CN109232190A - A kind of purification method of tetrabromobisphenol A circulating mother liquor - Google Patents
A kind of purification method of tetrabromobisphenol A circulating mother liquor Download PDFInfo
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- CN109232190A CN109232190A CN201811108698.3A CN201811108698A CN109232190A CN 109232190 A CN109232190 A CN 109232190A CN 201811108698 A CN201811108698 A CN 201811108698A CN 109232190 A CN109232190 A CN 109232190A
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- tetrabromobisphenol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/24—Halogenated derivatives
- C07C39/26—Halogenated derivatives monocyclic monohydroxylic containing halogen bound to ring carbon atoms
- C07C39/27—Halogenated derivatives monocyclic monohydroxylic containing halogen bound to ring carbon atoms all halogen atoms being bound to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/24—Halogenated derivatives
- C07C39/367—Halogenated derivatives polycyclic non-condensed, containing only six-membered aromatic rings as cyclic parts, e.g. halogenated poly-hydroxyphenylalkanes
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of methods of the purification of tetrabromobisphenol A circulating mother liquor, this method is that bisphenol-A is dissolved in monochloro-benzene, bromine is added and carries out bromination substitution reaction, obtain the monochloro-benzene solution of tetrabromobisphenol A, then it is neutralized and is washed using sodium sulfite, and pass through the operating process such as crystallisation by cooling, centrifugation, tetrabromobisphenol A solid product and centrifuge mother liquor is made；Separation heart Recycling Mother Solution is applied to bromination kettle, and another part enters purification system processing.The present invention is a kind of purification techniques that circulating mother liquor is generated in tetrabromobisphenol A production, improve tetrabromobisphenol A product quality, to can be used as product for sale by reprocessing for organic matter in recycling mother liquor, the waste water of generation can be realized qualified discharge after entering biochemical treatment apparatus, the requirement for having reached continuous production tetrabromobisphenol A realizes performance of enterprises maximization.
Description
Fields:
The present invention relates to a kind of purification method of tetrabromobisphenol A circulating mother liquor, in particular to it is a kind of using bisphenol-A, bromine,
Hydrogen peroxide, the production method that monochloro-benzene is Material synthesis tetrabromobisphenol A.
Background technique:
Currently, domestic each tetrabromobisphenol A manufacturing enterprise all uses bisphenol-A, bromine, hydrogen peroxide, monochloro-benzene for Material synthesis
Tetrabromobisphenol A, process route are as follows:
1, bromination process: chlorobenzene (circulation chlorobenzene) is added in bromination kettle and is used as solvent, the originals such as bisphenol-A, hydrogen peroxide are added
Expect, under stiring dropwise addition bromine progress bromination reaction, 20-25 DEG C of reaction temperature；Then 80-85 DEG C of continuation bromine is increased the temperature to
Change, obtains the chlorobenzene solution (bromination liquid) of tetrabromobisphenol A；
2, neutralization step: bromination liquid being added and is neutralized in kettle, and sodium sulfite aqueous solution is added under stiring and neutralize instead
It answers, to remove acidic materials and excessive bromine, after static layering, obtained water phase washes feeding biochemical treatment system, contains four
The organic phase of bromine bisphenol-A pumps crystallization kettle；
3, Crystallization Procedure: in crystallization kettle, being passed through cooling water and be stirred continuously, and temperature control is at 0-10 DEG C, tetrabromobisphenol A
It is crystallized out in chlorobenzene, and forms the slurry of tetrabromobisphenol A.
4, it centrifugation and drying process: adds slurry into centrifuge and is separated by solid-liquid separation, obtained among tetrabromobisphenol A solid
Product, and product is formed after the remaining chlorobenzene of removal is further dried；Centrifuge mother liquor, which is recycled to bromination kettle, to be continued to use as solvent；
Due to generating a certain amount of tribromphenol, tribromo bisphenol-A, dibromo bisphenol-A, and water solubility during bromination reaction
The impurity such as organic matter, these impurity are dissolved in mother liquor (chlorobenzene), and with the increase impurity concentration of Recycling Mother Solution access times
It gradually rises, after cycle-index obtains 20-30 times, impurity concentration adds up extremely serious in mother liquor, starts to influence tetrabromo pair
Phenol A product quality must use fresh chlorobenzene to replace circulating mother liquor at this time, to maintain normal production；The mother liquor of replacement need into
One step regeneration treatment；
5, it the regeneration treatment process of circulating mother liquor: after circulating mother liquor heating evaporation is concentrated 3-5 times, recycles chlorobenzene and recycles
It uses, remaining part is added certain density sodium sulfite solution and is rinsed and be layered, and obtains at aqueous phase substance pumping biochemistry
Reason system, organic phase go to crystallisation by cooling, through the isolated second level solid organic matters product of centrifuge and two-stage centrifugal mother liquor；
The impurity contents such as secondary mother liquor tribromphenol, tribromo bisphenol-A, dibromo bisphenol-A, chlorobenzene and water soluble organic substance are very
Height, committee arrives specialized company's burning disposal outside some enterprises, and some is then directly entered waste water treatment system, to cause wastewater treatment
It is unable to qualified discharge.
Summary of the invention:
A kind of purification method of tetrabromobisphenol A circulating mother liquor is led to using monochloro-benzene, bisphenol-A, bromine, hydrogen peroxide as raw material
Cross bromination reaction, sodium sulfite neutralizes and the processes such as washing, crystallisation by cooling, centrifuge separation, obtain tetrabromobisphenol A product and centrifugation
Mother liquor；The production carried out according to the following steps:
1) using bisphenol-A, hydrogen peroxide, bromine as raw material, bromination reaction is carried out in the reaction kettle that monochloro-benzene is solvent and is obtained
Bromination solution, reaction temperature are controlled at 20-25 DEG C；；
2) bromination solution enters neutralization reaction kettle, and a certain amount of sodium sulfite solution is added and carries out neutralization reaction, with removal
Impurity therein；Then organic phase and water phase are obtained by static layering, wherein water phase enters biochemical treatment dress after treatment
It sets, organic phase enters crystallisation by cooling kettle；Tetrabromobisphenol A slurry is obtained after crystallisation by cooling, and is entered centrifuge and filtered, separation
Solid tetrabromobisphenol A product and centrifuge mother liquor out；
3) centrifuge mother liquor of 80-90% is recycled to bromination kettle and uses as the solvent of bromination reaction, and 10-20% enters purification
System carries out purified treatment；The purification of 2-5 times of quantity of a certain concentration 5-50%wt and mother liquor amount is added in cleaning treatment system
Agent, and chemically reacted with the impurity in mother liquor, reaction temperature is controlled at 25-90 DEG C, and the reaction time is about 0.5-5h, stirring
Device revolving speed is 30-80rpm, and then static layering obtains organic phase and water phase；Organic phase may loop to bromination kettle as bromination
The solvent of reaction uses, and water phase then isolates the monochloro-benzene and waste water of recycling through pervaporation；
4) then waste water enters acidification reaction kettle, and certain density sulfuric acid is added and is neutralized, and obtains after reaching PH=0.6-6
To white depositions, filter filtering is pumped, solid organic matters filter cake and filtrate are obtained；Solid organic matters main component is tetrabromo
Bisphenol-A and tribromphenol, by further isolated tetrabromobisphenol A product and tribromphenol product, filtrate is pumped at biochemistry
Reason realizes qualified discharge.
Further, the purified treatment in step 3) be added cleanser be sodium sulfite, it is potassium hydroxide, potassium carbonate, pure
One of alkali, caustic soda, organic base, alkaloid or more than one combination；
Further, it is 5-50%, neutralization reaction temperature that sulfuric acid concentration, which is added, in the neutralization that sulfuric acid is added in waste water in step 4)
15-50℃；Liquor C OD≤2000mg/l of filtering.
The solution have the advantages that: the present invention is that one kind of generation circulating mother liquor in tetrabromobisphenol A (TBBA) production is net
Change technology improves tetrabromobisphenol A (TBBA) product quality, and the organic matter recycled in mother liquor can be used as product by reprocessing
For sale, the waste water of generation can be realized qualified discharge after entering biochemical treatment apparatus, and it is double to have reached continuous production tetrabromo
The requirement of phenol A realizes performance of enterprises maximization.
Detailed description of the invention:
Fig. 1 is purification process general flow chart of the present invention.
Specific embodiment:
In order to further understand the content, features and effects of the present invention, the following examples are hereby given, and cooperate attached drawing
Detailed description are as follows:
Referring to attached drawing 1, the purification method of tetrabromobisphenol A circulating mother liquor of the present invention, circulating mother liquor a part is looped back to
System continues to apply, and another part carries out purification system and handled, and successively carries out by following process:
(1) TBBA circulating mother liquor (PhCL) is added in purification pot by cleaning procedure, then by mother liquor quality 2 extraordinarily
Entering cleanser, cleanser is the caustic soda of concentration 32%wt, opens stirring, and speed of agitator controls 65rpm, and opens steam valve,
Begin to warm up heating, heating outlet temperature control is at 85 DEG C, and the insulated and stirred time is 1.0h later, after by mother liquor in tank point
To phase-splitter.
(2) split-phase process, after mother liquor enters phase-splitter, heat preservation stands 1.0h, it is ensured that organic phase and water phase are sufficiently separated, meter
When after, by lower layer's water phase liquid separation to pans, waste water evaporating kettle is got to using pump, upper organic phase liquid separation to pans,
It is spare to get to the head tank that feeds intake.
(3) waste water evaporization process, water phase contains a certain amount of water-soluble chlorobenzene, to recycle chlorobenzene, realizes wastewater to reach standard row
It puts, needs to handle split-phase.After the water phase of phase-splitter lower layer discharge enters waste water evaporating kettle, stirring is opened, and open steaming
Steam valve door begins to warm up heating, and heating outlet temperature control is at 93 DEG C or more, it is ensured that chlorobenzene azeotrope with water, later azeotropic timing
1.0h, in time after, waste water is assigned in waste water and kettle.The chlorobenzene and water steamed is after condensation, into separating bottle, separation
Chlorobenzene get to that the head tank that feeds intake is spare, it is spare that isolated water reaches process water head tank.
(4) waste water neutralization step opens stirring after waste water enters neutralization kettle, and the dilute sulfuric acid that concentration is 30% is added, adjusting
PH is controlled to 1.0 or so, 1.0h is stirred later, after timing, by discharge of wastewater to filtration feed surge tank.
(5) filter progress, waste water enter filtration feed surge tank, start filter feed pump, start to carry out filters pressing, filtrate
Into mother liquor tank, liquor C OD testing result is 1630mg/l, and the caustic soda that concentration is 32% is added later, adjusts PH to 7, it
Enter biochemical treatment afterwards.After charging, blowback, later discharging, pack recovery processing are carried out.
Embodiment described above only describe the preferred embodiments of the invention, not to model of the invention
It encloses and is defined, without departing from the spirit of the design of the present invention, those of ordinary skill in the art are to technical side of the invention
The various changes and improvements that case is made should all be fallen into the protection scope that claims of the present invention determines.
Claims (3)
1. a kind of purification method of tetrabromobisphenol A circulating mother liquor is passed through using monochloro-benzene, bisphenol-A, bromine, hydrogen peroxide as raw material
Bromination reaction, sodium sulfite neutralize and the processes such as washing, crystallisation by cooling, centrifuge separation, obtains tetrabromobisphenol A product and centrifugation is female
Liquid；It is characterized in that the production carried out according to the following steps:
1) using bisphenol-A, hydrogen peroxide, bromine as raw material, bromination reaction is carried out in the reaction kettle that monochloro-benzene is solvent and obtains bromination
Solution, reaction temperature are controlled at 20-25 DEG C；；
2) bromination solution enters neutralization reaction kettle, and a certain amount of sodium sulfite solution is added and carries out neutralization reaction, to remove wherein
Impurity；Then organic phase and water phase are obtained by static layering, wherein water phase enters biochemical treatment apparatus after treatment, has
Machine mutually enters crystallisation by cooling kettle；Tetrabromobisphenol A slurry is obtained after crystallisation by cooling, and enters centrifuge and filters, and is isolated solid
Body tetrabromobisphenol A product and centrifuge mother liquor；
3) centrifuge mother liquor of 80-90% is recycled to bromination kettle and uses as the solvent of bromination reaction, and 10-20% enters purification system
Carry out purified treatment；The cleanser of 2-5 times of quantity of a certain concentration 5-50%wt and mother liquor amount is added in cleaning treatment system, and
It is chemically reacted with the impurity in mother liquor, at 25-90 DEG C, the reaction time is about 0.5-5h for reaction temperature control, and blender turns
Speed is 30-80rpm, and then static layering obtains organic phase and water phase；Organic phase may loop to bromination kettle as bromination reaction
Solvent use, water phase then isolates the monochloro-benzene and waste water of recycling through pervaporation；
4) then waste water enters acidification reaction kettle, and certain density sulfuric acid is added and is neutralized, reach obtain after PH=0.6-6 it is white
Color sediment, pumping filter filtering, obtains solid organic matters filter cake and filtrate；Solid organic matters main component is tetrabromobisphenol
A and tribromphenol, by further isolated tetrabromobisphenol A product and tribromphenol product, filtrate pumps biochemical treatment, real
Existing qualified discharge.
2. the purification method of tetrabromobisphenol A circulating mother liquor according to claim 1, it is characterised in that: net in step 3)
Change processing is that addition cleanser is one of sodium sulfite, potassium hydroxide, potassium carbonate, soda ash, caustic soda, organic base, alkaloid
Or more than one combination.
3. the purification method of tetrabromobisphenol A circulating mother liquor according to claim 1, it is characterised in that: waste water in step 4)
It is 5-50%, 15-50 DEG C of neutralization reaction temperature that sulfuric acid concentration, which is added, in the neutralization that sulfuric acid is added；Liquor C OD≤2000mg/ of filtering
l。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201811108698.3A CN109232190A (en) | 2018-09-21 | 2018-09-21 | A kind of purification method of tetrabromobisphenol A circulating mother liquor |
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| CN201811108698.3A CN109232190A (en) | 2018-09-21 | 2018-09-21 | A kind of purification method of tetrabromobisphenol A circulating mother liquor |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113372197A (en) * | 2021-06-30 | 2021-09-10 | 山东迈特新材料科技有限公司 | Method for recovering tribromophenol and tetrabromobisphenol A from tetrabromobisphenol A byproduct organic waste residue |
| CN114656335A (en) * | 2022-04-13 | 2022-06-24 | 山东海王化工股份有限公司 | Tetrabromobisphenol A intermediate layer material recycling technology |
| CN116606195A (en) * | 2023-07-19 | 2023-08-18 | 天津长芦汉沽盐场有限责任公司 | Resource treatment method for tetrabromobisphenol A wastewater |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113372197A (en) * | 2021-06-30 | 2021-09-10 | 山东迈特新材料科技有限公司 | Method for recovering tribromophenol and tetrabromobisphenol A from tetrabromobisphenol A byproduct organic waste residue |
| CN114656335A (en) * | 2022-04-13 | 2022-06-24 | 山东海王化工股份有限公司 | Tetrabromobisphenol A intermediate layer material recycling technology |
| CN116606195A (en) * | 2023-07-19 | 2023-08-18 | 天津长芦汉沽盐场有限责任公司 | Resource treatment method for tetrabromobisphenol A wastewater |
| CN116606195B (en) * | 2023-07-19 | 2023-10-20 | 天津长芦汉沽盐场有限责任公司 | Resource treatment method for tetrabromobisphenol A wastewater |
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Application publication date: 20190118 |