CN102234104B - Processing method of hydrogen bromide gas generated in bromination reaction - Google Patents
Processing method of hydrogen bromide gas generated in bromination reaction Download PDFInfo
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- CN102234104B CN102234104B CN201010159631.XA CN201010159631A CN102234104B CN 102234104 B CN102234104 B CN 102234104B CN 201010159631 A CN201010159631 A CN 201010159631A CN 102234104 B CN102234104 B CN 102234104B
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- hydrogen gas
- bromination reaction
- hydrogen bromide
- acetic acid
- acid solution
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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
- B01D53/14—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
- B01D53/1406—Multiple stage absorption
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/202—Single element halogens
- B01D2257/2022—Bromine
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A processing method of hydrogen bromide gas generated in a bromination reaction. A lot of hydrogen bromide gas containing free bromine is generated during a bromination reaction; pure hydrogen bromide gas is generated by multistage absorption of the gas; polybrominated diphenyl ether is generated by multitime absorption of the diphenyl ether; decabromodiphenyl oxide is generated by a further bromination reaction of the polybrominated diphenyl ether; and the pure hydrogen bromide gas is used to prepare a hydrogen bromide acetate solution. The invention can treat free bromine in brominated gas generated during a bromination reaction, can use polybrominated diphenyl ether to produce decabromodiphenyl oxide, and use pure hydrogen bromide gas to prepare a hydrogen bromide acetate solution; the processing method has high comprehensive utilization of recovered resources, and has good social benefits and economic benefits.
Description
Technical field
The present invention relates to a kind for the treatment of process with free bromine gas, in especially a kind of bromination reaction, produce the treatment process of bromize hydrogen gas.
Background technology
On common market, in the time preparing bromide, it can produce a large amount of bromize hydrogen gas containing free bromine in preparation process, and this class waste gas has compared with niff, is directly discharged in atmosphere if do not controlled, and can cause larger pollution to environment.
In the prior art, disclose a kind of method of processing such waste gas, hydrogen bromide waste gas is passed into and in water, generates Hydrogen bromide, in water, generated Hydrogen bromide and have a large amount of free bromines but pass into, if utilize red phosphorus in a large number to remove free bromine, thereby cost is higher.
In addition in order to overcome the defect of above-mentioned technology, prior art discloses the treatment process of another kind of this type of waste gas, its principle of absorption is to utilize the absorptivity of liquid caustic soda itself to absorb processing to free bromine, and generate Sodium Bromide, need a large amount of steam but lower concentration Sodium Bromide will concentrate, processing cost is high, simultaneously because the market value of the Sodium Bromide finished product generating is lower, therefore this kind of its resource utilization of technology is not high, lacks the market competitiveness.
Therefore, what processes the bromize hydrogen gas with free bromine fully, reduces the pollution to environment, and the utilization ratio that simultaneously improves its resource becomes the problem that market is paid close attention to.
Summary of the invention
The object of this invention is to provide the treatment process that produces bromize hydrogen gas in a kind of bromination reaction, by the recyclable utilize resources synthetically of the method, resource utilization is high, without exhaust emission mark, has good economic benefit and social benefit.
The technical solution adopted in the present invention is: the treatment process that produces bromize hydrogen gas in a kind of bromination reaction, in bromination reaction process, can produce a large amount of free bromize hydrogen gas that contains, gas is become to pure bromize hydrogen gas through phenyl ether solution multistage absorption, phenyl ether is through repeatedly absorbing generation polybromodiphenyl ether, this polybromodiphenyl ether generates decabromodiphynly oxide through further bromination reaction, and then utilizes pure bromize hydrogen gas to prepare hydrogen bromide acetic acid solution.
According to another preferred embodiment, the treatment process that produces bromize hydrogen gas in a kind of bromination reaction further comprises that the holding temperature of the phenyl ether solution while passing into gas is 16～80 ℃.
According to another preferred embodiment, the treatment process that produces bromize hydrogen gas in a kind of bromination reaction further comprises that the mol ratio of bromine in the amount of phenyl ether and gas is 100: 1～10000: 1.
According to another preferred embodiment, the treatment process that produces bromize hydrogen gas in a kind of bromination reaction further comprises that described plural serial stage is absorbed as 1～5 grade.
According to another preferred embodiment, the treatment process that produces bromize hydrogen gas in a kind of bromination reaction further comprises that it is that polybromodiphenyl ether is added drop-wise in bromine that this described polybromodiphenyl ether generates decabromodiphynly oxide through further bromination reaction, dropwise rear insulation reaction 1-4h, temperature is raised to 58 ℃ of steamings except unnecessary bromine, obtains decabromodiphynly oxide.
According to another preferred embodiment, the treatment process that produces bromize hydrogen gas in a kind of bromination reaction further comprises that the preparation of described hydrogen bromide acetic acid solution is that pure bromize hydrogen gas is passed in glacial acetic acid solution, glacial acetic acid solution is cooling, circulation absorbs, make content and be 30%～40% hydrogen bromide acetic acid solution, there is micro-unabsorbed bromize hydrogen gas to absorb completely through second acetum, emptying up to standard.
According to another preferred embodiment, the treatment process that produces bromize hydrogen gas in a kind of bromination reaction further comprises that the described cooling temperature of glacial acetic acid solution is 15-20 ℃.
The decabromodiphynly oxide generating in the present invention, shown in the following row reaction in its reaction basis:
The invention has the beneficial effects as follows: in bromination reaction of the present invention, produce containing the bromize hydrogen gas of free bromine and adopt phenyl ether 1-5 level plural serial stage to absorb, remove free bromine, in hydrogen bromide product after purification, water-content is less than 0.3%, and free bromine content is not more than 0.03%; The present invention utilizes pure bromize hydrogen gas to prepare hydrogen bromide acetic acid solution, product yield is more than 96%, its market value is high more than the price of Sodium Bromide, utilize phenyl ether to absorb free bromine generation polybromodiphenyl ether simultaneously and enter the decabromodiphynly oxide that a reaction generates, be a kind of high-quality and efficient fire retardant, market outlook are large, the recyclable utilize resources synthetically of this treatment process, comprehensive utilization of resources rate is high, has good Social benefit and economic benefit.
Accompanying drawing explanation
Fig. 1 is the process flow sheet that produces the treatment process of bromize hydrogen gas in a kind of bromination reaction of the present invention.
Embodiment
The present invention is further detailed explanation with preferred embodiment by reference to the accompanying drawings now.These accompanying drawings are the schematic diagram of simplification, and basic structure of the present invention is only described in a schematic way, and therefore it only shows the formation relevant with the present invention.
As shown in Figure 1, the present invention utilizes in bromination reaction process to produce a large amount of bromize hydrogen gas that contains free bromine, gas is become to pure bromize hydrogen gas through phenyl ether solution multistage absorption, phenyl ether is through repeatedly absorbing generation polybromodiphenyl ether, this polybromodiphenyl ether generates decabromodiphynly oxide through further bromination reaction, and then utilizes pure bromize hydrogen gas to prepare hydrogen bromide acetic acid solution.
In above-mentioned steps, the holding temperature that passes into the phenyl ether solution of Hydrogen bromide gas is 16～80 ℃, in the amount of phenyl ether and gas, the mol ratio of bromine is 100: 1～10000: 1, the plural serial stage of phenyl ether absorbs and adopts 1～5 grade, it is that polybromodiphenyl ether is added drop-wise in bromine that this described polybromodiphenyl ether generates decabromodiphynly oxide through further bromination reaction, dropwise rear insulation reaction 1-4h, temperature is raised to 58 ℃ of steamings except unnecessary bromine, obtain decabromodiphynly oxide, the preparation of described hydrogen bromide acetic acid solution is that pure bromize hydrogen gas is passed in glacial acetic acid solution, glacial acetic acid solution is cooling, circulation absorbs, make content and be 30%～40% hydrogen bromide acetic acid solution, there is micro-unabsorbed bromize hydrogen gas to absorb completely through second acetum, emptying up to standard, the cooling temperature of described glacial acetic acid solution is 15-20 ℃.
The embodiment of the present invention is as follows:
Embodiment 1
In the reactor of 500L, drop into bromine kilogram, 20-35 ℃ of insulated and stirred, flow with 30kg/h left and right drips 100 kilograms of polybromodiphenyl ether, the bromize hydrogen gas that contains free bromine is along with device for cleaning pipeline makes free bromine react to obtain polybromodiphenyl ether with phenyl ether to 100kg phenyl ether one-level absorption unit is housed, holding temperature is 16 ℃, pure bromize hydrogen gas is along with device for cleaning pipeline is in 200kg glacial acetic acid solution, according to client's content requirement difference, throwing amount is also different, in the time absorbing hydrogen bromide, there is exothermic process, must control glacial acetic acid solution temperature between 10-20 degree, having a small amount of unabsorbed bromize hydrogen gas to pass into second glacial acetic acid solution absorbs again, after dripping off 30 kilograms of polybromodiphenyl ether, be incubated 2 hours, temperature is raised to 58 ℃ and starts to steam bromine, steam bromine and reclaim bromine through condenser, apply mechanically next time, consumption bromine is 293 kilograms, obtain hydrogen bromide content and be 274 kilograms of 30% hydrogen bromide acetic acid solutions, productive rate 96%, obtain decabromodiphynly oxide crude product, through pulverizing, dry, packing, go out 164 kilograms of finished products.
Embodiment 2
In the reactor of 1000L, add 800 kilograms of bromines, 20-30 ℃ of insulated and stirred, flow with 30kg/h left and right drips 60 kilograms of polybromodiphenyl ether, the bromize hydrogen gas that contains free bromine is along with device for cleaning pipeline makes free bromine react to obtain polybromodiphenyl ether with phenyl ether to the 100kg phenyl ether absorption unit that is equipped with of three series connection, holding temperature is 60 ℃, pure bromize hydrogen gas is along with device for cleaning pipeline is in 400kg glacial acetic acid solution, according to client's content requirement difference, throwing amount is also different, in the time absorbing hydrogen bromide, there is exothermic process, must control glacial acetic acid solution temperature between 10-20 degree, having a small amount of unabsorbed bromize hydrogen gas to pass into second glacial acetic acid solution absorbs again, after dripping off 60kg polybromodiphenyl ether, be incubated 2 hours, temperature is raised to 58 ℃ and starts to steam bromine, steam bromine and reclaim bromine through condenser, apply mechanically next time, consumption bromine is 594 kilograms, obtain hydrogen bromide content and be 596 kilograms of 35% hydrogen bromide acetic acid solutions, productive rate 97%, obtain decabromodiphynly oxide crude product, through pulverizing, dry, packing, go out 330 kilograms of finished products.
Embodiment 3
In the reactor of 1000L, add 1200 kilograms of bromines, 20-30 ℃ of insulated and stirred, flow with 30kg/h left and right drips 100 kilograms of polybromodiphenyl ether, the bromize hydrogen gas that contains free bromine is along with device for cleaning pipeline makes free bromine react to obtain polybromodiphenyl ether with phenyl ether to the 100kg phenyl ether absorption unit that is equipped with of five series connection, holding temperature is 80 ℃, pure bromize hydrogen gas is along with device for cleaning pipeline is in 750kg glacial acetic acid solution, according to client's content requirement difference, throwing amount is also different, in the time absorbing hydrogen bromide, there is exothermic process, must control glacial acetic acid solution temperature between 10-20 degree, having a small amount of unabsorbed bromize hydrogen gas to pass into second glacial acetic acid solution absorbs again, after dripping off 100 kilograms of polybromodiphenyl ether, be incubated 2 hours, temperature is raised to 58 degree and starts to steam bromine, steam bromine and reclaim bromine through condenser, apply mechanically next time, consumption bromine is 990 kilograms, obtain hydrogen bromide content and be 1213 kilograms of 40% hydrogen bromide acetic acid solutions, productive rate 97%, obtain decabromodiphynly oxide crude product, through pulverizing, dry, packing, go out 550 kilograms of finished product decabromodiphynly oxides.
Take above-mentioned foundation desirable embodiment of the present invention as enlightenment, by above-mentioned description, relevant staff can, not departing from the scope of this invention technological thought, carry out various change and modification completely.The technical scope of this invention is not limited to the content on specification sheets, must determine its technical scope according to claim scope.
Claims (5)
1. in a bromination reaction, produce the treatment process of bromize hydrogen gas, it is characterized in that: in bromination reaction process, can produce a large amount of bromize hydrogen gas that contains free bromine, the phenyl ether solution multistage absorption that is 16～80 ℃ through holding temperature by gas becomes pure bromize hydrogen gas, phenyl ether is through repeatedly absorbing generation polybromodiphenyl ether, polybromodiphenyl ether is added drop-wise in bromine, dropwise rear insulation reaction 1-4h, temperature is raised to 58 ℃ of steamings except unnecessary bromine, obtain decabromodiphynly oxide, and then utilize pure bromize hydrogen gas to prepare hydrogen bromide acetic acid solution.
2. the treatment process that produces bromize hydrogen gas in a kind of bromination reaction according to claim 1, is characterized in that: the mol ratio of phenyl ether and free bromine is 100:1～10000:1.
3. the treatment process that produces bromize hydrogen gas in a kind of bromination reaction according to claim 1, is characterized in that: described plural serial stage is absorbed as 1～5 grade.
4. in a kind of bromination reaction according to claim 1, produce the treatment process of bromize hydrogen gas, it is characterized in that: the preparation of described hydrogen bromide acetic acid solution is that pure bromize hydrogen gas is passed in glacial acetic acid solution, glacial acetic acid solution is cooling, circulation absorbs, make content and be 30%～40% hydrogen bromide acetic acid solution, there is micro-unabsorbed bromize hydrogen gas to absorb completely through second acetum, emptying up to standard.
5. the treatment process that produces bromize hydrogen gas in a kind of bromination reaction according to claim 1, is characterized in that: the cooling temperature of described glacial acetic acid solution is 15-20 ℃.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010159631.XA CN102234104B (en) | 2010-04-29 | 2010-04-29 | Processing method of hydrogen bromide gas generated in bromination reaction |
| PCT/CN2010/000786 WO2011134120A1 (en) | 2010-04-29 | 2010-06-03 | Processing method for hydrogen bromide gas derived from bromization reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010159631.XA CN102234104B (en) | 2010-04-29 | 2010-04-29 | Processing method of hydrogen bromide gas generated in bromination reaction |
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| Publication Number | Publication Date |
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| CN102234104A CN102234104A (en) | 2011-11-09 |
| CN102234104B true CN102234104B (en) | 2014-05-21 |
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| CN201010159631.XA Expired - Fee Related CN102234104B (en) | 2010-04-29 | 2010-04-29 | Processing method of hydrogen bromide gas generated in bromination reaction |
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| CN (1) | CN102234104B (en) |
| WO (1) | WO2011134120A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110407662A (en) * | 2019-07-08 | 2019-11-05 | 山东重山光电材料股份有限公司 | A kind of method and system producing bromotrifluoromethane and co-producing high-purity hydrogen bromide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008027779A1 (en) * | 2006-08-29 | 2008-03-06 | Albemarle Corporation | Preparation of decabromodiphenyl oxide |
| WO2008027776A2 (en) * | 2006-08-29 | 2008-03-06 | Albemarle Corporation | Preparation of high assay decabromodiphenyl oxide |
| US20080058559A1 (en) * | 2006-08-29 | 2008-03-06 | Albemarle Corporation | Preparation of high assay decabromodiphenyl oxide |
| CN101528654B (en) * | 2006-08-31 | 2012-12-26 | 溴化合物有限公司 | A process for preparing polybrominated compounds |
| WO2008097348A1 (en) * | 2007-02-08 | 2008-08-14 | Albemarle Corporation | Process for separation of bromine from gaseous hydrogen bromide and use of such process in production of decabromodiphenylethane |
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2010
- 2010-04-29 CN CN201010159631.XA patent/CN102234104B/en not_active Expired - Fee Related
- 2010-06-03 WO PCT/CN2010/000786 patent/WO2011134120A1/en active Application Filing
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| Publication number | Publication date |
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| WO2011134120A1 (en) | 2011-11-03 |
| CN102234104A (en) | 2011-11-09 |
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