CN105692956A - Treatment method for low-concentration organophosphorus wastewater - Google Patents
Treatment method for low-concentration organophosphorus wastewater Download PDFInfo
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- 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
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- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- 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
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- 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
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C02F2301/00—General aspects of water treatment
- C02F2301/04—Flow arrangements
- C02F2301/043—Treatment of partial or bypass streams
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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Abstract
The invention discloses a treatment method for low-concentration organophosphorus wastewater. The treatment method includes the following steps of 1, wastewater pretreatment, wherein sodium hypochlorite is added to the wastewater for sterilization, then sand filtration is conducted, and the water passes a precision filter to be subjected to ultra-filtration; 2, resin softening, wherein the pretreated wastewater passes a softening resin tower at the speed per hour of 20-25 m/h to be softened; 3, reverse osmosis concentration, wherein a reducing agent, a scale inhibitor and non-oxidizing bactericide are added to the softened water, then the water passes a cartridge filter, reverse osmosis concentration is conducted, and the concentrated water is subjected to secondary ultra-filtration and secondary reverse osmosis; 4, Fenton oxidation, wherein the PH value of the concentrated wastewater is adjusted, a Fenton reagent is added, and the water flows into an effluent storage tank after a heating reaction is conducted for 2-3 h. The organophosphorus wastewater is treated through combination of the membrane technology and Fenton, the content of phosphorus in the organophosphorus wastewater can be reduced to an emission standard, cost is low, economical efficiency is good, and the recovery rate of the wastewater is high.
Description
Technical field
The present invention relates to technical field of waste water processing, be specifically related to the processing method of a kind of low concentration organism P wastewater。
Background technology
Organic phosphorus compound mainly includes phosphate ester, phosphite ester, burnt phospholipid, phosphinate, ammonium phosphate etc., and some of them phosphate compounds has very big toxicity。Many pesticide all contain organophosphor composition, organophosphorus pesticide production process can produce substantial amounts of organism P wastewater unavoidably, its toxicity is big, constituent is complicated, it is difficult to biodegradation, these waste water enter whose bad water ecosystem rivers water body will destroy, and the living environment of the mankind can be caused great threat。The primary standard of China's integrated wastewater discharge standard (GB8978-1996) is phosphate (in P)≤0.5mg/L, and secondary standard is phosphate (in P)≤1.0mg/L。
The conventional processing method of phosphorus-containing wastewater mainly has chemical dephosphorization method, biological dephosphorization, electrolysis, embrane method, advanced oxidation processes, physisorphtion etc.。At present, what adopt senior high-level oxidation technology mainly has photocatalysis oxidation technique, ozonation technology, Fenton oxidation technology。Photochemical catalytic oxidation is mainly based on artificial light source, and organic discomposing effect is better, but light source utilization rate is low, energy consumption is big, and investment cost is high, catalyst easy in inactivation, the oxidability of ozone oxidation is strong, and reaction condition is gentle, non-secondary pollution, but it is complicated that ozone generates equipment, yield of ozone is low and utilization rate is low, and reaction selectivity is strong, energy consumption is big, processing cost is high, Fenton oxidation reaction condition is gentle, equipment and simple to operate, handling is with relatively low, applied widely。Now research shows, organophosphor is had Degradation by Fenton reagent, Fenton oxidation technology is applied to organism P wastewater process and has great researching value。
Summary of the invention
It is an object of the invention to, for prior art, it is provided that the processing method of a kind of low concentration organism P wastewater。
For achieving the above object, the present invention takes techniques below scheme: the processing method of a kind of low concentration organism P wastewater, comprises the following steps:
(1) Wastewater Pretreatment: phosphorus-containing wastewater is entered in phosphorus-containing wastewater raw water box by water pump lifting, add sodium hypochlorite to raw water box and carry out sterilizing, waste water after sterilizing enters Sand Filtration System through sand filtration elevator pump and is filtered, water after filtration enters in ultrafiltration raw water box, ultra-filtration filters equipment is entered by 50～60 μm of accurate filters then through water pump, it is 0.01～0.03Mpa at pressure, retain the float and colloidal solid that remove in water, waste water after ultrafiltration enters ultrafiltration and produces water tank, and concentrated stream returns raw water box；
(2) resin softening: ultrafiltration is produced the water in water tank through water pump, with speed per hour for 20～25m/h by softening resin tower, removes the calcium ions and magnesium ions in waste water, and the water after softening enters softening and produces water tank；
(3) reverse osmosis concentration: produce to softening and add reducing agent in water, 5～10 μm of cartridge filters are crossed through booster pump after antisludging agent and non-oxidative antimicrobial, reverse osmosis unit is passed through then through high-pressure pump, it is that 0.5～1Mpa concentrates at pressure, clear water after concentration is collected and is entered fresh water collecting case, detect rear discharge up to standard, below standard, pass into raw wastewater case, dense water after concentration is entered second ultrafiltration raw water box, enter after 50～60 μm of accurate filters entrance ultra-filtration filters equipment through booster pump, concentrate recirculation enters ultrafiltration raw water box, produce water entrance secondary counter and penetrate into water tank, 5～10 μm of cartridge filters are crossed by booster pump, permeate high-pressure pump then through secondary counter and pass through reverse osmosis unit, it is that 1～1.5Mpa concentrates at pressure, clear water after concentration is collected and is entered fresh water collecting case, detect rear discharge up to standard, below standard, pass in second ultrafiltration raw water box, dense water enters dense water tank；
(4) Fenton oxidation: enter Fenton oxidation pond by elevator pump after regulating the pH value in dense water tank with sulphuric acid, by hydrogen peroxide and Fe2+Solution mixes, and regulates solution ph with dilute hydrochloric acid and makes Fenton reagent to 3.0, in the dosage of 1000mg/L interpolation Fenton reagent to Fenton oxidation pond, to pass into water outlet storage box after reacting by heating 2～3h。
Wherein, in described ultra-filtration filters equipment, ultrafilter membrane is PVD hollow-fibre membrane, and aperture is 0.01～0.5 μm。
Wherein, in described Fenton reagent, the mol ratio of hydrogen peroxide and Fe2+ is: 4:1。
Wherein, described Fe2+ is green vitriol。
Wherein, the pH value regulating dense water in described step (4) is 2.5～4.0。
Wherein, the described reaction temperature in Fenton oxidation pond is: 50～60 DEG C。
Further, sand filtration of the present invention, as the pretreatment of ultrafiltration, can remove the macromolecular solid in water and colloid, reduces turbidity of wastewater, alleviates film blocking and the fouling membrane of ultrafilter membrane, delays the service life of ultrafilter membrane。
Further, raw wastewater first passes through ultrafiltration and removes macromole and dissolubility large particulate matter, and ultra-filtration water softens hardness through resin and substantially reduces, it is ensured that the requirement of feed water by reverse osmosis water quality, it is prevented that the stifled film of concentration process and fouling。
Further, before accurate filter and cartridge filter are respectively applied to ultra-filtration filters and osmosis filtration, the subtitle substance stayed after filtering before can filtering, protection ultrafiltration and reverse osmosis original paper be not by the damage of large particulate matter。
Further, the organophosphor in waste water can be concentrated by reverse osmosis technology, improves Fenton oxidation reaction density, reduces the reaction cost of reaction。
Further, reverse osmosis concentration is carried out again supermembrane filtration, the macromolecular particle easily precipitated out in water can be removed, also can will occur that because cycles of concentration is too high floccule is removed, ultra-filtration water performed twice at reverse osmosis concentration, is obtaining more clear water, the recovery utilization rate of waste water can be improved。
Further, Fenton reagent is ferrous sulfate and the hydrogen peroxide solution of certain mol proportion, hydrogen peroxide is under ferrous catalysis under certain conditions, can resolve into efficiently and there is Strong oxdiative ability and high electronegativity or electrophilicity hydroxyl radical free radical, organic pollution in hydroxyl radical free radical energy oxidative degradation water so that it is mineralising is carbon dioxide, water and inorganic salt。
The invention has the beneficial effects as follows: the present invention adopts membrane technology and Fenton oxidation method that organism P wastewater is carried out dephosphorization process, first low concentration organism P wastewater is concentrated, Fenton oxidation is adopted to have high concentration organism P wastewater to aoxidize again, Fenton system continuous-stable, operating cost is low, good economy performance, waste water dephosphorization is effective, can reaching discharge standard, the waste water energy after process recycles, and waste water reclamation rate is up to 70%。
Detailed description of the invention
Below in conjunction with specific embodiment, to further instruction of the present invention。
Embodiment 1
The processing method of a kind of low concentration organism P wastewater, comprises the following steps:
(1) Wastewater Pretreatment: phosphorus-containing wastewater is entered in phosphorus-containing wastewater raw water box by water pump lifting, add sodium hypochlorite to raw water box and carry out sterilizing, waste water after sterilizing enters Sand Filtration System through sand filtration elevator pump and is filtered, water after filtration enters in ultrafiltration raw water box, entering ultrafilter membrane then through water pump by 60 μm of accurate filters is PVD hollow-fibre membrane, aperture is the ultra-filtration filters equipment of 0.5 μm, it is 03Mpa at pressure, retain the float and colloidal solid that remove in water, waste water after ultrafiltration enters ultrafiltration and produces water tank, and concentrated stream returns raw water box；
(2) resin softening: ultrafiltration is produced the water in water tank through water pump, with speed per hour for 25m/h by softening resin tower, removes the calcium ions and magnesium ions in waste water, and the water after softening enters softening and produces water tank；
(3) reverse osmosis concentration: produce to softening and add reducing agent in water, 10 μm of cartridge filters are crossed through booster pump after antisludging agent and non-oxidative antimicrobial, reverse osmosis unit is passed through then through high-pressure pump, it is that 1Mpa concentrates at pressure, clear water after concentration is collected and is entered fresh water collecting case, detect rear discharge up to standard, below standard, pass into raw wastewater case, dense water after concentration is entered second ultrafiltration raw water box, enter after 60 μm of accurate filters entrance ultra-filtration filters equipment through booster pump, concentrate recirculation enters ultrafiltration raw water box, produce water entrance secondary counter and penetrate into water tank, 10 μm of cartridge filters are crossed by booster pump, permeate high-pressure pump then through secondary counter and pass through reverse osmosis unit, it is that 1.5Mpa concentrates at pressure, clear water after concentration is collected and is entered fresh water collecting case, detect rear discharge up to standard, below standard, pass in second ultrafiltration raw water box, dense water enters dense water tank；
(4) Fenton oxidation: the pH value regulated in dense water tank with sulphuric acid is enter Fenton oxidation pond by elevator pump after 4.0, hydrogen peroxide is mixed for 4:1 in molar ratio with green vitriol solution, regulate solution ph with dilute hydrochloric acid and make Fenton reagent to 3.0, with in the dosage of 1000mg/L interpolation Fenton reagent to Fenton oxidation pond, heating, to 60 DEG C, passes into water outlet storage box after reaction 3h。
Embodiment 2
The processing method of a kind of low concentration organism P wastewater, comprises the following steps: the processing method of a kind of low concentration organism P wastewater, comprises the following steps: the processing method of a kind of low concentration organism P wastewater, comprises the following steps:
(1) Wastewater Pretreatment: phosphorus-containing wastewater is entered in phosphorus-containing wastewater raw water box by water pump lifting, add sodium hypochlorite to raw water box and carry out sterilizing, waste water after sterilizing enters Sand Filtration System through sand filtration elevator pump and is filtered, water after filtration enters in ultrafiltration raw water box, entering ultrafilter membrane then through water pump by 50 μm of accurate filters is PVD hollow-fibre membrane, aperture is the ultra-filtration filters equipment of 0.01 μm, it is 0.01Mpa at pressure, retain the float and colloidal solid that remove in water, waste water after ultrafiltration enters ultrafiltration and produces water tank, and concentrated stream returns raw water box；
(2) resin softening: ultrafiltration is produced the water in water tank through water pump, with speed per hour for 20m/h by softening resin tower, removes the calcium ions and magnesium ions in waste water, and the water after softening enters softening and produces water tank；
(3) reverse osmosis concentration: produce to softening and add reducing agent in water, 5 μm of cartridge filters are crossed through booster pump after antisludging agent and non-oxidative antimicrobial, reverse osmosis unit is passed through then through high-pressure pump, it is that 0.5Mpa concentrates at pressure, clear water after concentration is collected and is entered fresh water collecting case, detect rear discharge up to standard, below standard, pass into raw wastewater case, dense water after concentration is entered second ultrafiltration raw water box, enter after 50 μm of accurate filters entrance ultra-filtration filters equipment through booster pump, concentrate recirculation enters ultrafiltration raw water box, produce water entrance secondary counter and penetrate into water tank, 5 μm of cartridge filters are crossed by booster pump, permeate high-pressure pump then through secondary counter and pass through reverse osmosis unit, it is that 1Mpa concentrates at pressure, clear water after concentration is collected and is entered fresh water collecting case, detect rear discharge up to standard, below standard, pass in second ultrafiltration raw water box, dense water enters dense water tank；
(4) Fenton oxidation: the pH value regulated in dense water tank with sulphuric acid is enter Fenton oxidation pond by elevator pump after 2.5, hydrogen peroxide is mixed for 4:1 in molar ratio with green vitriol solution, regulate solution ph with dilute hydrochloric acid and make Fenton reagent to 3.0, with in the dosage of 1000mg/L interpolation Fenton reagent to Fenton oxidation pond, heating, to 50 DEG C, passes into water outlet storage box after reaction 2h。
Embodiment 3
The processing method of a kind of low concentration organism P wastewater, comprises the following steps: the processing method of a kind of low concentration organism P wastewater, comprises the following steps: the processing method of a kind of low concentration organism P wastewater, comprises the following steps:
(1) Wastewater Pretreatment: phosphorus-containing wastewater is entered in phosphorus-containing wastewater raw water box by water pump lifting, add sodium hypochlorite to raw water box and carry out sterilizing, waste water after sterilizing enters Sand Filtration System through sand filtration elevator pump and is filtered, water after filtration enters in ultrafiltration raw water box, entering ultrafilter membrane then through water pump by 55 μm of accurate filters is PVD hollow-fibre membrane, aperture is the ultra-filtration filters equipment of 0.1 μm, it is 0.02Mpa at pressure, retain the float and colloidal solid that remove in water, waste water after ultrafiltration enters ultrafiltration and produces water tank, and concentrated stream returns raw water box；
(2) resin softening: ultrafiltration is produced the water in water tank through water pump, with speed per hour for 22m/h by softening resin tower, removes the calcium ions and magnesium ions in waste water, and the water after softening enters softening and produces water tank；
(3) reverse osmosis concentration: produce to softening and add reducing agent in water, 8 μm of cartridge filters are crossed through booster pump after antisludging agent and non-oxidative antimicrobial, reverse osmosis unit is passed through then through high-pressure pump, it is that 0.9Mpa concentrates at pressure, clear water after concentration is collected and is entered fresh water collecting case, detect rear discharge up to standard, below standard, pass into raw wastewater case, dense water after concentration is entered second ultrafiltration raw water box, enter after 55 μm of accurate filters entrance ultra-filtration filters equipment through booster pump, concentrate recirculation enters ultrafiltration raw water box, produce water entrance secondary counter and penetrate into water tank, 8 μm of cartridge filters are crossed by booster pump, permeate high-pressure pump then through secondary counter and pass through reverse osmosis unit, it is that 1.2Mpa concentrates at pressure, clear water after concentration is collected and is entered fresh water collecting case, detect rear discharge up to standard, below standard, pass in second ultrafiltration raw water box, dense water enters dense water tank；
(4) Fenton oxidation: the pH value regulated in dense water tank with sulphuric acid is enter Fenton oxidation pond by elevator pump after 3, hydrogen peroxide is mixed for 4:1 in molar ratio with green vitriol solution, regulate solution ph with dilute hydrochloric acid and make Fenton reagent to 3.0, with in the dosage of 1000mg/L interpolation Fenton reagent to Fenton oxidation pond, heating, to 55 DEG C, passes into water outlet storage box after reaction 2.5h。
Claims (6)
1. the processing method of a low concentration organism P wastewater, it is characterised in that comprise the following steps:
(1) Wastewater Pretreatment: phosphorus-containing wastewater is entered in phosphorus-containing wastewater raw water box by water pump lifting, add sodium hypochlorite to raw water box and carry out sterilizing, waste water after sterilizing enters Sand Filtration System through sand filtration elevator pump and is filtered, water after filtration enters in ultrafiltration raw water box, ultra-filtration filters equipment is entered by 50～60 μm of accurate filters then through water pump, it is 0.01～0.03Mpa at pressure, retain the float and colloidal solid that remove in water, waste water after ultrafiltration enters ultrafiltration and produces water tank, and concentrated stream returns raw water box；
(2) resin softening: ultrafiltration is produced the water in water tank through water pump, with speed per hour for 20～25m/h by softening resin tower, removes the calcium ions and magnesium ions in waste water, and the water after softening enters softening and produces water tank；
(3) reverse osmosis concentration: produce to softening and add reducing agent in water, 5～10 μm of cartridge filters are crossed through booster pump after antisludging agent and non-oxidative antimicrobial, reverse osmosis unit is passed through then through high-pressure pump, it is that 0.5～1Mpa concentrates at pressure, clear water after concentration is collected and is entered fresh water collecting case, detect rear discharge up to standard, below standard, pass into raw wastewater case, dense water after concentration is entered second ultrafiltration raw water box, enter after 50～60 μm of accurate filters entrance ultra-filtration filters equipment through booster pump, concentrate recirculation enters ultrafiltration raw water box, produce water entrance secondary counter and penetrate into water tank, 5～10 μm of cartridge filters are crossed by booster pump, permeate high-pressure pump then through secondary counter and pass through reverse osmosis unit, it is that 1～1.5Mpa concentrates at pressure, clear water after concentration is collected and is entered fresh water collecting case, detect rear discharge up to standard, below standard, pass in second ultrafiltration raw water box, dense water enters dense water tank；
(4) Fenton oxidation: enter Fenton oxidation pond by elevator pump after regulating the pH value in dense water tank with sulphuric acid, by hydrogen peroxide and Fe2+Solution mixes, and regulates solution ph with dilute hydrochloric acid and makes Fenton reagent to 3.0, in the dosage of 1000mg/L interpolation Fenton reagent to Fenton oxidation pond, to pass into water outlet storage box after reacting by heating 2～3h。
2. the processing method of a kind of low concentration organism P wastewater according to claim 1, it is characterised in that in described ultra-filtration filters equipment, ultrafilter membrane is PVD hollow-fibre membrane, and aperture is 0.01～0.5 μm。
3. the processing method of a kind of low concentration organism P wastewater according to claim 1, it is characterised in that in described Fenton reagent, the mol ratio of hydrogen peroxide and Fe2+ is 4:1。
4. the processing method of a kind of low concentration organism P wastewater according to claim 1, it is characterised in that described Fe2+ is green vitriol。
5. the processing method of a kind of low concentration organism P wastewater according to claim 1, it is characterised in that the pH value regulating dense water in described step (4) is 2.5～4.0。
6. the processing method of a kind of low concentration organism P wastewater according to claim 1, it is characterised in that the described reaction temperature in Fenton oxidation pond is 50～60 DEG C。
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107715844A (en) * | 2017-10-23 | 2018-02-23 | 青岛理工大学 | A kind of parathion-methyl sorbing material preparation method and its usage |
| CN109019999A (en) * | 2018-08-09 | 2018-12-18 | 江苏中电创新环境科技有限公司 | A kind of processing method of the low concentration containing strong complexing nickel waste water |
| CN112723616A (en) * | 2020-12-14 | 2021-04-30 | 九江德福科技股份有限公司 | Wastewater recycling method |
| CN114212940A (en) * | 2021-12-13 | 2022-03-22 | 浙江新安化工集团股份有限公司 | Glyphosate production sewage treatment system and method |
| CN115159731A (en) * | 2022-07-13 | 2022-10-11 | 徐州水处理研究所 | Protective application method of reverse osmosis membrane by adopting alkali hardness-reducing adsorption bed |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107715844A (en) * | 2017-10-23 | 2018-02-23 | 青岛理工大学 | A kind of parathion-methyl sorbing material preparation method and its usage |
| CN107715844B (en) * | 2017-10-23 | 2020-06-16 | 青岛理工大学 | Preparation method and application of methyl parathion adsorption material |
| CN109019999A (en) * | 2018-08-09 | 2018-12-18 | 江苏中电创新环境科技有限公司 | A kind of processing method of the low concentration containing strong complexing nickel waste water |
| CN112723616A (en) * | 2020-12-14 | 2021-04-30 | 九江德福科技股份有限公司 | Wastewater recycling method |
| CN114212940A (en) * | 2021-12-13 | 2022-03-22 | 浙江新安化工集团股份有限公司 | Glyphosate production sewage treatment system and method |
| CN115159731A (en) * | 2022-07-13 | 2022-10-11 | 徐州水处理研究所 | Protective application method of reverse osmosis membrane by adopting alkali hardness-reducing adsorption bed |
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Application publication date: 20160622 |