CN102923662B - Method for separating hydrogen fluoride and hydrogen chloride in chloropyridine derivative fluorination process - Google Patents
Method for separating hydrogen fluoride and hydrogen chloride in chloropyridine derivative fluorination process Download PDFInfo
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- CN102923662B CN102923662B CN201210502033.7A CN201210502033A CN102923662B CN 102923662 B CN102923662 B CN 102923662B CN 201210502033 A CN201210502033 A CN 201210502033A CN 102923662 B CN102923662 B CN 102923662B
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- hydrogen fluoride
- hydrogenchloride
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- hydrochloric acid
- hydrogen chloride
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Abstract
The invention provides a separation technology of the mixed tail gas of hydrogen fluoride and hydrogen chloride in the chloropyridine derivative fluorination process. The tail gas after fluorination contains the mixture of hydrogen chloride and hydrogen fluoride; the molar ratio of the hydrogen chloride to hydrogen fluoride is (98:2)-(60:40); and the reparation method comprises the following steps: performing pressure cooling of the mixed gas so as to change the hydrogen fluoride into liquid and realize separation, and performing one-level or multi-level water absorption and recovery of the gas hydrogen chloride and trace hydrogen fluoride to obtain a qualified technical hydrochloric acid product. The separation method provided by the invention can recover raw materials, reduce the consumption of the raw materials and realize recovery of the byproduct.
Description
Technical field
The present invention relates to the separating technology of hydrogen fluoride and hydrogenchloride in chloro-pyridine derivative fluorination process.
Background technology
Operation is fluoridized in DTMP synthesis, requirement hydrogen fluoride is excessive, and in reaction process, generate hydrogen chloride gas, what such reaction system ejected is hydrogenchloride and hydrofluoric mixed gas, if this mixed gas is without separation, be to recycle, thus cause the increase of raw material consumption and the increase of three wastes discharge amount.
And traditional separation method has chemical precipitation, flocculation sediment, absorption etc. three kinds, chemical precipitation method generally adopts calcium salt precipitation method, namely to feeding lime in waste water, makes fluorion and calcium ion generate CaF2 and precipitates and remove.This technique has the advantages such as method is simple, process is convenient, expense is low, but deposits water outlet after treatment and be difficult to up to standard, body refuse sedimentation slowly and the shortcomings such as dehydration difficulty; The flocculation agent that flocculent precipitation is conventional is aluminium salt.Aluminium salt is added to after in water, utilizes Al
3+with F
-complexing and aluminium salt hydrolysis intermediate product and the last Al (OH) generated
3(am) alumen ustum removes the fluorion in water to the ligand exchange of fluorion, physical adsorption, the volume effect of sweeping.Compared with calcium salt precipitation method, aluminium salt flocculent precipitation has that added amount of chemical is few, treatment capacity is large, can reach the advantage of discharging standards after primary treatment, aluminium salt flocculent precipitation also also exists obvious shortcoming, namely use range is little, if fluorine content is large, coagulating agent usage quantity is many, and processing costs is comparatively large, produces sludge quantity many; Fluoride ion removing effect is by SO in the operation factors such as agitation condition, settling time and water
4 2-, Cl
-impact Deng negatively charged ion is comparatively large, and effluent quality is stable not; Suction type is used for except the conventional sorbent material of fluorine mainly contains activated alumina, clinoptilolite, activated magnesia, there was reported the higher hydroxyapatite of adsorption capacity of fluoride ion, zirconium white etc. in recent years, absorption method is effective for the fluoride ion removing of trace, but there is the problems such as the process water yield is little, loading capacity is low and be not suitable for scale operation, present invention focuses on the difference according to hydrogenchloride and hydrogen fluoride boiling point difference and solubleness, and then inhale the device strengthening differences such as absorption by pressurization, reach both and be separated.
Summary of the invention
The object of the invention is to provide the separating technology of hydrogen fluoride in a kind of chloro-pyridine derivative fluorination process and hydrogenchloride, to reclaim raw material, reduces raw material consumption, and realizes the recovery of by product.
The present invention is achieved by the following technical solutions:
The separating technology of hydrogen fluoride and hydrogenchloride mixed tail gas in one class chloro-pyridine derivative fluorination process is provided, described fluoridize after the tail gas that obtains contain hydrogenchloride and hydrofluoric mixture, wherein hydrogenchloride and hydrofluoric molar ratio are 98/2 ~ 60/40, it is characterized in that: mixed gas is first by pressurization cooling, hydrogen fluoride is made to become liquid, realizing being separated, is still that hydrogenchloride and the micro-hydrogen fluoride of gas obtains qualified technical hydrochloric acid goods through one or more levels water absorption recovery again.
The preferred 2-chloro-5-trichloromethylpyridine of described chloro-pyridine derivative or 2,3-bis-chloro-5-trichloromethylpyridine (DTMP).
Described pressurization cooling, pressure is preferably in 0.1-5Mpa scope.
Described pressurization cooling can complete through one or more levels pressurization refrigerating unit.
Described hydrogenchloride and micro-hydrogen fluoride, when one-level water absorbs recovery, preferably control to pump dilute hydrochloric acid under F ion concentration is less than 100PPM.
Described hydrogenchloride and micro-hydrogen fluoride through multi-level water absorb reclaim time, can according to following two kinds of mode process:
First order absorption controls F ion concentration and is less than 100PPM, and the F ion concentration obtaining different concns at different levels is less than the hydrochloric acid goods of 100PPM thereafter;
Or
First order absorption HCl is to saturated, and the F ion concentration that adjustment at different levels subsequently obtains different concns is less than the hydrochloric acid goods of 100PPM; Further, when one-level accumulation HF concentration is greater than 5% aftertreatment first order absorption liquid, the mother liquor reuse that after process, F ion concentration reduces is to system.Processing mode process routinely, such as, when HF concentration reaches 20%, adds calcium chloride under room temperature, and reaction generates precipitation Calcium Fluoride (Fluorspan), and filter out Calcium Fluoride (Fluorspan), at this moment in mother liquor, hydrogen fluoride concentration drops to about 3%, continues retrieval system again apply mechanically with this mother liquor.
Compared with prior art, the separation method of invention can reclaim raw material, reduces raw material consumption, and realizes the recovery of by product.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of separating technology of the present invention.
Embodiment:
In following embodiment, pressurization heat-eliminating medium is the water of-20 DEG C, and it is the recirculated water of ambient temperature that water absorbs falling-film tower heat-eliminating medium.
Embodiment 1
System pressure 3.5MPa-4.0MPa, adopt one-level pressurization cooling, tertiary effluent absorbs, and institute goes out hydrochloric acid one-level content 32%, hydrofluoric acid 80ppm, hydrochloric acid secondary content 31.5%, hydrofluoric acid 30ppm, and hydrochloric acid three grades of content 31.5% hydrofluoric acid are 2ppm.
Embodiment 2
System pressure 3.5MPa-4.0MPa, adopt two-stage pressurizing cooling, tertiary effluent absorbs, and institute goes out hydrochloric acid one-level content 32.6%, hydrofluoric acid 10ppm, hydrochloric acid secondary content 31.5%, hydrofluoric acid 5ppm, and hydrochloric acid three grades of content 31.1% hydrofluoric acid are 2ppm.
Embodiment 3
System pressure 3.5MPa-4.0MPa, adopt three times' lifting cooling, tertiary effluent absorbs, and institute goes out hydrochloric acid one-level content 33.6%, hydrofluoric acid 5ppm, hydrochloric acid secondary content 31.5%, hydrofluoric acid 2ppm, hydrochloric acid three grades of content 31.1%, and hydrofluoric acid is zero 2ppm.
Embodiment 4
System pressure 3.5MPa-4.0MPa, adopt two-stage pressurizing cooling, secondary water absorbs, and institute goes out hydrochloric acid one-level content 33.6%, hydrofluoric acid 5ppm, hydrochloric acid secondary content 31.5%, hydrofluoric acid 2ppm.
Claims (1)
1. the separating technology of hydrogen fluoride and hydrogenchloride mixed tail gas in chloro-pyridine derivative fluorination process, described chloro-pyridine derivative is 2-chloro-5-trichloromethylpyridine or 2,3-bis-chloro-5-trichloromethylpyridine; The tail gas obtained after fluoridizing contains hydrogenchloride and hydrofluoric mixture, wherein hydrogenchloride and hydrofluoric molar ratio are 98/2 ~ 60/40, it is characterized in that: by mixed gas first by pressurization cooling, hydrogen fluoride is made to become liquid, realizing being separated, is still that hydrogenchloride and the micro-hydrogen fluoride of gas obtains qualified technical hydrochloric acid goods through multi-level water absorption recovery again; Described pressurization cooling, pressure is in 0.1-5MPa scope; Described pressurization is cooled through one or more levels pressurization refrigerating unit and completes; During described multi-level water absorbs and reclaims, first order absorption HCl is to saturated, and the F ion concentration that adjustment at different levels subsequently obtains different concns is less than the hydrochloric acid goods of 100ppm; Further, when one-level accumulation HF concentration is greater than 5% aftertreatment first order absorption liquid, the mother liquor reuse that after process, F ion concentration reduces is to system.
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| CN201210502033.7A CN102923662B (en) | 2012-11-30 | 2012-11-30 | Method for separating hydrogen fluoride and hydrogen chloride in chloropyridine derivative fluorination process |
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| CN201210502033.7A CN102923662B (en) | 2012-11-30 | 2012-11-30 | Method for separating hydrogen fluoride and hydrogen chloride in chloropyridine derivative fluorination process |
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| CN102923662B true CN102923662B (en) | 2015-04-08 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103539069B (en) * | 2013-11-08 | 2015-12-02 | 中国恩菲工程技术有限公司 | The method and system of process polycrystalline silicon reduction exhaust |
| CN111777514B (en) * | 2020-07-17 | 2023-04-07 | 多氟多新材料股份有限公司 | Comprehensive utilization method of mixed gas containing hydrogen fluoride and hydrogen chloride |
| CN112357950B (en) * | 2020-10-30 | 2023-02-24 | 昆明冶金研究院有限公司 | Method for removing and recovering fluorine and chlorine from zinc sulfate solution |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4299606A (en) * | 1976-12-30 | 1981-11-10 | Hooker Chemicals & Plastics Corp. | Recovery of HF and HCl from gaseous mixtures thereof |
| CN101342441A (en) * | 2008-08-20 | 2009-01-14 | 江苏扬农化工股份有限公司 | Method for treating tail gas of acyl chlorination |
| CN100546903C (en) * | 2007-08-06 | 2009-10-07 | 江阴市润玛电子材料有限公司 | Purifying method of ultrahigh pure hydrofluoric acid |
| CN101791487A (en) * | 2010-03-30 | 2010-08-04 | 中国天辰工程有限公司 | Method for recycling hydrogen chloride in tail gas of polysilicon production |
-
2012
- 2012-11-30 CN CN201210502033.7A patent/CN102923662B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4299606A (en) * | 1976-12-30 | 1981-11-10 | Hooker Chemicals & Plastics Corp. | Recovery of HF and HCl from gaseous mixtures thereof |
| CN100546903C (en) * | 2007-08-06 | 2009-10-07 | 江阴市润玛电子材料有限公司 | Purifying method of ultrahigh pure hydrofluoric acid |
| CN101342441A (en) * | 2008-08-20 | 2009-01-14 | 江苏扬农化工股份有限公司 | Method for treating tail gas of acyl chlorination |
| CN101791487A (en) * | 2010-03-30 | 2010-08-04 | 中国天辰工程有限公司 | Method for recycling hydrogen chloride in tail gas of polysilicon production |
Non-Patent Citations (1)
| Title |
|---|
| 二氟甲烷制备中副产物氯化氢的干法分离浅析;樊英杰 等;《甘肃科技》;20100531;第26卷(第10期);21页第2栏第7行至最后一行，图3,20页第1栏倒数第2行至最后一行 * |
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Owner name: JIANGSU YOUJIA CHEMISTRY CO., LTD. Free format text: FORMER OWNER: YANGNONG CHEMICAL CO., LTD., JIANGSU Effective date: 20140307 Owner name: YANGNONG CHEMICAL CO., LTD., JIANGSU Effective date: 20140307 |
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Effective date of registration: 20140307 Address after: 226407, Jiangsu, Nantong province Rudong County mouth chemical gathering area, foreign mouth road three Applicant after: Jiangsu Youjia Chemistry Co., Ltd. Applicant after: Yangnong Chemical Co., Ltd., Jiangsu Address before: 225009 Wenfeng Road, Jiangsu, China, No. 39, No. Applicant before: Yangnong Chemical Co., Ltd., Jiangsu |
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