CN102976561A - Technique for treating phenol/anisole-containing production wastewater - Google Patents
Technique for treating phenol/anisole-containing production wastewater Download PDFInfo
- Publication number
- CN102976561A CN102976561A CN2012105476941A CN201210547694A CN102976561A CN 102976561 A CN102976561 A CN 102976561A CN 2012105476941 A CN2012105476941 A CN 2012105476941A CN 201210547694 A CN201210547694 A CN 201210547694A CN 102976561 A CN102976561 A CN 102976561A
- Authority
- CN
- China
- Prior art keywords
- phenoxide
- methyl
- production wastewater
- enters
- extraction
- 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.)
- Pending
Links
Images
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Physical Water Treatments (AREA)
Abstract
The invention discloses a technique for treating phenol/anisole-containing production wastewater, particularly a method for treating phenol/anisole-containing production wastewater by a floatation-high efficiency extraction-membrane bioreactor (MBR)-catalytic oxidation technique. The technique comprises steps as follows: raw water firstly enters a floatation unit to remove suspended substances, and then enters an extraction unit, wherein an extractant composed of N-octanoylpyrrolidine, tributyl phosphate, dimethyl carbonate and solvent kerosene in a ratio of 0.8:1.2:2.9:7 is utilized to carry out dephenolization treatment; the treated wastewater enters an MBR unit to carry out biochemical degradation of methanol; and the wastewater finally enters a sodium hypochlorite-alpha-Fe2O3 catalytic oxidation unit to remove anisole by deep oxidation. The invention provides a new technique for efficiently treating phenol/anisole-containing production wastewater; and by using the technique, the removal rates of wastewater COD (chemical oxygen demand), volatile phenols, methanol and anisole are respectively up to 99.7%, 99.99%, 99.12% and 99.97%.
Description
Technical field
The present invention relates to the technique that a kind of processing contains phenol methyl-phenoxide factory effluent, particularly relate to a kind of air supporting-efficient extraction-membrane bioreactor-catalytic oxidation technique that adopts and process the method for the methyl-phenoxide factory effluent that contains phenol.
Background technology
Phenolic compound is a kind of important industrial chemicals and chemical intermediate, also is simultaneously the byproduct in a lot of chemical processs.The a lot of production processes of chemical industry comprise that coking, oil refining, resin, Coal Chemical Industry etc. all can produce phenolic wastewater.Aldehydes matter is prototype matter poisonous substance as a kind of environmental hormone, takes in when a certain amount of when human body, will cause protein denaturation and solidifies, and the acute poisoning symptom can occur, the symptoms such as headache, dizzy, weak, expiratory dyspnea occur.When containing the phenol amount at 0.1-0.2ppm in the water, can make the flesh of fish of growth fish that peculiar smell is arranged; And if be used for irrigating greater than the phenolic wastewater of 100ppm, will cause the underproduction of farm crop and withered, environment is caused serious pollution, therefore all attach great importance to the processing of phenolic wastewater both at home and abroad.The overall inclusion logos of the treatment process of phenolic wastewater, chemical method and biological process specifically comprise again the methods such as absorption method, extraction process, oxidation style, electrolytic process.In these methods, complexing abstraction can reclaim the phenolic compound in the waste water, and process cost is low, and is pollution-free, but will select suitable extraction agent aborning.At present industrial commonly used be the mixed extractant that N503 adds kerosene, but low, the easy emulsification of this extraction agent extraction efficiency, not easily separated, the shortcoming such as regeneration cost is high, so the efficient extraction agent of development of new is problem demanding prompt solution during present phenolic wastewater is processed.
The handled waste water of the present invention is the phenolic wastewater that produces in the methyl-phenoxide production process, because production process adopts phenol methanolizing method, therefore in the methyl-phenoxide production process, can produce phenol and the methyl-phenoxide waste water of a large amount of difficult for biological degradation, and waste water composition is complicated, COD is high, phenol concentration is high, and biodegradability is poor.Traditional treatment process generally adopts first the phenol in physics or the chemical process removal waste water, then can adopt biochemical method further to process.Biochemical process adopts A/O technique usually, and this technique has simple to operate, low cost and other advantages, and load is low, occupation area of equipment large, the sludge creation amount is many and cause easily secondary pollution but process.In addition, this technique is not good to the removal effect of methyl-phenoxide in the waste water.
At present a lot of to the phenolic wastewater treatment process in the methyl-phenoxide production process, comprise evaporation, extraction, absorption, electrolysis, biochemical process etc., the present invention adopts air supporting-extraction-membrane bioreactor (MBR)-catalytic oxidation technique that phenolic wastewater is carried out comprehensive treating process, and used extraction agent is independently developed efficient extraction agent; Biochemical unit adopts detachable membrane bioreactor; It is oxygenant that oxidizing process adopts clorox, nanometer alpha-Fe
2O
3Be catalyzer, the methyl-phenoxide in the water carried out deep oxidation process.Through this art breading, the clearance of waste water COD, volatile phenol, methyl alcohol and methyl-phenoxide can reach respectively 99.7%, 99.99%, 99.12% and 99.97%.Adopt at present this technique that the treatment process of the phenolic wastewater in the methyl-phenoxide production process be there is not yet relevant report.
The meaning of this patent is to provide a kind of environmental-friendly new method for the recovery of Phenols In Industrial Liquid Waste class material and processing, China's exploitation is had wastewater processing technology efficient, simple and easy, low consumption have important directive significance.
Summary of the invention
The technique that the present invention proposes a kind of air supporting-efficient extraction-membrane bioreactor-catalyzed oxidation is processed the phenolic wastewater in the methyl-phenoxide production process, this method has efficiently, simply, the characteristics such as cost is low.
Technical scheme of the present invention is summarized as follows:
A kind of air supporting-efficient extraction-membrane bioreactor-catalytic oxidation technique that adopts is processed the method for the methyl-phenoxide factory effluent that contains phenol, is comprised the steps:
(1) air flotation cell, waste water enters air flotation pool through lift pump, air flotation pool length and width height is 2m * 1m * 0.6m, the gas flotation aids polymerize aluminum chloride accurately adds in the air flotation cell after the volume pump metering, drug concentration is controlled at 100-5000mg/L, and the air flotation cell bottom passes into the steam water interface from the pressure air-dissolving tank, and dissolved air release is the TJ-II type, dissolving pressure is at 0.1-0.3MPa, and the residence time of waste water in air flotation pool is controlled at 1-5h.
(2) extraction cells, waste water enters equalizing tank 1 through impeller pump after air flotation cell is processed, regulate pH=5-7.Equalizing tank 1 water outlet enters multistage filler extraction top of tower through impeller pump, extraction tower tower height 3.5m, segregation section Φ 0.25 * 0.75m wherein, extraction section Φ 0.1 * 2m, in-built plastics ball filler, it is 5-10 that extraction tower effectively extracts progression, extraction agent enters the extraction tower bottom through magnetic drive pump, the extraction water oil ratio is controlled at 1/3-1/8, extraction agent consist of N-decoyl tetramethyleneimine (OPOD), tributyl phosphate (TBP), methylcarbonate (DMC) and solvent kerosene, its composition and ratio is 0.5-1: 0.8-1.5: 2.5-3: 6-8 in order, waste water goes out to enter oil trap from the extraction tower bottom from top to bottom, extraction agent goes out from the extraction tower cat head, enters extraction agent reclaiming tower.Regenerator column is the adverse current soda-wash tower, and soda-wash tower adopts stainless steel sieve plate tower, and tower height 2.5m wherein goes up segregation section Φ 0.3 * 1m, stripping section Φ 0.15 * 1.5m.Extraction phase enters at the bottom of the regeneration Tata through magnetic drive pump, and alkali lye adopts 20% (wt%) NaOH solution, adds from the regenerator column cat head, and the extraction agent after the regeneration recycles, and reclaims phenol sodium at the bottom of the regeneration Tata.
(3) MBR unit,
Enter equalizing tank 2 from extraction cells oil trap waste water out through impeller pump, regulate pH=6-8, equalizing tank 2 water outlets enter the MBR reactor through impeller pump, reactor adopts split type, sludge concentration is 5-10g/L in the reactor, and dissolved oxygen in the pond (DO) concentration is 2-5mg/L, and membrane module adopts hollow-fibre membrane (the film mean pore size is 2.0 microns), the MBR reactor waterpower residence time (HRT) is controlled at 4-6h, and waste water is extracted out by vacuum primingpump behind the MBR reactor.
(4) catalytic oxidation unit, the waste water that goes out from the MBR unit enters equalizing tank 3 through impeller pump, regulate pH=6-8, equalizing tank 3 water outlets enter oxidation reactor through impeller pump, and (Φ 0.5 * 1.0m), apparatus with catalyst inside, oxygenant adopts clorox, and concentration is 0.1%-2%, and the present invention adopts nanometer α-Fe
2O
3Be catalyzer, α-Fe
2O
3Particle diameter is 30-200nm, and concentration is 1g/L, and the reaction times is 20-50min.The oxidation pond water outlet is discharged after equalizing tank 4 is regulated pH=7.
Preferably:
In the described step (1), gas flotation aids polymerize aluminum chloride concentration is at 500mg/L, and dissolving pressure is at 0.2MPa, and the residence time of waste water in air flotation pool is controlled at 3h.
In the described step (2), the pH=5 of equalizing tank 1, it is 8 that extraction tower effectively extracts progression, the extraction water oil ratio is controlled at 1: 5, and it is 0.8: 1.2: 2.9 that extraction agent forms N-decoyl tetramethyleneimine (OPOD), tributyl phosphate (TBP), methylcarbonate (DMC) and solvent kerosene proportioning: 7.
In the described step (3), sludge concentration is 10g/L in the pH=6.5 of equalizing tank 2, reactor, and dissolved oxygen concentration is 4mg/L in the pond, and the MBR reactor waterpower residence time (HRT) is controlled 6h.
In the described step (4), the pH=6.5 of equalizing tank 3, clorox concentration is 0.8%, α-Fe
2O
3Particle diameter is 30nm, and the reaction times is 30min.
The present invention relates to a kind of methyl-phenoxide production wastewater treatment technique that contains phenol, adopt air supporting-efficient extraction-MBR-catalytic oxidation technique Phenol-Containing Wastewater Treatment.Compare with traditional treatment method, the present invention adopts independently developed efficient extractant formulation, and the phenol extraction rate can reach 99.99%.Simultaneously, the present invention adopts catalytic oxidation technique, with nano level Fe
2O
3Be catalyzer, catalytic effect is obvious, can significantly reduce methyl-phenoxide and COD content in the waste water.
Description of drawings
Process flow sheet of the present invention is as follows:
The full technical process schematic block diagram of Fig. 1
Fig. 2 air flotation cell schematic flow sheet
Fig. 3 extraction cells schematic flow sheet
Fig. 4 MBR unit schematic flow sheet
Fig. 5 catalytic oxidation unit schematic flow sheet
Embodiment
The former water of waste water consists of COD:49000mg/L, volatile phenol: 6000mg/L, methyl alcohol: 4500mg/L, methyl-phenoxide: 1400mg/L.Waste water at first enters air flotation cell, and the concentration of gas flotation aids polymerize aluminum chloride is 500mg/L, and the air flotation cell bottom passes into the steam water interface from the pressure air-dissolving tank, and dissolving pressure is 0.2MPa, and the residence time of waste water in air flotation pool is controlled to be 3h.Waste water is after air flotation cell is processed, enter equalizing tank 1, regulating pH is 5, enter the multi-stage solvent extraction top of tower from equalizing tank 1 water outlet through impeller pump, it is 8 that extraction tower effectively extracts progression, extraction agent enters the extraction tower bottom through magnetic drive pump, the extraction water oil ratio is controlled at 1: 5, extraction agent consist of N-decoyl tetramethyleneimine (OPOD), tributyl phosphate (TBP), methylcarbonate (DMC) and solvent kerosene, its composition and ratio is 0.8: 1.2: 2.9 in order: 7, and waste water goes out from the extraction tower bottom from top to bottom, enters oil trap, extraction agent goes out from the extraction tower cat head, enters afterwards extraction agent reclaiming tower.The waste water that goes out from oil trap enters equalizing tank 2 through impeller pump, regulate pH=6.5, equalizing tank 2 water outlets enter the MBR reactor through impeller pump, sludge concentration is 10g/L in the reactor, dissolved oxygen concentration is 4mg/L in the pond, membrane module adopts hollow fiber film assembly, and the MBR reactor waterpower residence time (HRT) is 6h, and waste water is extracted out by vacuum primingpump behind the MBR reactor.Water outlet is regulated pH=6.5 through equalizing tank 3, and equalizing tank 3 water outlets enter the catalyzed oxidation pond through impeller pump, and oxygenant adopts clorox, and concentration is 0.8%, and particle diameter is α-Fe of the 1g/L of 30nm
2O
3Be catalyzer, the reaction times is 30min.Oxidation pond water outlet (pH=7) discharging after settling tank and equalizing tank 4 adjustings.The discharging water outlet consists of COD:150mg/L, volatile phenol after this art breading: 0.4mg/L, methyl alcohol: 40mg/L, methyl-phenoxide: 0.5mg/L.
Claims (10)
1. a methyl-phenoxide production wastewater treatment processing method that contains phenol is characterized in that, this processing method divides following steps to implement:
(1) waste water at first enters air flotation cell and removes suspended substance, gas flotation aids polymerize aluminum chloride concentration in the pond is 500mg/L, the air flotation pool bottom passes into the steam water interface from the pressure air-dissolving tank, and dissolving pressure is at 0.1-0.3MPa, and the residence time of waste water in air flotation pool is 1-5h;
(2) extraction cells, waste water is after air flotation cell is processed, enter equalizing tank, the equalizing tank water outlet enters the multi-stage solvent extraction tower through impeller pump, extraction agent enters the extraction tower bottom through magnetic drive pump, waste water goes out to enter oil trap from the extraction tower bottom from top to bottom, and extraction agent goes out to enter regenerator column from the extraction tower cat head and reclaims phenol by the alkali lye reextraction;
(3) waste water that goes out from oil trap enters equalizing tank through impeller pump, regulates pH=6-8, and the equalizing tank water outlet enters the MBR reactor through impeller pump, and waste water is extracted out by vacuum primingpump behind the MBR reactor;
(4) waste water that goes out from the MBR unit enters equalizing tank through impeller pump, regulates pH=6-8, and the equalizing tank water outlet enters catalyst oxidation reactor through impeller pump, carries out catalytic oxidation, and the catalyst oxidation reactor water outlet is discharged after regulating pH=7 through settling tank, equalizing tank.
2. a kind of methyl-phenoxide production wastewater treatment technique that contains phenol according to claim 1 is characterized in that described in the step (1), gas flotation aids is the polymerize aluminum chloride of 500mg/L.
3. a kind of methyl-phenoxide production wastewater treatment technique that contains phenol according to claim 1 is characterized in that described in the step (1), the residence time of waste water in air flotation pool is 1-5h.
4. a kind of methyl-phenoxide production wastewater treatment technique that contains phenol according to claim 1, it is characterized in that described in the step (2) that it is 0.8: 1.2: 2.9 that extraction agent forms N-decoyl tetramethyleneimine (OPOD), tributyl phosphate (TBP), methylcarbonate (DMC) and solvent kerosene proportioning: 7.
5. a kind of methyl-phenoxide production wastewater treatment technique that contains phenol according to claim 1 is characterized in that described in the step (2), and the extraction water oil ratio is controlled at 1: 5.
6. a kind of methyl-phenoxide production wastewater treatment technique that contains phenol according to claim 1 is characterized in that described in the step (2), and alkali lye adopts 20% (wt%) NaOH solution.
7. a kind of methyl-phenoxide production wastewater treatment technique that contains phenol according to claim 1 is characterized in that described in the step (3), and sludge concentration is 5-10g/L in the reactor.
8. a kind of methyl-phenoxide production wastewater treatment technique that contains phenol according to claim 1 is characterized in that described in the step (3), the MBR reactor waterpower residence time (HRT) is controlled to be 4-6h.
9. a kind of methyl-phenoxide production wastewater treatment technique that contains phenol according to claim 1 is characterized in that described in the step (4), and catalyzer is the nanometer α-Fe of the 30-200nm of 1g/L
2O
3
10. a kind of methyl-phenoxide production wastewater treatment technique that contains phenol according to claim 1 is characterized in that described in the step (4), oxygenant is the clorox of 0.1%-2%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105476941A CN102976561A (en) | 2012-12-17 | 2012-12-17 | Technique for treating phenol/anisole-containing production wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105476941A CN102976561A (en) | 2012-12-17 | 2012-12-17 | Technique for treating phenol/anisole-containing production wastewater |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102976561A true CN102976561A (en) | 2013-03-20 |
Family
ID=47850978
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012105476941A Pending CN102976561A (en) | 2012-12-17 | 2012-12-17 | Technique for treating phenol/anisole-containing production wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102976561A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106865853A (en) * | 2017-02-27 | 2017-06-20 | 广东工业大学 | A kind of method for separating Phenolic Compounds From Wastewater Containing Phenols compound |
| CN109052595A (en) * | 2018-08-20 | 2018-12-21 | 上海优帛环境技术有限公司 | A kind of compound coagulant quickly handled for quenching waste water and its application method |
| CN111115740A (en) * | 2019-12-31 | 2020-05-08 | 中钢集团鞍山热能研究院有限公司 | Cycloalkanamide dephenolizing extraction agent and application thereof |
| CN114106220A (en) * | 2020-08-31 | 2022-03-01 | 中国石油化工股份有限公司 | Method for reducing phenolic substance odor in molybdenum series 1, 2-polybutadiene production |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1364606A1 (en) * | 1986-01-27 | 1988-01-07 | Воронежский технологический институт | Method of extracting cresols from acid aqueous solutions |
| US6071409A (en) * | 1998-07-07 | 2000-06-06 | Abb Lummus Global Inc. | Phenolic wastewater treatment with ethers for removal and recovery of phenolics |
| CN1403394A (en) * | 2001-08-27 | 2003-03-19 | 中国石油化工股份有限公司 | Pre-treating method of metacresol production effluent |
| CN1569831A (en) * | 2004-04-27 | 2005-01-26 | 上海大学 | Phenol-containing wastewater extraction agent N-octanoyl pentazane and its synthesis method |
| CN101781038A (en) * | 2010-03-02 | 2010-07-21 | 济南冶金化工设备有限公司 | Phenol and cyanogen waste water physical chemical method control process and equipment |
| CN102491581A (en) * | 2011-11-14 | 2012-06-13 | 中国海洋石油总公司 | Advanced treatment method for production waste water of acrylic acid and ester device |
-
2012
- 2012-12-17 CN CN2012105476941A patent/CN102976561A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1364606A1 (en) * | 1986-01-27 | 1988-01-07 | Воронежский технологический институт | Method of extracting cresols from acid aqueous solutions |
| US6071409A (en) * | 1998-07-07 | 2000-06-06 | Abb Lummus Global Inc. | Phenolic wastewater treatment with ethers for removal and recovery of phenolics |
| CN1403394A (en) * | 2001-08-27 | 2003-03-19 | 中国石油化工股份有限公司 | Pre-treating method of metacresol production effluent |
| CN1569831A (en) * | 2004-04-27 | 2005-01-26 | 上海大学 | Phenol-containing wastewater extraction agent N-octanoyl pentazane and its synthesis method |
| CN101781038A (en) * | 2010-03-02 | 2010-07-21 | 济南冶金化工设备有限公司 | Phenol and cyanogen waste water physical chemical method control process and equipment |
| CN102491581A (en) * | 2011-11-14 | 2012-06-13 | 中国海洋石油总公司 | Advanced treatment method for production waste water of acrylic acid and ester device |
Non-Patent Citations (1)
| Title |
|---|
| 邵德智等: "DNBP生产废水处理工艺探讨", 《环境科学与技术》, vol. 31, no. 9, 30 September 2008 (2008-09-30) * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106865853A (en) * | 2017-02-27 | 2017-06-20 | 广东工业大学 | A kind of method for separating Phenolic Compounds From Wastewater Containing Phenols compound |
| CN106865853B (en) * | 2017-02-27 | 2020-10-27 | 广东工业大学 | Method for separating phenolic compounds in phenol-containing wastewater |
| CN109052595A (en) * | 2018-08-20 | 2018-12-21 | 上海优帛环境技术有限公司 | A kind of compound coagulant quickly handled for quenching waste water and its application method |
| CN111115740A (en) * | 2019-12-31 | 2020-05-08 | 中钢集团鞍山热能研究院有限公司 | Cycloalkanamide dephenolizing extraction agent and application thereof |
| CN114106220A (en) * | 2020-08-31 | 2022-03-01 | 中国石油化工股份有限公司 | Method for reducing phenolic substance odor in molybdenum series 1, 2-polybutadiene production |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104944646B (en) | Wastewater advanced treatment method coupling membrane and electricity | |
| CN102976561A (en) | Technique for treating phenol/anisole-containing production wastewater | |
| CN1119286C (en) | Process for pre-treating waste liquid of p-benzoic acid by complexing and extraction | |
| CN201762209U (en) | Integrally combined device for recycling coking wastewater | |
| CN105858950A (en) | Dyeing wastewater advanced treatment method and device by using ozone, oxydol and activated carbon | |
| CN105174577A (en) | Coal chemical wastewater pretreatment process and device | |
| CN103613159A (en) | Treatment process of phenol-containing wastewater in dicumyl peroxide production | |
| CN100420508C (en) | Microemulsion and its preparation process and use in treating industrial phenolic waste water | |
| CN103818982B (en) | Centrifugal extracting wastewater dephenolization technology | |
| CN105037131A (en) | Novel process for recovering PTA (purified terephthalic acid) wastewater | |
| CN102146101B (en) | Method for extracting humic acid substances from methane fluid | |
| CN102963960B (en) | Method for simultaneously recycling sulfuric acid and organic substances in m-cresol production wastewater | |
| CN105417793A (en) | Treatment method for organic wastewater | |
| CN107935094A (en) | Resin adsorption regenerates the treatment process device and method of high concentrated organic waste liquid | |
| CN103570196B (en) | Device for removing high-concentration ammonia nitrogen from oil refining wastewater by using surfactant | |
| CN202744500U (en) | Treatment device for light oil deodorizing caustic sludge | |
| CN110117034A (en) | A kind of method of Centrifugical extraction high-concentration phenolic wastewater and its recycling | |
| CN114534501B (en) | Electrodialysis device and method for separating nitric acid and acetic acid | |
| CN212740968U (en) | System for treating and recycling J acid | |
| CN204981457U (en) | Coal chemical wastewater preprocessing device | |
| CN216972179U (en) | High-precision treatment system for high-salt organic wastewater | |
| CN204824439U (en) | Natural pond liquid preprocessing device | |
| CN205616677U (en) | Ozone, hydrogen peroxide solution and active carbon are to printing and dyeing wastewater advanced treatment unit | |
| CN210065340U (en) | System for high concentration COD waste water resourceful treatment | |
| CN210885671U (en) | Recovery unit of metribuzin production waste acid water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130320 |