CN109052800A - A kind of sodium sulfate wastewater containing phenol cleans circulation utilization method - Google Patents
A kind of sodium sulfate wastewater containing phenol cleans circulation utilization method Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 79
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 71
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 title claims abstract description 65
- 229910052938 sodium sulfate Inorganic materials 0.000 title claims abstract description 59
- 235000011152 sodium sulphate Nutrition 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000000605 extraction Methods 0.000 claims abstract description 147
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 58
- 230000003647 oxidation Effects 0.000 claims abstract description 53
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 47
- 150000002989 phenols Chemical class 0.000 claims abstract description 46
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 16
- 239000012528 membrane Substances 0.000 claims abstract description 16
- 238000004140 cleaning Methods 0.000 claims abstract description 15
- 230000000694 effects Effects 0.000 claims abstract description 13
- 230000001698 pyrogenic effect Effects 0.000 claims abstract description 9
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 239000002904 solvent Substances 0.000 claims description 32
- 238000011084 recovery Methods 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 8
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 6
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 238000006056 electrooxidation reaction Methods 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000000284 extract Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000006213 oxygenation reaction Methods 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 abstract description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000011280 coal tar Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000003672 processing method Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- FTDXCHCAMNRNNY-UHFFFAOYSA-N phenol Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1 FTDXCHCAMNRNNY-UHFFFAOYSA-N 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- BZTCDDUZCMKTES-UHFFFAOYSA-L disodium;phenol;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.OC1=CC=CC=C1 BZTCDDUZCMKTES-UHFFFAOYSA-L 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- OQUKIQWCVTZJAF-UHFFFAOYSA-N phenol;sulfuric acid Chemical compound OS(O)(=O)=O.OC1=CC=CC=C1 OQUKIQWCVTZJAF-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
Circulation utilization method is cleaned the present invention relates to a kind of sodium sulfate wastewater containing phenol.Using two-stage extraction procedure, phenols most of in waste water is extracted in extraction phase, extractant and phenols are separated by way of rectifying, compared with traditional alkali washing method recycles extractant, rectificating method reduces the loss of extractant while improving cleaning for extractant removal process；Through waste water extracted after an effect vaporising device F101 effect, the a small amount of extractant contained in waste water and a small amount of phenols are steamed, aqueous sodium persulfate solution is concentrated to and is reached simultaneously the relevant temperature into oxidation unit O101, in oxidation unit O101, being saturated remaining phenols in metabisulfite solution, COD by exhaustive oxidation is H2O and CO2；After bipolar membrane device M101 effect, metabisulfite solution is broken down into dilute sulfuric acid and NaOH solution is returned for pyrogenic acid alkaline cleaner, realizes cleaning and recycling for the sodium sulfate wastewater containing phenol.
Description
Technical field
The invention belongs to coal chemical technology sheets, and in particular to a kind of method for cleaning of waste water, in particular to it is a kind of to contain phenol
Sodium sulfate wastewater cleans circulation utilization method.
Background technique
It is often sour alkali wash that the method for phenol is removed during coal tar deep processing, passes through sodium hydroxide solution and coal tar
Phenols in fraction, which is reacted, enters water phase at sodium phenolate, and water phase reacts production phenol and sulfuric acid with sodium phenolate using dilute sulfuric acid after split-phase
Sodium water solution contains a certain amount of phenols so as to cause the sodium sulfate wastewater generated in sour alkaline cleaning procedure, at sodium sulfate wastewater containing phenol
Reason is difficult, and high phenol content, high COD and high content of salt prevent waste water from directly handling into biochemistry pool, simultaneously because the presence of phenol, system
Standby sodium sulphate product is not up to standard.Sodium sulfate wastewater containing phenol is very big to environmental hazard, the serious ecological balance for destroying water body, simultaneously
If phenols and sodium sulphate cannot recycle, the waste of resource will also result in.
Chinese patent CN201510354644.5 proposes a kind of sodium sulfate wastewater for being related to coal tar processing except phenol method,
Static mixer is added with extractant in sodium sulfate wastewater and is sufficiently mixed, the mixture being obtained by extraction is sent into coalescer, coalescence
The lower layer's sodium sulfate wastewater being obtained by extraction in device is discharged downstream for further processing；Upper layer extractant and coalescer in coalescer
Middle part carries out after mixing with lye because the third phase flocculence substance that two-phase extraction generates is sent into another static mixer together
Back extraction processing；The mixture that back extraction obtains is sent into another coalescer and carries out water-oil separating, wherein extractant is sent back to
Storage tank recycling；And the sodium phenolate solution obtained after back extraction is sent into sulfuric acid decomposition technique.
Chinese patent CN201410662662.5 proposes the sodium sulfate wastewater comprehensive utilization side in a kind of coal tar processing
Method and device, the invention provides the sodium sulfate wastewater method of comprehensive utilization in a kind of coal tar processing, to sodium sulfate wastewater into
Row water-oil separating, obtained degreased wastewater carry out Centrifugical extraction, and the solvent containing phenol that Centrifugical extraction is obtained carries out centrifugation back extraction
Alkali cleaning removes phenol, and dephenolize solution is successively carried out to secondary oil removing, neutralization and absorption, and further by the sulphur of obtained purification
Acid sodium solution is evaporated crystallization.
Chinese patent CN201710188779.8 proposes a kind of method for extracting and dephenolizing of phenol wastewater, and phenol wastewater is existed
Multi-stage counter current extraction is carried out using extractant at a temperature of 20-35 DEG C, obtains extraction phase and raffinate phase, extractant is cyclic ketones class,
The pH value of phenol wastewater is 6-7.
Chinese patent CN201710703388.5 proposes a kind of processing method of phenol wastewater, use magnetic active carbon for
Catalyst, catalytic ozonation Phenol-Containing Wastewater Treatment.The absorption property of the invention combination magnetic active carbon material and catalysis are smelly
The activity of oxygen oxidation, mild condition is lower to the degree of dependence of the conditions such as temperature, pH, and composite material is magnetic agent because of load
(Fe3O4), Magnetic Isolation can be rapidly completed, there is good recyclability.
However, to the processing method of phenol wastewater in sodium sulfate wastewater containing phenol performance difficulty, ozone oxidation is at high cost,
It is difficult to carry out in actual production.Although Chinese patent CN201510354644.5 and Chinese patent CN201410662662.5 is proposed
The processing method of the sodium sulfate wastewater containing phenol, but its technique carries out water-oil separating in extraction agent in coalescer, extraction
It takes agent to be dissolved in water the secondary pollution for causing water, increases processing cost；It is only difficult to that phenol sulfuric acid will be contained by way of extraction
Neutral oil and phenols in sodium waste water are totally removed, so the sodium sulphate of its metabisulfite solution evaporative crystallization preparation is difficult to qualification,
And two kinds of techniques are difficult to continuous operation, are not suitable for industrial applications.
It would therefore be highly desirable to that develops a kind of sodium sulfate wastewater containing phenol suitable for industrial applications cleans technique, it should
Phenols in efficient removal sodium sulfate wastewater containing phenol, make purified waste water phenol content≤50ppm, COD≤1000ppm reach into
The discharge standard of biochemistry pool, at the same by sodium sulfate wastewater containing phenol phenol and sodium sulphate effectively recycle, reach industrial products
Index.
Summary of the invention
It is an object of the invention to propose a kind of sodium sulfate wastewater containing phenol to clean circulation utilization method, can efficiently take off
Except the phenols in sodium sulfate wastewater containing phenol, make purified waste water phenol content≤50ppm, COD≤1000ppm, while by dephenolize
Metabisulfite solution after de- COD carries out film process, is translated into NaOH solution and dilute sulfuric acid returns to pyrogenic acid alkaline cleaner.It should
Method not only by sodium sulfate wastewater containing phenol phenol and sodium sulphate effective recycling, but also operate plus single, can continuous metaplasia
It produces, realizes cleaning for the sodium sulfate wastewater containing phenol.
To achieve the above object, the present invention adopts the following technical scheme that.
A kind of sodium sulfate wastewater containing phenol cleans circulation utilization method, including level-one extraction tower T101, second level extraction tower
T102, evaporator F101, oxidation unit O101, bipolar membrane device M101 and solvent recovery tower T103；From second level extraction tower
Extractant at the top of T102 is added from the level-one lower part extraction tower T101, and sodium sulfate wastewater containing phenol is extracted with after dilute sulfuric acid tune pH from level-one
It takes the top tower T101 to be added, enters on second level extraction tower T102 through water phase extracted from the extraction of level-one extraction tower T101 tower bottom
Portion, the extraction phase being made of extractant and phenols are entered in the middle part of recovery tower T103 by level-one extraction tower T101 overhead extraction；It is fresh
Extractant is added from the second level lower part extraction tower T102, and the extraction phase being made of extractant and phenols is from second level extraction tower T102 tower top
Extraction enters the lower part level-one extraction tower T101, produces through second level water phase extracted from second level extraction tower T102 tower bottom and enters evaporation
Device F101；Recovered water and the extractant and a small amount of volatile phenol that are dissolved into water, the partial material are made at the top of evaporator F101
Match alkali water for pyrogenic acid alkali cleaning complex acid, extraction saturation metabisulfite solution in bottom enters oxidation unit O101；In oxidation unit
In O101, it is saturated remaining phenols, COD in metabisulfite solution and is oxidized to H2O and CO2, through oxidation unit O101, that treated is useless
Phenol content≤50ppm, COD≤1000ppm in water；The waste water of oxidation unit O101 extraction enters bipolar membrane device M101, through double
The effect of pole film M101, sodium sulfate wastewater are broken down into dilute sulfuric acid and NaOH solution；Enter solvent recovery from T101 extraction phase
In the middle part of tower T103, solvent is produced at the top of solvent recovery tower T103, tower reactor can be used as phenol treating device containing the phenols of a small amount of solvent
Raw material.
The extractant that the extraction process uses is one of methyl iso-butyl ketone (MIBK), methyl ethyl ketone or mixed solvent.
The sodium sulfate wastewater containing phenol enters level-one extraction tower T101 before with dilute sulfuric acid tune pH=1-5.
The extractant quality that the extraction process uses: material quality extracts ratio as 0.5-3:1.
Mode of oxidizing used by the oxidation unit O101 is in ozone oxidation, hydrogen peroxide oxidation or electrochemical oxidation
One or more combinations.
PH=2-6 needed for oxidation reaction in the oxidation unit O101.
A kind of sodium sulfate wastewater containing phenol cleans circulation utilization method, to phenols removal efficiency in sodium sulfate wastewater containing phenol >=
90%, COD removal efficiency >=95%.
A kind of sodium sulfate wastewater containing phenol cleans circulation utilization method, to the phenols rate of recovery in sodium sulfate wastewater containing phenol >=
90%, while producing dilute sulfuric acid and NaOH solution.
A kind of sodium sulfate wastewater containing phenol cleans circulation utilization method, uses two-stage extraction procedure first, will
Most phenols is extracted in extraction phase in waste water, is then separated extractant and phenols by way of rectifying, with
Traditional alkali washing method recycling extractant is compared, and rectificating method reduces the loss of extractant while improving extractant removal process
Clean；Through waste water extracted through one effect vaporising device F101 effect after, by waste water a small amount of extractant contained and
A small amount of phenols steams, while entering oxidation unit O101 after aqueous sodium persulfate solution is concentrated, and in oxidation unit O101, satisfies
H is oxidized to phenols remaining in metabisulfite solution, COD2O and CO2；After bipolar membrane device M101 effect, metabisulfite solution
It is broken down into dilute sulfuric acid and NaOH solution is returned for pyrogenic acid alkaline cleaner, realize cleaning and following for the sodium sulfate wastewater containing phenol
Ring utilizes.
The advantages of this method is:
(1) solve the problems, such as that sodium sulfate wastewater containing phenol can not be handled；
(2) this method is not related to sour alkaline cleaning procedure, reduces the consumption of extractant, shortens process flow, effectively realizes
The cleaning of the sodium sulfate wastewater containing phenol；
(3) this method is low to the processing cost of the sodium sulfate wastewater containing phenol, it is easy to accomplish, and sodium sulphate containing phenol can not only be recycled
Phenolic substances in waste water, and metabisulfite solution is become into dilute sulfuric acid and NaOH solution, recycling for waste water is realized, greatly
The economic benefit and social benefit of enterprise are improved greatly.
Detailed description of the invention
Fig. 1 cleans circulation utilization method schematic diagram for a kind of sodium sulfate wastewater containing phenol
T101 level-one extraction tower, T102 second level extraction tower, T103 solvent recovery tower, F101 evaporator, O101 oxidation unit,
M101 bipolar membrane device.
Specific embodiment
Implementation method is further described below in conjunction with attached drawing.
A kind of sodium sulfate wastewater containing phenol cleans circulation utilization method, including level-one extraction tower T101, second level extraction tower
T102, evaporator F101, oxidation unit O101, bipolar membrane device M101 and solvent recovery tower T103；From second level extraction tower
Extractant at the top of T102 is added from the level-one lower part extraction tower T101, and sodium sulfate wastewater containing phenol is extracted with after dilute sulfuric acid tune pH from level-one
It takes the top tower T101 to be added, enters on second level extraction tower T102 through water phase extracted from the extraction of level-one extraction tower T101 tower bottom
Portion, the extraction phase being made of extractant and phenols are entered in the middle part of recovery tower T103 by level-one extraction tower T101 overhead extraction；It is fresh
Extractant is added from the second level lower part extraction tower T102, and the extraction phase being made of extractant and phenols is from second level extraction tower T102 tower top
Extraction enters the lower part level-one extraction tower T101, produces through second level water phase extracted from second level extraction tower T102 tower bottom and enters evaporation
Device F101；Recovered water and the extractant and a small amount of volatile phenol that are dissolved into water, the partial material are made at the top of evaporator F101
Match alkali water for pyrogenic acid alkali cleaning complex acid, extraction saturation metabisulfite solution in bottom enters oxidation unit O101；In oxidation unit
In O101, it is saturated remaining phenols, COD in metabisulfite solution and is oxidized to H2O and CO2, through oxidation unit O101, that treated is useless
Phenol content≤50ppm, COD≤1000ppm in water；The waste water of oxidation unit O101 extraction enters bipolar membrane device M101, through double
The effect of pole film M101, sodium sulfate wastewater are broken down into dilute sulfuric acid and NaOH solution；Enter solvent recovery from T101 extraction phase
In the middle part of tower T103, solvent is produced at the top of solvent recovery tower T103, tower reactor can be used as phenol treating device containing the phenols of a small amount of solvent
Raw material.
Embodiment 1
A kind of sodium sulfate wastewater containing phenol cleans circulation utilization method, including level-one extraction tower T101, second level extraction tower
T102, evaporator F101, oxidation unit O101, bipolar membrane device M101 and solvent recovery tower T103；From second level extraction tower
Extractant at the top of T102 is added from the level-one lower part extraction tower T101, sodium sulfate wastewater containing phenol with after dilute sulfuric acid tune pH=1 from one
The grade top extraction tower T101 is added, and enters second level extraction tower T102 from the extraction of level-one extraction tower T101 tower bottom through water phase extracted
Top, the extraction phase being made of extractant and phenols are entered in the middle part of recovery tower T103 by level-one extraction tower T101 overhead extraction；Newly
Fresh extractant is added from the second level lower part extraction tower T102, and the extraction phase being made of extractant and phenols is from second level extraction tower T102 tower
Top extraction enters the lower part level-one extraction tower T101, produces to enter from second level extraction tower T102 tower bottom through second level water phase extracted and steam
Transmitting apparatus F101；Recovered water and the extractant and a small amount of volatile phenol that are dissolved into water, the partial material at the top of evaporator F101
Match alkali water as pyrogenic acid alkali cleaning complex acid, extraction saturation metabisulfite solution in bottom enters oxidation unit O101；In oxidation unit
In O101, it is saturated remaining phenols, COD in metabisulfite solution and is oxidized to H2O and CO2, through oxidation unit O101, that treated is useless
Phenol content≤50ppm, COD≤1000ppm in water；The waste water of oxidation unit O101 extraction enters bipolar membrane device M101, through double
The effect of pole film M101, sodium sulfate wastewater are broken down into dilute sulfuric acid and NaOH solution；Enter solvent recovery from T101 extraction phase
In the middle part of tower T103, solvent is produced at the top of solvent recovery tower T103, tower reactor can be used as phenol treating device containing the phenols of a small amount of solvent
Raw material.
Extractant used by the extraction process is methyl ethyl ketone, and extraction is than being 0.5.
Mode of oxidizing used by the oxidation unit O101 is that ozone oxidation and electrochemical oxidation combine.
PH range 2 needed for oxidation reaction in the oxidation unit O101.
Using this method, phenols removal efficiency >=90%, COD removal efficiency >=95%, the phenols rate of recovery >=90%, dilute sulfuric acid and
NaOH solution.
Embodiment 2
A kind of sodium sulfate wastewater containing phenol cleans circulation utilization method, including level-one extraction tower T101, second level extraction tower
T102, evaporator F101, oxidation unit O101, bipolar membrane device M101 and solvent recovery tower T103；From second level extraction tower
Extractant at the top of T102 is added from the level-one lower part extraction tower T101, sodium sulfate wastewater containing phenol with after dilute sulfuric acid tune pH=3 from one
The grade top extraction tower T101 is added, and enters second level extraction tower T102 from the extraction of level-one extraction tower T101 tower bottom through water phase extracted
Top, the extraction phase being made of extractant and phenols are entered in the middle part of recovery tower T103 by level-one extraction tower T101 overhead extraction；Newly
Fresh extractant is added from the second level lower part extraction tower T102, and the extraction phase being made of extractant and phenols is from second level extraction tower T102 tower
Top extraction enters the lower part level-one extraction tower T101, produces to enter from second level extraction tower T102 tower bottom through second level water phase extracted and steam
Transmitting apparatus F101；Recovered water and the extractant and a small amount of volatile phenol that are dissolved into water, the partial material at the top of evaporator F101
Match alkali water as pyrogenic acid alkali cleaning complex acid, extraction saturation metabisulfite solution in bottom enters oxidation unit O101；In oxidation unit
In O101, it is saturated remaining phenols, COD in metabisulfite solution and is oxidized to H2O and CO2, through oxidation unit O101, that treated is useless
Phenol content≤50ppm, COD≤1000ppm in water；The waste water of oxidation unit O101 extraction enters bipolar membrane device M101, through double
The effect of pole film M101, sodium sulfate wastewater are broken down into dilute sulfuric acid and NaOH solution；Enter solvent recovery from T101 extraction phase
In the middle part of tower T103, solvent is produced at the top of solvent recovery tower T103, tower reactor can be used as phenol treating device containing the phenols of a small amount of solvent
Raw material.
Extractant used by the extraction process is methyl iso-butyl ketone (MIBK), and extraction is than being 1.
Mode of oxidizing used by the oxidation unit O101 is ozone oxidation or hydrogen peroxide oxidation.
PH range 4 needed for the electroxidation device O101 oxidation reaction.
Using this method, phenols removal efficiency >=90%, COD removal efficiency >=95%, the phenols rate of recovery >=90%, dilute sulfuric acid and
NaOH solution.
Embodiment 3
A kind of sodium sulfate wastewater containing phenol cleans circulation utilization method, including level-one extraction tower T101, second level extraction tower
T102, evaporator F101, oxidation unit O101, bipolar membrane device M101 and solvent recovery tower T103；From second level extraction tower
Extractant at the top of T102 is added from the level-one lower part extraction tower T101, sodium sulfate wastewater containing phenol with after dilute sulfuric acid tune pH=5 from one
The grade top extraction tower T101 is added, and enters second level extraction tower T102 from the extraction of level-one extraction tower T101 tower bottom through water phase extracted
Top, the extraction phase being made of extractant and phenols are entered in the middle part of recovery tower T103 by level-one extraction tower T101 overhead extraction；Newly
Fresh extractant is added from the second level lower part extraction tower T102, and the extraction phase being made of extractant and phenols is from second level extraction tower T102 tower
Top extraction enters the lower part level-one extraction tower T101, produces to enter from second level extraction tower T102 tower bottom through second level water phase extracted and steam
Transmitting apparatus F101；Recovered water and the extractant and a small amount of volatile phenol that are dissolved into water, the partial material at the top of evaporator F101
Match alkali water as pyrogenic acid alkali cleaning complex acid, extraction saturation metabisulfite solution in bottom enters oxidation unit O101；In oxidation unit
In O101, it is saturated remaining phenols, COD in metabisulfite solution and is oxidized to H2O and CO2, through oxidation unit O101, that treated is useless
Phenol content≤50ppm, COD≤1000ppm in water；The waste water of oxidation unit O101 extraction enters bipolar membrane device M101, through double
The effect of pole film M101, sodium sulfate wastewater are broken down into dilute sulfuric acid and NaOH solution；Enter solvent recovery from T101 extraction phase
In the middle part of tower T103, solvent is produced at the top of solvent recovery tower T103, tower reactor can be used as phenol treating device containing the phenols of a small amount of solvent
Raw material.
Mode of oxidizing used by the oxidation unit O101 is electrochemical oxidation.
PH range 6 needed for the oxidation unit O101 oxidation reaction.
Using this method, phenols removal efficiency >=90%, COD removal efficiency >=95%, the phenols rate of recovery >=90%, dilute sulfuric acid and
NaOH solution.
A kind of sodium sulfate wastewater containing phenol that the present invention is disclosed and proposed cleans circulation utilization method, those skilled in the art
Member can be by using for reference present disclosure, and the appropriate links such as condition route that change are realized, although method and technology of preparing of the invention are
It is described by preferred embodiment, related technical personnel can obviously not depart from the content of present invention, in spirit and scope
Methods and techniques described herein route is modified or is reconfigured, to realize final technology of preparing.Especially need to refer to
Out, all similar replacements and change are apparent to those skilled in the art, they are considered as wrapping
It includes in spirit of that invention, range and content.
Claims (6)
1. a kind of sodium sulfate wastewater containing phenol cleans circulation utilization method；It is characterized in that including level-one extraction tower T101, second level
Extraction tower T102, evaporator F101, oxidation unit O101, bipolar membrane device M101 and solvent recovery tower T103；Extract from second level
Take extractant at the top of tower T102 to be added from the level-one lower part extraction tower T101, sodium sulfate wastewater containing phenol with after dilute sulfuric acid tune pH from one
The grade top extraction tower T101 is added, and enters second level extraction tower T102 from the extraction of level-one extraction tower T101 tower bottom through water phase extracted
Top, the extraction phase being made of extractant and phenols are entered in the middle part of recovery tower T103 by level-one extraction tower T101 overhead extraction；Newly
Fresh extractant is added from the second level lower part extraction tower T102, and the extraction phase being made of extractant and phenols is from second level extraction tower T102 tower
Top extraction enters the lower part level-one extraction tower T101, produces to enter from second level extraction tower T102 tower bottom through second level water phase extracted and steam
Transmitting apparatus F101；Recovered water and the extractant and a small amount of volatile phenol that are dissolved into water, the partial material at the top of evaporator F101
Match alkali water as pyrogenic acid alkali cleaning complex acid, extraction saturation metabisulfite solution in bottom enters oxidation unit O101；In oxidation unit
In O101, being saturated remaining phenols in metabisulfite solution, COD by exhaustive oxidation is H2O and CO2, after oxidation unit O101 processing
Waste water enter bipolar membrane device M101, the effect through Bipolar Membrane M101, sodium sulfate wastewater is broken down into dilute sulfuric acid and NaOH is molten
Liquid；Enter in the middle part of solvent recovery tower T103 from T101 extraction phase, solvent is produced at the top of solvent recovery tower T103, tower reactor is containing a small amount of
Raw material of the phenols of solvent as phenol treating device.
2. the method as described in claim 1, it is characterized in that the extractant that extraction process uses is methyl iso-butyl ketone (MIBK), methyl second
One of base ketone or mixed solvent.
3. the method as described in claim 1, it is characterized in that sodium sulfate wastewater containing phenol enters level-one extraction tower T101 before with dilute
Sulfuric acid tune pH=1-5.
4. the method as described in claim 1, it is characterized in that the extractant quality that extraction process uses: material quality extraction than for
0.5-3:1.
5. the method as described in claim 1, it is characterized in that mode of oxidizing used by oxidation unit O101 be ozone oxidation, it is double
One of oxygen water oxygen or electrochemical oxidation or multiple combinations.
6. the method as described in claim 1, it is characterized in that pH=2-6 needed for oxidation reaction in oxidation unit O101.
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| CN114195307A (en) * | 2021-11-30 | 2022-03-18 | 乌海黑猫炭黑有限责任公司 | Treatment system and method for recycling phenol-containing sodium sulfate wastewater |
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