CN1125630A - Purification method of by-product hydrobromic acid - Google Patents
Purification method of by-product hydrobromic acid Download PDFInfo
- Publication number
- CN1125630A CN1125630A CN 95112103 CN95112103A CN1125630A CN 1125630 A CN1125630 A CN 1125630A CN 95112103 CN95112103 CN 95112103 CN 95112103 A CN95112103 A CN 95112103A CN 1125630 A CN1125630 A CN 1125630A
- Authority
- CN
- China
- Prior art keywords
- extractant
- hydrobromic acid
- product
- purification process
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Extraction Or Liquid Replacement (AREA)
- Fireproofing Substances (AREA)
Abstract
The purifying process for high output of hydrobromic acid features use of two-stage cascaded countercurrent extraction to remove impurities from hydrobromic acid and obtain transparent hydrobromic acid. The extractant is tributyl phosphate, trioctyl phosphorus oxide, primary amine N1923, or trioctyl amine and may be reused cyclically, so having low cost.
Description
The invention belongs to the purification technique field of inorganic chemical product.
Along with the raising of science and technology development and living standards of the people, fire-retardant problem more and more causes people's attention, has caused the rapid raising of fire retardant output thus, and only just there is tens of family fire retardant factory the our province Weifang Prefecture.These producers are when producing fire retardant such as decabromodiphenyl oxide etc., and by-product goes out to contain in a large number the waste liquid of high concentration of hydrogen bromic acid (HBr＞46% generally speaking), and ground such as Jiangsu also have this a large amount of class hydrobromic acids to produce every year.In addition, the also a large amount of hydrobromic acid of by-product when producing medicine intermediate such as two bromals.Contain the impurity of a large amount of component complexity in these hydrobromic acids, major impurity is the inorganic impurity of benzene series organic matter and iron, bromine etc. and so on, and its utilization is very limited, and price is extremely low, and per ton only have about 3000 yuan.And these hydrobromic acids are difficult to handle with conventional impurity-removing method, and for example if directly distill, impurity will distillate as azeotropic mixture simultaneously with hydrobromic acid, is a problem demanding prompt solution.Through the document investigation, still there is not bibliographical information to the technology that the present invention is close or similar.
The object of the present invention is to provide a kind of technology of this class by-product hydrobromic acid being carried out purification process.
The present invention adopts two stage countercurrent cascade extraction technologies to remove organic impurities in the hydrobromic acid and the inorganic impurity that exists with the macroanion form, directly obtains water white hydrobromic acid, and extractant is recycling after regenerating.Extractant of the present invention is tributyl phosphate (TBP), trioctyl phosphine oxide (TOPO), primary amine N1923 or trioctylamine (TOA), the regenerative agent of extractant is the sodium hydroxide solution of 30-40% or sodium carbonate liquor and the metabisulfite solution of 15-25% or the sodium chloride solution of 20-25% of 20-30%, the volume ratio of by-product hydrobromic acid and extractant is 5: 1-10: 1, the volume ratio of load extractant and regenerative agent is 1 during regeneration: 1-3: 1, and operating temperature is 10-40 ℃.
Operating procedure of the present invention is as follows:
1. the extractant of getting certain volume is checked lower floor's ph value of aqueous phase＜1 with 46% hydrobromic acid acidifying.
2. get the by-product hydrobromic acid of certain volume, extract with extractant by volume, lower floor's water (acid solution) pale red, after the phase-splitting, water carries out the secondary extraction with new extractant again, and lower floor's acid solution water white transparency is the hydrobromic acid product of purifying.Tell the upper strata extractant with following step cycling extraction.
3. get the by-product hydrobromic acid of certain volume in addition, use earlier secondary extraction in the step circulation with mistake extractant extract, lower floor's water (acid solution) is pale red, after the phase-splitting, water carries out the secondary extraction with the extractant of new regeneration again, tells the upper strata extractant with following step cycling extraction.Lower floor's acid solution water white transparency is the hydrobromic acid product of purifying.
The above-mentioned water white transparency acid solution that obtains if concentration is lower than 46%, is distilled processing by analysis again, and the fraction of collecting 120-124 ℃ gets final product.
The regeneration step of extractant is: earlier with NaOH or sodium carbonate liquor neutralization, the upper strata extractant is reduced to water white transparency, again with metabisulfite solution or sodium chloride solution washing to neutral, with 46% hydrobromic acid acidifying, be regenerating extracting agent before using.
After 10 circulations, extractant loses less than 2%, and extracting power does not have significant change.Cycle-index is not limit.
The present invention has following characteristics: (1) technology is simple, workable; (2) with low cost, extractant can be regenerated.The hydrobromic acid of technology purifying of the present invention is a colourless transparent solution, and the hydrobromic acid that existing distillating method obtains is a dark red solution.Can thoroughly solve the problem of outlet of fire retardant manufacturer by-product hydrobromic acid after this technology is applied, be worth, make full use of the bromine resource to improving bromine, development bromine fire-retardant agent industry has great importance.
Accompanying drawing is a process chart of the present invention.
The invention will be further described below in conjunction with drawings and Examples:
Example one: Jiangsu factory produces the by-product hydrobromic acid of decabromodiphenyl oxide, is dark brown red, contains HBr47%.When directly distilling removal of impurities, all there is dark brown red impurity to distillate at whole still-process.Adopt this invention removal of impurities, step is as follows: get 500 milliliters in this sample, extract with 50 milliliters of tributyl phosphates, tributyl phosphate is used 10 milliliter 46% hydrobromic acid acidifying in advance, lower floor's water (acid solution) is pale red, after the phase-splitting, water carries out secondary extraction with 50 milliliters of tributyl phosphates again, tells the upper strata extractant with following step cycling extraction.Lower floor's acid solution water white transparency, directly as product, every index is as follows: HBr 〉=46%, SO
4 -≤ 0.005%, Cl
-≤ 0.05%.
Other gets 500 milliliters in this sample, extract with 50 milliliters of tributyl phosphates of going up secondary extraction in the step circulation earlier, lower floor's water (acid solution) is pale red, after the phase-splitting, water carries out the secondary extraction with the tributyl phosphate of 50 milliliters of regeneration again, tells the upper strata extractant in order to next cycling extraction.Lower floor's acid solution water white transparency, every index is identical with upper product.
The regeneration step of tributyl phosphate is: elder generation neutralizes with 50 milliliter 35% NaOH, the upper strata extractant is reduced to water white transparency, extremely neutral with 50 milliliter 20% metabisulfite solution washing again, use 10 milliliter 46% hydrobromic acid acidifying at last, be regenerating extracting agent.
After 10 circulations, extractant loss 2%, extracting power does not have significant change.
Example two: Weifang factory produces the by-product hydrobromic acid of two bromals, is dark brown red, contains HBr35%.Adopt extraction process removal of impurities of the present invention, step is with example one, and the volume ratio of different is by-product hydrobromic acid and extractant is 8: 1.Because hydrobromic acid content is low, distills again, collects 120-124 ℃ of fraction, the every index of products obtained therefrom is not less than example one.
Example three: Weifang factory produces the by-product hydrobromic acid of two bromals, is dark brown red, contains HBr35%.Adopt the extraction process removal of impurities, extractant is primary amine N1923, and regenerative agent is sodium carbonate liquor and sodium chloride solution, and other steps are with example two.
Example four: Jiangsu factory produces the by-product hydrobromic acid of decabromodiphenyl oxide, is dark brown red, contains HBr47%.Adopt this invention removal of impurities, extractant is a trioctyl phosphine oxide, and regenerative agent is NaOH and metabisulfite solution.Other steps are with example one.
Claims (5)
1. method that is used for the by-product hydrobromic acid of production processes such as fire retardant, medicine intermediate such as decabromodiphenyl oxide, two bromals is carried out purification process, it is characterized in that, adopt the impurity in the two stage countercurrent cascade extraction technologies removal hydrobromic acid, extractant is tributyl phosphate (TBP), trioctyl phosphine oxide (TOPO), primary amine N1923 or trioctylamine (TOA), the volume ratio of by-product hydrobromic acid and extractant is 5: 1-10: 1, and step is as follows: the acidifying of a. extractant; B. by-product hydrobromic acid extracts with the acidizing extraction agent, and with the extraction of new extractant secondary, lower floor's water white transparency acid solution is the hydrobromic acid product of purifying to water again after the phase-splitting; C. with secondary extractant among the b by-product hydrobromic acid is extracted, water is told the upper strata extractant and is used for step circulation down with the extraction of regenerating extracting agent secondary after the phase-splitting, and lower floor's water white transparency acid solution is a purified hydrogen bromic acid product; D. repeat above-mentioned circulation.
2. newspaper is characterized in that according to the described purification process of claim 1, and used extractant is with 46% hydrobromic acid acidifying, the water pH of lower floor＜1.
3. purification process according to claim 1 is characterized in that, adopting the sodium hydroxide solution of 30-40% or the sodium carbonate liquor of 20-30% and the metabisulfite solution of 15-25% or the sodium chloride solution of 20-25% is regenerative agent.
4. according to claim 1 or 3 described purification process, it is characterized in that the volume ratio of load extractant and regenerative agent is 1 during extractant regeneration: 1-3: 1.
5. purification process according to claim 1 is characterized in that, the extracting operation temperature during purifying is 10-40 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95112103A CN1049157C (en) | 1995-08-28 | 1995-08-28 | Purification method of by-product hydrobromic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95112103A CN1049157C (en) | 1995-08-28 | 1995-08-28 | Purification method of by-product hydrobromic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1125630A true CN1125630A (en) | 1996-07-03 |
| CN1049157C CN1049157C (en) | 2000-02-09 |
Family
ID=5079325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95112103A Expired - Fee Related CN1049157C (en) | 1995-08-28 | 1995-08-28 | Purification method of by-product hydrobromic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1049157C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102676853A (en) * | 2012-05-28 | 2012-09-19 | 五矿（北京）稀土研究院有限公司 | Rare earth separation method with material linkage cyclic utilization function |
| CN102774811A (en) * | 2012-07-13 | 2012-11-14 | 清华大学 | Method for preparing hydrogen chloride gas from hydrochloric acid solution |
| CN106186147A (en) * | 2016-07-26 | 2016-12-07 | 北京惠宇乐邦环保科技有限公司 | A kind of recovery and treatment method of high concentration waste organic acid |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU566816A1 (en) * | 1974-10-16 | 1977-07-30 | Предприятие П/Я В-8046 | Method of joint production of 1,2-dibromopropane and bromine |
| JP2890434B2 (en) * | 1989-01-27 | 1999-05-17 | 東ソー株式会社 | Recovery method for hydrobromic acid and methanol |
-
1995
- 1995-08-28 CN CN95112103A patent/CN1049157C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102676853A (en) * | 2012-05-28 | 2012-09-19 | 五矿（北京）稀土研究院有限公司 | Rare earth separation method with material linkage cyclic utilization function |
| CN102676853B (en) * | 2012-05-28 | 2013-11-20 | 五矿（北京）稀土研究院有限公司 | Rare earth separation method with material linkage cyclic utilization function |
| CN102774811A (en) * | 2012-07-13 | 2012-11-14 | 清华大学 | Method for preparing hydrogen chloride gas from hydrochloric acid solution |
| CN106186147A (en) * | 2016-07-26 | 2016-12-07 | 北京惠宇乐邦环保科技有限公司 | A kind of recovery and treatment method of high concentration waste organic acid |
| CN106186147B (en) * | 2016-07-26 | 2020-05-19 | 北京惠宇乐邦环保科技有限公司 | Recovery treatment method of high-concentration organic acid wastewater |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1049157C (en) | 2000-02-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101012501A (en) | Method for fully separating high-purity rare earth oxide from yttrium-rich rare earth ore | |
| CN107720820A (en) | The technique that a kind of solvent extraction and separation zirconium and hafnium prepare core level hafnium oxide and zirconium oxide | |
| CN104961100A (en) | Method for extracting iodine from iodine-containing solution | |
| CN111804704B (en) | Method for treating tetrachloro sodium aluminate solid slag | |
| CN110002649A (en) | A kind of method that graphene waste acid resource utilizes | |
| CN1049157C (en) | Purification method of by-product hydrobromic acid | |
| ATE226181T1 (en) | METHOD FOR PURIFYING WET PROCESS PHOSPHORIC ACID | |
| CN1259310C (en) | Process for extracting and separating caprolactam from amide oil | |
| US20040247504A1 (en) | Process for recovery of high purity uranium from fertilizer grade weak phosphoric acid | |
| US4781905A (en) | Process for producing phosphoric acid and/or phosphates from wet-process phosphoric acid and an extractant therein | |
| JPH01230426A (en) | Separation of thorium and rare earth element from concentrate of borides thereof | |
| US2757081A (en) | Method for separating and purifying zirconium and hafnium | |
| SU888812A3 (en) | Method of purifying extraction phosphoric acid | |
| CN1009546B (en) | Treatment of chlorhydric acid pickling waste containing iron | |
| CA1235906A (en) | Process for separating antimony from columbium solutions | |
| CN86100720A (en) | With extracting deironing in the aluminium sulfate solution with tertiary amine | |
| EP0176613A1 (en) | A process for producing phosphoric acid and/or phosphates from wet-process phosphoric acid and an extractant used therein | |
| CN1024926C (en) | Method for recovering germanium from solution | |
| US3578391A (en) | Yttrium purification | |
| US3284508A (en) | Recovery of p-tolualdehyde | |
| CA1184948A (en) | Producing solvent-grade methyl-naphthalene | |
| CA2318823A1 (en) | Solvent extraction of ferric chloride | |
| CN112250547B (en) | Phenol recovery method for potassium phenol-containing wastewater from production of diafenthiuron | |
| CN108425012A (en) | The P204 extraction separating methods of ferro-uranium in a kind of sulfuric acid system | |
| CN1019473B (en) | Technology for calcium bydrogen phosphate forage |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |