CN1834003A - Method of removing and reclaiming free chlorine in hydrochloric acid of chlorized by-product - Google Patents
Method of removing and reclaiming free chlorine in hydrochloric acid of chlorized by-product Download PDFInfo
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- CN1834003A CN1834003A CN 200510130999 CN200510130999A CN1834003A CN 1834003 A CN1834003 A CN 1834003A CN 200510130999 CN200510130999 CN 200510130999 CN 200510130999 A CN200510130999 A CN 200510130999A CN 1834003 A CN1834003 A CN 1834003A
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- hydrochloric acid
- ferric trichloride
- chlorine
- free chlorine
- compressed air
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Abstract
This invention relates to a method to remove and recycle dissociative chlorine from hydrogen chloride as chlorification byproduct. Most dissociative chlorine is blown out of hydrogen chloride by compressed air and reacts with iron chippings to produce ferric trichloride, while standard air is discharged after purification. Then, proper organic acid is added for thorough reaction with remnant chloride according to its amount in hydrogen chloride so as to produce eligible industrial hydrogen chloride. In this method, continuous manufacture can be realized, and it is applicable in all kinds of chlorine chlorification chemical engineering process such as the production of chlorified paraffin, chorobenzene, polyvinyl chloride, etc.
Description
The invention relates to a method for removing free chlorine from chlorination by-product hydrochloric acid and recycling the same.
At present, in the chlorination process of chlorine in China, such as the production process of chlorinated paraffin, chlorobenzene and the like, a large amount of by-product hydrogen chloride is generated and is absorbed by water to prepare hydrochloric acid, but because a large amount of unreacted chlorine is mixed in hydrogen chloride gas, the chlorine is dissolved in the hydrogen chloride gas to form free chlorine in the process of preparing the hydrochloric acid by absorbing with water. Because the free chlorine can be emitted in the using process of users to cause serious pollution to the production environment, and because the free chlorine is very active and can participate in a plurality of chemical reactions, the application of the byproduct hydrochloric acid is greatly limited, and a plurality of manufacturers can directly discharge the byproduct hydrochloric acid because the byproduct hydrochloric acid cannot be applied. On one hand, the production cost is increased because the byproduct hydrochloric acid cannot be recovered, and on the other hand, the direct discharge of the byproduct hydrochloric acid causes serious pollution to the environment. Although the blowing method has been reported and applied in the past, the blowing method has not been widely popularized and applied because of the secondary pollution of chlorine gas and the difficulty in completely blowing free chlorine in the hydrochloric acid as a byproduct.
The invention aims to provide a method for preparing qualified hydrochloric acid by removing free chlorine from hydrochloric acid as a chlorination by-product and recycling the free chlorine to prepare solid or liquid ferric trichloride, so as to solve the defects of the prior art.
The invention relates to a method for removing and recycling free chlorine in chlorination by-product hydrochloric acid, which comprises the following steps:
(1) removing organic matters from the byproduct hydrogen chloride gas by activated carbon adsorption, and circularly absorbing with water to prepare concentrated hydrochloric acid;
(2) introducing compressed air into the concentrated hydrochloric acid for bubbling, and blowing out part of free chlorine in the hydrochloric acid;
(3) the concentrated hydrochloric acid-containing compressed air is introduced into the filler tower filled with the iron filings, so that the chlorine and the iron filings react to generate ferric trichloride, the purpose of recycling the chlorine is achieved, and the specific reaction formula is as follows:
(4) according to the content of the residual free chlorine in the hydrochloric acid treated by the blowing-cleaning method, a proper amount of organic acid is added to convert a small amount of free chlorine into the hydrochloric acid so as to achieve the purposes of thoroughly removing the free chlorine and preparing the qualified hydrochloric acid.
The invention has the following advantages:
1. blowing out most of free chlorine in the hydrochloric acid by using an air blowing method, and adding organic acid according to the amount of residual chlorine in the hydrochloric acid to thoroughly remove the free chlorine in the hydrochloric acid, so that qualified industrial hydrochloric acid can be prepared;
2. the chlorine gas blown out by the air blowing-out method reacts with the scrap iron, so that on one hand, the chlorine gas is recycled, air pollution is avoided, and obvious social benefits are achieved; on the other hand, industrial solid or liquid ferric trichloride can be obtained, so that the product variety is increased, and the economic benefit is improved;
3. the process method is simple and feasible, has less investment and quick response, has the concepts of changing waste into valuable, recycling economy, sustainable development and the like, and should be supported and supported by relevant national departments.
The following are further commented by examples:
example (b):
1. removing organic matters from a byproduct hydrogen chloride gas generated in the chlorination process through activated carbon adsorption, introducing the hydrogen chloride gas into a graphite absorber, circularly absorbing the hydrogen chloride gas with water or dilute hydrochloric acid in the graphite absorber to prepare concentrated hydrochloric acid, simultaneously carrying unreacted chlorine into the concentrated hydrochloric acid, and pressing the unreacted chlorine and the hydrogen chloride gas into the concentrated hydrochloric acid by using compressed air;
2. pumping concentrated hydrochloric acid reaching a preset concentration (28-31%) into a closed dechlorination kettle by using an acid-resistant pump, and then introducing compressed air for bubbling to blow out chlorine in the concentrated hydrochloric acid;
3. introducing compressed air containing chlorine into the lower part of a packed tower filled with scrap iron by using a guide pipe, discharging the purified compressed air into the atmosphere from the top of the tower after the purified compressed air passes through the packed tower, reacting the chlorine with the scrap iron to generate ferric trichloride, pumping water or dilute hydrochloric acid into the upper part of the packed tower, flowing through an iron scrap packing layer from top to bottom, dissolving the ferric trichloride, discharging from the bottom of the tower to obtain a dilute ferric trichloride solution, circularly pumping the dilute ferric trichloride solution into the top of the packed tower, repeatedly absorbing the dilute ferric trichloride solution to obtain a saturated ferric trichloride solution, and crystallizing to obtain a solid ferric trichloride product;
4. iron filings are supplemented regularly according to actual conditions.
Claims (1)
1. A method for removing and recycling free chlorine in chlorination by-product hydrochloric acid is characterized by comprising the following steps:
(1) introducing compressed air into concentrated hydrochloric acid for bubbling, and blowing out part of free chlorine in the hydrochloric acid;
(2) introducing the compressed air containing chlorine into the bottom of a filled tower filled with scrap iron, allowing the chlorine and the scrap iron to react to generate ferric trichloride through an iron scrap filling layer, and discharging the purified compressed air into the atmosphere from the top of the tower;
(3) and (2) pumping water or dilute hydrochloric acid into the top of the filled tower filled with the iron filings, enabling the water or the dilute hydrochloric acid to flow through the iron filings filling layer from top to bottom, dissolving ferric trichloride, and then discharging the ferric trichloride from the bottom of the tower to obtain a dilute ferric trichloride solution.
(4) Injecting the dilute ferric trichloride solution into the upper part of the packed tower filled with the scrap iron to circularly absorb ferric trichloride to obtain a saturated ferric trichloride solution;
(5) crystallizing the saturated ferric trichloride solution to obtain a solid ferric trichloride product;
(6) adding a proper amount of organic acid according to the content of residual free chlorine in the hydrochloric acid treated by the blowing method in the step (1) to enable the residual free chlorine to fully react with the free chlorine and convert the free chlorine into the hydrochloric acid so as to prepare qualified industrial hydrochloric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101309992A CN100361891C (en) | 2005-12-19 | 2005-12-19 | Method of removing and reclaiming free chlorine in hydrochloric acid of chlorized by-product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101309992A CN100361891C (en) | 2005-12-19 | 2005-12-19 | Method of removing and reclaiming free chlorine in hydrochloric acid of chlorized by-product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1834003A true CN1834003A (en) | 2006-09-20 |
| CN100361891C CN100361891C (en) | 2008-01-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101309992A Expired - Fee Related CN100361891C (en) | 2005-12-19 | 2005-12-19 | Method of removing and reclaiming free chlorine in hydrochloric acid of chlorized by-product |
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| CN (1) | CN100361891C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100591648C (en) * | 2006-12-27 | 2010-02-24 | 贵州蓝天化工有限公司 | Technique for coproducing polyvinyl chloride from by-product hydrogen chloride of trichloroethylene |
| CN101210900B (en) * | 2006-12-30 | 2010-11-17 | 仇晓丰 | Free chloride on-line detection process during hydrogenchloride synthesis and the device therefor |
| CN106219612A (en) * | 2016-06-30 | 2016-12-14 | 栗晓光 | A kind of processing method of waste chlorine |
| CN107043090A (en) * | 2017-01-06 | 2017-08-15 | 江苏吉华化工有限公司 | It is a kind of to be used to improve the devices and methods therefor for reclaiming removal rate of sulfur dioxide in hydrochloric acid |
| CN108079771A (en) * | 2017-12-29 | 2018-05-29 | 攀枝花钢企欣宇化工有限公司 | The absorption processing method of chlorinated exhaust |
| CN109467134A (en) * | 2019-01-22 | 2019-03-15 | 安徽久易农业股份有限公司 | A kind of recovery method of useless ferrous chloride aqueous solution |
| CN109704281A (en) * | 2019-01-17 | 2019-05-03 | 太原理工大学 | A method of go to demineralizing acid middle reaches from chlorine using organic reducing agent |
| CN111439726A (en) * | 2019-01-17 | 2020-07-24 | 太原理工大学 | Purification method of byproduct hydrochloric acid in technological process of producing chloroacetic acid |
| CN113277473A (en) * | 2021-05-13 | 2021-08-20 | 万华化学（宁波）有限公司 | Process for decomposing residual chlorine in hydrochloric acid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19536976A1 (en) * | 1995-10-04 | 1997-04-10 | Basf Ag | Process for the selective separation and recovery of chlorine from gas mixtures |
-
2005
- 2005-12-19 CN CNB2005101309992A patent/CN100361891C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100591648C (en) * | 2006-12-27 | 2010-02-24 | 贵州蓝天化工有限公司 | Technique for coproducing polyvinyl chloride from by-product hydrogen chloride of trichloroethylene |
| CN101210900B (en) * | 2006-12-30 | 2010-11-17 | 仇晓丰 | Free chloride on-line detection process during hydrogenchloride synthesis and the device therefor |
| CN106219612A (en) * | 2016-06-30 | 2016-12-14 | 栗晓光 | A kind of processing method of waste chlorine |
| CN106219612B (en) * | 2016-06-30 | 2017-12-22 | 栗晓光 | A kind of processing method of waste chlorine |
| CN107043090A (en) * | 2017-01-06 | 2017-08-15 | 江苏吉华化工有限公司 | It is a kind of to be used to improve the devices and methods therefor for reclaiming removal rate of sulfur dioxide in hydrochloric acid |
| CN107043090B (en) * | 2017-01-06 | 2019-08-06 | 江苏吉华化工有限公司 | It is a kind of for improve recycling hydrochloric acid in removal rate of sulfur dioxide devices and methods therefor |
| CN108079771A (en) * | 2017-12-29 | 2018-05-29 | 攀枝花钢企欣宇化工有限公司 | The absorption processing method of chlorinated exhaust |
| CN109704281A (en) * | 2019-01-17 | 2019-05-03 | 太原理工大学 | A method of go to demineralizing acid middle reaches from chlorine using organic reducing agent |
| CN111439726A (en) * | 2019-01-17 | 2020-07-24 | 太原理工大学 | Purification method of byproduct hydrochloric acid in technological process of producing chloroacetic acid |
| CN109467134A (en) * | 2019-01-22 | 2019-03-15 | 安徽久易农业股份有限公司 | A kind of recovery method of useless ferrous chloride aqueous solution |
| CN113277473A (en) * | 2021-05-13 | 2021-08-20 | 万华化学（宁波）有限公司 | Process for decomposing residual chlorine in hydrochloric acid |
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| Publication number | Publication date |
|---|---|
| CN100361891C (en) | 2008-01-16 |
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Granted publication date: 20080116 Termination date: 20101219 |