CN102942275B - Method for treating medicament waste water with organic phosphorous water - Google Patents
Method for treating medicament waste water with organic phosphorous water Download PDFInfo
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- CN102942275B CN102942275B CN 201210452793 CN201210452793A CN102942275B CN 102942275 B CN102942275 B CN 102942275B CN 201210452793 CN201210452793 CN 201210452793 CN 201210452793 A CN201210452793 A CN 201210452793A CN 102942275 B CN102942275 B CN 102942275B
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Abstract
The invention discloses a method for treating medicament waste water with organic phosphorous water. The method is characterized in that waste water is treated under the condition of normal temperature and normal pressure through a photoelectric catalytic oxidation process, and is discharged within controlling indexes of a national standard after chemical treatment. A specific process flow comprises the following steps of: homogenizing medicament waste water with organic phosphorous water by a regulating reservoir 1; feeding into a photoelectric catalytic oxidation device 2 by a water supply pump; enabling water to react in the device under the action of a catalyst; enabling effluent to flow into a reactor 3; adding Ca(OH)2 into the front end of the reactor 3; adding one or more substances of polyaluminium chloride, bodied ferric sulfate and polyaluminum sulfate into the middle part of the reactor; adding a polyacrylamide substance into the tail part of the reactor; enabling effluent to flow into an inclined-plate settler 4; and precipitating a supernatant to directly discharge water within controlling index of a national standard.
Description
Technical field
The present invention relates to a kind for the treatment of process of organophosphorus water treatment agent waste water, the main combined treatment process that adopts photoelectrocatalysioxidization oxidization to combine with chemical treatment, make water treatment agent production and Wastewater Form Circulating Cooling Water waste water realize qualified discharge, belong to the environmental engineering technical field of sewage.
Background technology
Industrial circulating water system mainly adopts the organic inhibiter at present; the organic inhibiter mainly includes the compounds such as machine phosphorus, organic amine; wherein take as the leading factor with organophosphorus compound again; as Amino Trimethylene Phosphonic Acid (ATMP), hydroxy ethylene diphosphonic acid (HEDP), 2-phosphinylidyne butane-1; 2,4-tricarboxylic acid (PBTC), Soxylat A 25-7 glycerol phosphoric acid ester etc. are organic phosphates anti-incrustation corrosion inhibitor commonly used.
Up to the present, the phosphorus removing method that generally adopts both at home and abroad mainly contains chemical dephosphorization method and biological dephosphorization, and biochemical dephosphorization method chemical and that biological phosphate-eliminating combines.
(1) biological phosphate-eliminating
PolyP bacteria is active sludge prolific a kind of aerobic bacteria in the anaerobic-aerobic alternation procedure, though competitive capacity is very poor, can store poly-β hydroxybutyric acid (PHB) and poly-phosphate (Poly-P) in cell.In the anaerobic-aerobic process, polyP bacteria is dominant bacteria in anaerobic pond, consisted of the main body of active sludge flco, it absorbs the organism (as lipid acid) of molecule, to be stored in simultaneously the phosphorus in poly-phosphate in cell (Poly-P), discharge by hydrolysis, and necessary energy is provided.Oxidized decomposition also provides energy, simultaneously can absorb the more phosphorus that discharges than anaerobic condition from sewage, quantitatively considerably beyond the synthetic required phosphorus amount of its cell, the form of phosphorus with poly-phosphate is housed in thalline, and forming high phosphorus sludge, system discharges by excess sludge.
Adopt the method to have advantages of that processing cost is low, but finally be difficult to realize the qualified discharge of phosphorus.
(2) physico-chemical processes dephosphorization
Chemical method and physico-chemical processes mainly contain the techniques such as coagulant sedimentation, crystallization process, ion exchange adsorption, electrodialysis, reverse osmosis, the main processing inorganic states phosphorus-containing wastewater that is fit to.Its advantage is that dephosphorization efficiency by using is higher, is beneficial to the qualified discharge of phosphorus.
the present invention mainly adopts photoelectrocatalysioxidization oxidization and chemical treatment combination process, adopting the photoelectrocatalysioxidization oxidization technology that organophosphorus waste water is processed makes it be converted into the phosphorus-containing wastewater of inorganic states, thereby photocatalysis oxidation technique is to utilize photochemical method to produce the multiple strong oxidizer such as hydroxyl radical free radical OH the organic pollutant exhaustive oxidation is inorganic molecules, electro-catalytic oxidation technology produces the strong oxidizer degradation of organic substances by anode, thereby make pollution substance direct oxidation or utilize the active substance generation oxidizing reaction that electrode surface produces to reach the purpose of removing pollutent on electrode surface.The coupling of photochemical catalytic oxidation and catalytic oxidation process has produced certain synergy, impels the photoelectric catalysis degrading process to have higher degradation efficiency.Realized the integrated of two kinds of high-level oxidation technologies and had complementary advantages.Simultaneously realized that also the toxicity of organic pollutant removes the accumulation of having avoided the high toxicity organic substance.
Phosphorus-containing wastewater for the inorganic states after transforming adopts chemical treatment method to make its precipitation, finally realizes the qualified discharge of waste water.The present invention finds to use the photoelectrocatalysioxidization oxidization technology that organophosphorus waste water is processed through repetition test research, can obtain good effect.
Summary of the invention
The present invention is directed to organophosphorus water treatment agent waste water, propose a kind of novel treatment process, this process using " photoelectrocatalysioxidization oxidization and chemical treatment combination process ".Waste water first by photoelectrocatalysioxidization oxidization technique will be wherein the difficult degradation organophosphates be converted into inorganic phosphorus, then will inorganic Phosphorus material method removal by chemical precipitation.
Present method has realized effective processing of organophosphorus water treatment agent waste water by this cover integrated technique, avoided such waste water owing to adopting biochemistry to be difficult to the shortcomings such as effectively processing
The present invention is a kind of organophosphorus water treatment agent method of wastewater treatment, it is characterized in that: under normal temperature and pressure conditions, waste water after the photoelectrocatalysioxidization oxidization art breading, then is realized its qualified discharge by chemical treatment:
The concrete technology flow process is as follows:
After organophosphorus water treatment agent waste water process equalizing tank 1 homogeneous, enter photoelectrocatalysioxidization oxidization device 2 through working shaft, water reacts through catalyst action in this device, and in water outlet inflow reactor 3, reactor 3 front ends add Ca(OH)
2The reactor middle part adds one or more materials in polymerize aluminum chloride, bodied ferric sulfate, polyaluminium sulfate, the reactor afterbody adds polyacrylamide substances, and water outlet flows in inclined-plate clarifying basin 4, and the supernatant liquor after precipitation can direct water outlet be realized qualified discharge.
According to the method described in the present invention, it is characterized in that: waste water residence time in the photoelectrocatalysioxidization oxidization device is 1～2 hour.
According to the method described in the present invention, it is characterized in that: photoelectrocatalysioxidization oxidization device loading catalyst is central in reactor bottom and pole plate, one or more in described catalyzer employing Alpha-alumina or silicon-dioxide are carrier, and one or more active substances in surface load titanium dioxide, Cadmium Sulfide, ferric oxide, Manganse Dioxide consist of; Have cracking and open loop function, and the pore structure tunable characteristic, and be prepared into the honeycomb vesicular structure.
According to the method described in the present invention, it is characterized in that: add the salt of 1g/L ~ 3g/L in the photoelectrocatalysioxidization oxidization device, salt is by NaCl, Na
2SO
4, Na
2CO
3, NaHCO
3In one or more materials consist of.
According to the method described in the present invention, it is characterized in that: electrode materials adopts the immobilized precious metal material of titanium substrate surface to be prepared from, and the precious metal material adopts one or more materials in the oxide compounds such as platinum, ruthenium, iridium, rubidium, zirconium to consist of.
According to the method described in the present invention, it is characterized in that: it is one or more in high voltage mercury lamp, medium pressure mercury lamp and the ultraviolet lamp of 200～400nm that light source adopts wavelength.
Catalyzer of the present invention has stronger cracking and open loop function, and effectively utilize the pore structure tunable characteristic, be prepared into the honeycomb vesicular structure, increased the contact area with waste water, be beneficial to larger molecular organics enrichment in the catalyzer duct, accelerated the photoelectrocatalysioxidization oxidization speed of reaction, the loop chain of biodegradable organic compounds has been opened, and further obtained oxidative degradation.
Description of drawings
Fig. 1 is the process flow diagram of a kind of organophosphorus water treatment agent of the present invention method of wastewater treatment embodiment.Wherein 1 is the water treatment agent phosphorus-containing wastewater, and 2 is the optoelectronic integration reactor, and 3 are chemical precipitation and coagulated agent device, and 4 is inclined plate sedimentation device.
Fig. 2 is the structural representation of the device 2 part optoelectronic integration reactors in accompanying drawing one.
Embodiment
Embodiment one:
Tianjin production water treatment agent factory, to produce organic phosphates inhibiter, Scale inhibitors as main, externally discharged waste water is mainly take the cask washing kettle washing water as main, per hour sewage effluent is 100 tons, because the water time is unfixing, biological inoculum is poor to the organophosphates degradation property simultaneously, and the equal severe overweight of COD and phosphorus can't reach relevant water outlet emission standard.adopt photoelectrocatalysioxidization oxidization and chemical treatment combination process to carry out engineering Application Research to this phosphorus-containing wastewater, influent COD cr is 300 ~ 500mg/L, total phosphorus is 30 ~ 40mg/L, positive phosphorus is in the situation of 2 ~ 3mg/L, add the NaCl of 1g/L and the Na2SO4 of 0.5g/L in the photoelectrocatalysioxidization oxidization reactor, in the photoelectrocatalysioxidization oxidization reactor, hydraulic detention time is 3 hours, after the anionic polyacrylamide of 0.2g/L polyaluminium sulfate and 0.01g/L is added in water outlet, in final outflow water water quality, CODcr is 30 ~ 40mg/L, total phosphorus is 0.2 ~ 0.4mg/L, satisfied the qualified discharge water quality requirement.
Embodiment two:
Tianjin petrochemical plant circulating water system is added the various medicaments such as Scale inhibitors, inhibiter, and this system sewerage COD and phosphorus all exceed standard, and can't reach relevant water outlet emission standard.Adopt photoelectrocatalysioxidization oxidization and chemical treatment combination process to carry out engineering Application Research to this phosphorus-containing wastewater, influent COD cr is 100 ~ 150mg/L, total phosphorus is in the situation of 15 ~ 20mg/L, adds the NaCl of 1.5g/L and the Na of 0.25g/L in the photoelectrocatalysioxidization oxidization reactor
2SO
4In the photoelectrocatalysioxidization oxidization reactor, hydraulic detention time is 1.5 hours, and after the anionic polyacrylamide of 0.15g/L polyaluminium sulfate and 0.01g/L was added in water outlet, in final outflow water water quality, CODcr was 40 ~ 50mg/L, total phosphorus is 0.4 ~ 0.5mg/L, has satisfied the qualified discharge water quality requirement.
Claims (5)
1. organophosphorus water treatment agent method of wastewater treatment is characterized in that: under normal temperature and pressure conditions, waste water after the photoelectrocatalysioxidization oxidization art breading, then is realized its qualified discharge by chemical treatment:
The concrete technology flow process is as follows:
After organophosphorus water treatment agent waste water process equalizing tank (1) homogeneous, enter photoelectrocatalysioxidization oxidization device (2) through working shaft, water reacts through catalyst action in this device, and in water outlet inflow reactor (3), reactor (3) front end adds Ca(OH)
2The reactor middle part adds one or more materials in polymerize aluminum chloride, bodied ferric sulfate, polyaluminium sulfate, the reactor afterbody adds polyacrylamide substances, and water outlet flows in inclined-plate clarifying basin (4), and the direct water outlet of the supernatant liquor after precipitation realizes qualified discharge;
Described photoelectrocatalysioxidization oxidization device loading catalyst is central in reactor bottom and pole plate, one or more in described catalyzer employing Alpha-alumina or silicon-dioxide are carrier, and one or more active substances in surface load titanium dioxide, Cadmium Sulfide, ferric oxide, Manganse Dioxide consist of; Have cracking and open loop function, and the pore structure tunable characteristic, and be prepared into the honeycomb vesicular structure.
2. it is characterized in that in accordance with the method for claim 1: waste water residence time in the photoelectrocatalysioxidization oxidization device is 1～2 hour.
3. in accordance with the method for claim 1, it is characterized in that: add the salt of 1g/L ~ 3g/L in the photoelectrocatalysioxidization oxidization device, salt is by NaCl, Na
2SO
4, Na
2CO
3, NaHCO
3In one or more materials consist of.
4. in accordance with the method for claim 1, it is characterized in that: the electrode materials in described photoelectrocatalysioxidization oxidization device adopts the immobilized precious metal material of titanium substrate surface to be prepared from, and the precious metal material adopts one or more materials in platinum, ruthenium, iridium, rubidium, Zirconium oxide to consist of.
5. it is characterized in that in accordance with the method for claim 1: it is one or more in high voltage mercury lamp, medium pressure mercury lamp and the ultraviolet lamp of 200～400nm that light source in described photoelectrocatalysioxidization oxidization device adopts wavelength.
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| CN103382062B (en) * | 2013-07-10 | 2014-07-09 | 安徽农业大学 | Method for using tea extract as underwater organophosphorus pesticide chlorpyrifos treatment agent |
| CN104058516B (en) * | 2014-05-30 | 2015-11-25 | 安徽国星生物化学有限公司 | A kind for the treatment of process of the phosphorus-containing wastewater in glyphosate production process generation |
| CN104591335A (en) * | 2015-01-13 | 2015-05-06 | 安徽国星生物化学有限公司 | New method for treating chlorpyrifos wastewater by using semiconductor nano materials |
| CN104826854B (en) * | 2015-05-07 | 2017-08-25 | 环境保护部南京环境科学研究所 | A kind of regeneration treating method of the dangerous solid waste containing organophosphorus insecticide |
| CN109336235A (en) * | 2018-12-04 | 2019-02-15 | 苏州西姆提纳米科技有限公司 | A kind of composite flocculation agent and its application |
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| CN202193674U (en) * | 2011-07-22 | 2012-04-18 | 浙江环耀环境建设有限公司 | Organophosphorus-containing waste water treatment device |
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Address after: 100010 Chaoyangmen North Street, Dongcheng District, Dongcheng District, Beijing Co-patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE CO., LTD. Patentee after: China Offshore Oil Group Co., Ltd. Address before: 100010 Chaoyangmen North Street, Dongcheng District, Dongcheng District, Beijing Co-patentee before: CNOOC Tianjin Chemical Research & Design Institute Patentee before: China National Offshore Oil Corporation |