silane can be 5 (2-5) to 1-3 when the defluorination agent is used in a mixing way.
Wherein in the step 1), the density of the defluorinating agent is 0.85-0.90 g/m3(ii) a Controlling the defluorination pressure to be 0.03-0.05 Mpa and the defluorination temperature to be 40-45 ℃.
Wherein in the step 2), the clarifying and layering pressure is controlled to be normal pressure, and the temperature is controlled to be 35-40 ℃; the ratio of the upper layer liquid level to the lower layer liquid level is 1 (2-4); the retention time of the mixed liquid in the clarification layering tank is 30-35 min.
In the step 3), the pressure of the regeneration tower is controlled to be normal pressure, the operation temperature of the tower kettle is controlled to be 30-35 ℃, and the ratio of the upper layer liquid level to the lower layer liquid level in the tower is 1 (1-3).
In the step 3), the retention time of the liquid in the tower kettle is 30-35 min, the effective retention time of the liquid in the filler is 2-3 min, and the full regeneration of the liquid is ensured; the concentration of the alkali liquor in the tower kettle is controlled to be 5-10% by supplementing fresh alkali liquor.
And 3) continuously discharging the waste liquid containing sodium fluoride, wherein the amount of the waste liquid is about 1-5% (volume ratio) of the amount of the circulating liquid.
Wherein the dosage of the defluorinating agent relative to the pyrolysis gas material is 0.3-0.5 kg/t. Because the defluorinating agent is recycled after regeneration, the dosage of the defluorinating agent refers to the dosage of fresh added defluorinating agent in continuous operation.
A system for removing hydrogen fluoride comprises a defluorination tower, a clarification layering tank, a mixer and a regeneration tower;
the top of the defluorination tower is connected with a pyrolysis gas feeding pipe and a defluorination agent feeding pipe, the bottom of the defluorination tower is connected with the clarification layering tank through a pipeline, the clarification layering tank is connected with the mixer through a pipeline, and the mixer is connected with the regeneration tower; the lower part of the regeneration tower is connected to the mixer through an alkali liquor circulating pipeline; the bottom of the regeneration tower is provided with a sodium fluoride waste liquid discharge outlet.
The defluorination tower comprises a tube array structure, a cooling medium is fed on a shell side, and a material is fed on a tube side; and a cooling coil is arranged in the clarification layering tank, and a cooling coil is arranged in the regeneration tower.
Wherein the regeneration tower is a packed tower, and polypropylene (PP) pall rings are randomly piled in the tower; the regeneration tower is connected to the defluorinating agent feed pipe by a pipeline and a pump.
The method for removing the hydrogen fluoride provided by the invention has the following advantages:
1. effectively reduces the content of hydrogen fluoride in the cracking product.
2. The defluorinating agent has low consumption and low cost while achieving good defluorinating effect.
3. The invention has simple process operation and can realize industrial automation.
4. The method can obviously reduce the content of fluorine ions in the by-product hydrochloric acid and improve the quality of the hydrochloric acid.
5. The invention can obviously reduce the content of hydrogen fluoride in the tetrafluoroethylene monomer, so that the quality of the tetrafluoroethylene monomer is stepped, the quality of a downstream polytetrafluoroethylene product can be ensured, and a foundation is laid for producing a high-end tetrafluoroethylene product.
6. The defluorinating agent and the alkali liquor have low consumption, can greatly save the waste of materials and reduce the environmental pollution, thereby creating good economic and social benefits.
Drawings
FIG. 1 is a schematic diagram of a system for removing hydrogen fluoride according to the present invention.
The corresponding relation between the parts and the numbers in the figure is as follows: the device comprises a defluorination tower 1, a pyrolysis gas feeding pipe 101, a defluorination agent feeding pipe 102, a gas phase material outlet 103, a clarification layering tank 2, a mixer 3, a regeneration tower 4, a sodium fluoride waste liquid discharge port 401, an exhaust valve 402, a cooling medium inlet 501, a cooling medium outlet 502 and a pump 6.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
Referring to fig. 1, the system for removing hydrogen fluoride adopted by the method comprises a defluorination tower 1, a clarification layering tank 2, a mixer 3 and a regeneration tower 4;
the top of the defluorination tower is connected with a pyrolysis gas feeding pipe 101 and a defluorination agent feeding pipe 102, and a gas phase material outlet 103 arranged at the lower part of the defluorination tower is used for conveying the defluorinated pyrolysis gas to a subsequent system; the bottom of the defluorination tower is connected with the clarification layering tank 2 through a pipeline, the clarification layering tank is connected with the mixer 3 through a pipeline, and the mixer 3 is connected with the regeneration tower 4; the lower part of the regeneration tower is connected to the mixer through an alkali liquor circulating pipeline; the bottom of the regeneration tower is provided with a sodium fluoride waste liquid discharge port 401, and the top is provided with an emptying valve 402. The mixer 3 is connected with a fresh lye inlet 301.
The defluorination tower comprises a tube array structure, a shell pass is used for passing cooling medium and is connected with a cooling medium inlet 501 and a cooling medium outlet 502, and a mixture material passes through a tube pass; and a cooling coil is arranged in the clarification layering tank, and a cooling coil is arranged in the regeneration tower. The cooling coil is connected with a cooling medium inlet 501 and a cooling medium outlet 502.
The regeneration tower 4 is a packed tower, and PP pall rings of DN50 are disorderly stacked in the tower; the regeneration column is connected to the defluorinating agent feed line 102 by piping and pump 6.
The operation of removing hydrogen fluoride comprises three steps:
the first step is extraction reaction defluorination: the temperature of pyrolysis gas containing tetrafluoroethylene, water vapor and hydrogen fluoride from a quencher is 135-150 ℃, the material is 135-150 ℃ after passing through the quencher, the temperature of the material at 135-150 ℃ is reduced to 40-45 ℃ after passing through a defluorination tower, the material and a defluorination agent from a regeneration tower flow in parallel and enter the defluorination device, the pyrolysis gas after defluorination enters a subsequent system, and the mixed liquid after defluorination enters a clarification layering tank. The defluorinating agent is a mixed solution of tetrabutoxy silane, tetra-sec-butoxy silane and tetraethoxy silane, and the density of the mixed solution is 0.88g/m3(when the mixture is used, the mass ratio of the tetra-butoxy silane to the tetra-sec-butoxy silane to the tetraethoxy silane is 5:3: 2); controlling the defluorination pressure to be 0.03-0.05 Mpa and the defluorination temperature to be 40-45 ℃; the liquid-gas mass ratio is 6: 1; supplement defluorinating agent relative to cracking gasThe material consumption is 0.4kg/t, and the retention time of the material in the defluorinating device is 2-3 min.
The second step is clarification and demixing: the mixed liquid from the defluorinating device enters a clarifying layering tank, and because hydrogen fluoride is easy to react with the defluorinating agent, the reacted substances are insoluble in water and have density less than that of water, the defluorinating agent which is extracted and reacted on the upper layer enters a regeneration tower, and hydrochloric acid which does not contain hydrogen fluoride on the lower layer enters an acid tank. Controlling the clarifying and layering pressure to be normal pressure and the temperature to be 35-40 ℃; the ratio of the upper layer liquid level to the lower layer liquid level is 1: 3; the retention time of the mixed liquid in the clarification layering tank is 30-35 min.
The third step is defluorination agent regeneration: the regeneration tower adopts defluorinating agent from the clarifying and layering tank to mix with circulating alkali liquor from the regeneration tower kettle, and simultaneously, fresh alkali liquor (sodium hydroxide solution) is intermittently supplemented to the mixer. The mixed liquid is regenerated in the packing in the tower, continuously flows to the tower kettle from the tower top, is divided into layers in the tower, the upper layer liquid is recycled to the defluorinating device, one part of the lower layer liquid is removed from the treatment device, one part of the lower layer liquid is discharged continuously from the circulating waste liquid containing sodium fluoride in the tower, and the amount of the waste liquid is about 2 percent (volume ratio) of the amount of the circulating liquid. Controlling the pressure of the regeneration tower to be normal pressure, the operating temperature of the tower kettle to be 30-35 ℃, and the ratio of the upper-layer liquid level to the lower-layer liquid level of the tower kettle to be 1: 2; the retention time of the liquid in the tower kettle is 30-35 min, the effective retention time of the liquid in the filler is 2-3 min, and the full regeneration of the liquid is ensured; the mass concentration of the alkali liquor in the tower bottom is controlled to be 10 percent so as to achieve the best regeneration effect.
The content of HF in the hydrochloric acid discharged from the bottom of the clarifying and layering tank after the pyrolysis gas with the hydrogen fluoride content of 0.5 percent (mass percentage) is treated by the method is 5 ppm.
Example 2
With the system of example 1, the hydrogen fluoride removal operation included the steps of:
the first step is extraction reaction defluorination: and (3) enabling pyrolysis gas containing tetrafluoroethylene, water vapor and hydrogen fluoride to flow with a defluorinating agent from a regeneration tower at 135-150 ℃ and enter a defluorinating device, enabling the defluorinated pyrolysis gas to enter a subsequent system, and enabling mixed liquid after defluorination to enter a clarification layering tank. The defluorinating agent is tetrabutoxy silane with densityIs 0.899g/m3Adding defluorinating agent in an amount of 0.3kg/t relative to the amount of the cracking gas material; controlling the defluorination pressure to be 0.05Mpa and the defluorination temperature to be 45 ℃; the liquid-gas mass ratio is 7: 1; the retention time of the materials in the defluorinating device is 2-3 min.
The second step is clarification and demixing: the mixed liquid from the defluorinating device enters a clarifying and layering tank, and the clarifying and layering pressure is controlled to be normal pressure and the temperature is controlled to be 38 ℃; the ratio of the upper layer liquid level to the lower layer liquid level is 1: 3; the retention time of the mixed liquid in the clarifying and demixing tank is 30 min.
The third step is defluorination agent regeneration: the regeneration tower adopts defluorinating agent from the clarifying and layering tank to mix with circulating alkali liquor from the regeneration tower kettle, and simultaneously, fresh alkali liquor is intermittently supplemented to the mixer. The mixed liquid is regenerated in the packing in the tower, continuously flows to the tower kettle from the tower top, is layered in the tower kettle, the upper layer liquid is recycled to the defluorinating device, one part of the lower layer liquid is removed from the treatment device, one part of the lower layer liquid is self-circulated in the tower, the sodium fluoride waste liquid is continuously discharged, and the waste liquid amount is about 4 percent (volume ratio) of the circulating liquid amount. Controlling the pressure of the regeneration tower to be normal pressure, the operating temperature of the tower kettle to be 35 ℃, and the ratio of the upper-layer liquid level to the lower-layer liquid level of the tower kettle to be 1: 2; the retention time of the liquid in the tower kettle is 30-35 min, the effective retention time of the liquid in the filler is 2-3 min, and the full regeneration of the liquid is ensured; and controlling the concentration of the alkali liquor in the tower bottom to be 10 percent.
The content of HF in the hydrochloric acid discharged from the bottom of the clarifying and layering tank after the pyrolysis gas with the hydrogen fluoride content of 0.5 percent (mass percentage) is treated by the method is 6 ppm.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A method for removing hydrogen fluoride in the production process of tetrafluoroethylene is characterized by comprising the following steps:
1) and (3) defluorination by extraction reaction: enabling pyrolysis gas containing tetrafluoroethylene, water vapor and hydrogen fluoride and a defluorinating agent to flow into a defluorinating device in parallel, and enabling the defluorinated pyrolysis gas to enter a subsequent system; the defluorination agent is selected from one or a mixture of more of tetrabutoxy silane, tetra-sec-butoxy silane and tetraethoxy silane;
2) clarifying and layering: allowing the defluorinated mixed liquid to enter a clarifying layering tank, standing for 30-40 min for layering, allowing the defluorinating agent subjected to extraction reaction to enter a regeneration tower at the upper layer, and allowing hydrochloric acid containing no hydrogen fluoride to enter an acid tank at the lower layer;
3) and (3) regenerating a defluorination agent: the regeneration tower adopts defluorinating agent from the clarification layering tank to mix with circulating alkali liquor from a regeneration tower kettle, the mixed liquid is regenerated in the regeneration tower and continuously flows to the tower kettle from the tower top, layering is completed in the tower, the upper layer liquid is conveyed to the defluorinating device for recycling, the lower layer liquid is used for separating sodium fluoride, the rest part is self-circulated in the regeneration tower, and the discharge amount of the sodium fluoride waste liquid is 1-5% of the circulating liquid amount.
2. The method according to claim 1, wherein in the step 1), the temperature of the pyrolysis gas is 135-150 ℃, and the liquid-gas mass ratio of the pyrolysis gas to the defluorinating agent is 6-8: 1; the retention time of the materials in the defluorinating device is 2-3 min.
3. The method according to claim 1, wherein in step 1), the density of the defluorinating agent is 0.85-0.90 g/m3(ii) a Controlling the defluorination pressure to be 0.03-0.05 Mpa and the defluorination temperature to be 40-45 ℃.
4. The method according to claim 1, wherein in the step 2), the clarifying and demixing pressure is controlled to be normal pressure and the temperature is controlled to be 35-40 ℃; the ratio of the upper layer liquid level to the lower layer liquid level is 1 (2-4); the retention time of the mixed liquid in the clarification layering tank is 30-35 min.
5. The method according to any one of claims 1 to 4, wherein in the step 3), the pressure of the regeneration tower is controlled to be normal pressure, the operation temperature of the tower kettle is controlled to be 30 to 35 ℃, and the ratio of the liquid level of the upper layer of the tower kettle to the liquid level of the lower layer of the tower kettle is 1 (1 to 3).
6. The method according to any one of claims 1 to 4, wherein in the step 3), the residence time of the liquid in the tower kettle is 30 to 35min, and the effective residence time of the liquid in the packing is 2 to 3min, so that the full regeneration of the liquid is ensured; the concentration of the alkali liquor in the tower kettle is controlled to be 5-10% by supplementing fresh alkali liquor.
7. The method according to any one of claims 1 to 4, wherein the amount of the defluorinating agent used is 0.3 to 0.5kg/t relative to the charge of cracked gas.
8. The device for removing the hydrogen fluoride is characterized by comprising a defluorination tower, a clarification layering tank, a mixer and a regeneration tower;
the top of the defluorination tower is connected with a pyrolysis gas feeding pipe and a defluorination agent feeding pipe, the bottom of the defluorination tower is connected with the clarification layering tank through a pipeline, the clarification layering tank is connected with the mixer through a pipeline, and the mixer is connected with the regeneration tower; the lower part of the regeneration tower is connected to the mixer through an alkali liquor circulating pipeline; the bottom of the regeneration tower is provided with a sodium fluoride waste liquid discharge outlet.
9. The apparatus of claim 8, wherein the defluorinating column comprises a tube array structure, a shell side is used for removing a cooling medium, and a material is used for removing a tube side; and a cooling coil is arranged in the clarification layering tank, and a cooling coil is arranged in the regeneration tower.
10. The apparatus of claim 8 or 9, wherein the regeneration column is a packed column, in-column random polypropylen pall rings; the regeneration tower is connected to the defluorinating agent feed pipe by a pipeline and a pump.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| FR1453510A (en) * | 1965-08-13 | 1966-06-03 | Electro Chimie Soc D | Purification of dichlorotetrafluoroethane |
| JPS5549119A (en) * | 1978-10-06 | 1980-04-09 | Hitachi Chem Co Ltd | Upward moving bed filtration method |
| ATE99662T1 (en) * | 1989-05-25 | 1994-01-15 | Du Pont | PROCESS FOR THE PRODUCTION OF 1,1-DICHLORO-1FLUORETHANE. |
| JPH07330640A (en) * | 1994-06-10 | 1995-12-19 | Daikin Ind Ltd | Method for removing 1,1-dichloroethylene in 1,1-dichloro-1-fluoroethane |
| EP1109766B1 (en) * | 1998-09-03 | 2004-11-03 | Solvay Fluor und Derivate GmbH | Purification of 1,1,1,3,3-pentafluorobutane |
| CN1680232A (en) * | 1998-12-18 | 2005-10-12 | 索尔维公司 | Method for synthesis of hydrofluoroalkane |
| JP5800805B2 (en) * | 2009-06-26 | 2015-10-28 | ダウ アグロサイエンシィズ エルエルシー | Selective dehydrohalogenation of tertiary halogenated hydrocarbons and removal of tertiary halogenated hydrocarbon impurities |
| CN101985452B (en) * | 2010-11-17 | 2012-07-04 | 中化重庆涪陵化工有限公司 | Regeneration technology of tributyl phosphate |
| CN102942235B (en) * | 2012-11-28 | 2014-01-08 | 中国科学院南京土壤研究所 | Stirring extraction tower-back extraction tower combined device for processing high chemical oxygen demand (COD) waste water and technology of combined device |
| CN103232087B (en) * | 2013-05-17 | 2014-05-21 | 新昌德力石化设备有限公司 | Method for continuously treating sulfonic acid wastewater |
| CN108404932A (en) * | 2018-02-06 | 2018-08-17 | 禾信天成科技（天津）有限公司 | A kind of liquid phase hydrogenating catalyst for unsaturated olefin synthesis saturated alkane |
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