CN101519251A - Process for treating bio-refractory waste water by up-flow multi-phase oxidation column - Google Patents
Process for treating bio-refractory waste water by up-flow multi-phase oxidation column Download PDFInfo
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- CN101519251A CN101519251A CN200910113967A CN200910113967A CN101519251A CN 101519251 A CN101519251 A CN 101519251A CN 200910113967 A CN200910113967 A CN 200910113967A CN 200910113967 A CN200910113967 A CN 200910113967A CN 101519251 A CN101519251 A CN 101519251A
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Abstract
The invention relates to a process for treating bio-refractory waste water by an up-flow multi-phase oxidation column. Fenton reagent and waste water to be treated are pumped into the up-flow multi-phase oxidation column for reacting 0.5-1h by a pump, wherein the molar ratio of H2O2 to Fe<2+> is 5-20:1 in the process of adding Fenton reagent, wherein the mass ratio of the added hydrogen peroxide and the COD in the waste water to be treated is 2-3:1. The waste water processed in the oxidation column enters a neutralization tank, a degassing tank and a coagulating precipitation tank in sequence, the pH value of the waste water is adjusted to be neutral in the neutralization tank, the waste water is blasted and degassed for 10-20 min in the degassing tank to degas small oxygen bubbles generated in the process of reacting, and is coagulated and precipitated by adding polyacrylamide in the coagulating precipitation tank to obtain supernatant fluid which reaches the discharge standard and is discharged. Experiments prove that the removal rates of the COD and the colority are both larger than 70 percent. The process has simple operation, easy obtaining of reactants, cheapness, no complex equipment, short treating time and high contamination removing rate.
Description
Technical field
The present invention relates to handle the processing method of trade effluent, specifically is the processing method for the treatment of bio-refractory waste water by up-flow multi-phase oxidation column.
Background technology
The waste water of the toxic or bio-refractory of some that produce in the Industrial processes relies on conventional biochemistry and materialization to handle to be difficult to reach emission request, therefore need to do further advanced treatment to bio-chemical effluent merely.In numerous advanced treatment technology, utilizing Fenton reagent to handle waste water technology has simple to operate, reactant is easy to get, expense is cheap, no complex apparatus and advantage such as environmentally friendly, is applied to gradually in the waste water treatment engineerings such as pulping and paper-making, dyestuff, sanitas, photographic developer, agricultural chemicals.
French scientist H.J.Fenton had found Fe in 1894
2+Can pass through H
2O
2The oxidizing reaction of catalysis oxysuccinic acid effectively, the combination that studies show that the two afterwards all is a kind of effective oxygenant to the organism of numerous species.The descendant is the scientist of this greatness in honor of, with Fe
2+And H
2O
2The reagent called after Fenton reagent of forming uses the reaction of this reagent to claim Fenton's reaction.Fenton reagent mainly applies in the research of enzyme reaction and the influence of hydroxyl radical free radical (OH) pair cell subsequently.1964, Canadian scholar H.R.Eisenhaner successfully was applied to Fenton reagent in the wastewater treatment, and he uses Fe
2+And H
2O
2Various organism in oxidation of phenol waste water and the alkyl waste water.Fenton reagent successfully applies to the processing of various industrial sewage in the research of nearly more than ten years, and receives concern both domestic and external day by day.
Why Fenton reagent has very strong oxidation capacity, is because wherein contain Fe
2+And H
2O
2, H
2O
2Generated hydroxyl radical free radical (OH) by the ferrous ion catalytic decomposition, and cause more other free radicals, its reaction mechanism is as follows:
Fe
2++H
2O
2→Fe
3++OH
-+·OH
Fe
3++H
2O
2→Fe
2++HO
2·+H
+
Fe
2++·OH→OH
-+Fe
3+
RH+·OH→R·+H
2O
R·+Fe
3+→R
++Fe
2+
R
++O
2→ROO
+→…→CO
2+H
2O
The hydroxyl radical free radical that above chain reaction produces has following critical nature:
(1) hydroxyl radical free radical (OH) is a kind of very strong oxygenant, and its oxidizing electrode current potential (E) is 2.80V, is only second to F in known oxygenant
2
(2) have higher electronegativity or electron affinity (569.3kJ), the easy high cloud density point of attack, the attack of hydroxyl radical free radical (OH) simultaneously has certain selectivity;
(3) hydroxyl radical free radical (OH) also has addition, when carbon-carbon double bond exists, unless had highly active hydrocarbon key by the molecule of attack, otherwise addition reaction will take place.
It is exactly that hydroxyl radical free radical and organism react that Fenton reagent is handled organic essence.
The common Fenton reagent processing waste water drug dosage that utilizes is big, and produces a large amount of chemical sludges, and processing cost is higher, so far, overcomes the problem that exists when Fenton reagent is handled waste water and does not appear in the newspapers as yet.
Summary of the invention
The objective of the invention is to handle the weak point that exists in the waste water technology, a kind of processing method that can reduce the Fenton reagent drug dosage, reduce the treating bio-refractory waste water by up-flow multi-phase oxidation column of chemical sludge is provided in order to solve the above-mentioned existing Fenton reagent that utilizes.
In order to solve the problems of the technologies described above, the present invention is achieved through the following technical solutions:
A kind of processing method for the treatment of bio-refractory waste water by up-flow multi-phase oxidation column may further comprise the steps and processing condition:
1) waste water is sent into the inlet flume of upflowing heterogeneous oxidation top of tower with pump by water inlet pipe, be assigned to 2 circulating water channels, in 2 circulating water channels, add H respectively by inlet flume
2O
2And FeSO
47H
2O, wherein H
2O
2With Fe
2+Mol ratio be 5～20: 1, the COD mass ratio is 2～3: 1 in hydrogen peroxide and the pending water.Waste water, Fenton reagent, waste water is delivered to oxidizing tower bottom rotation water distributing system by water circulating pump after circulation groove mixes after treatment, and waste water is the eddy flow fluidised form and enters in the heterogeneous oxygen district and react, and waste water is at oxidizing tower internal reaction time 0.5～1h.
Simultaneously be added with small-particle carrier quartz sand, make oxidation zone form the heterogeneous oxidation district in oxidizing tower carrier input port.Recirculated water keeps certain upflow velocity 50～80m/h, makes carrier granule be fluidization; Fe in the oxidizing reaction
2+With H
2O
2The Fe that generates
3+Be adsorbed onto on the surface of carrier this part Fe with crystallization or sedimentary form
3+Thereby, the heterocatalysis oxidizing reaction reduces the add-on of Fenton reagent and the chemical sludge of generation because taking place.
After the solid-liquid separator of quartz sand and waste water process oxidizing tower separated, waste water overflowed through overflow weir, and the water that reaches emission standard is discharged by rising pipe.
An oxidizing tower water outlet part flow into neutralization tank and carries out subsequent disposal; A part is back to oxidizing tower to guarantee certain upflow velocity.
2) through 1) waste water after handling enters neutralization tank, degassing pond and coagulative precipitation tank successively: in neutralization tank, adds sodium hydroxide, regulates waste water ph 7～8; Waste water enters degassing pond after neutralizing, and the air blast degassing 10～20min sloughs the small oxygen bubble that produces in the reaction in degassing pond, avoids back coagulate sludge come-up; Waste water after the degassing enters coagulative precipitation tank, adds polyacrylamide 2～4mg/L and carry out coagulating sedimentation in coagulative precipitation tank, settling tank surface load 1～2m
3/ m
2H, retention time of sewage 2～3h sloughs the suspended substance in the water, the supernatant liquor qualified discharge.
The equipment that technical process of the present invention relates to has upflowing multi-phase oxidation column, neutralization tank, degassing pond and coagulative precipitation tank.
The coagulative precipitation tank of the above, its surface load are 1～2m
3/ m
2H.
The upflowing multi-phase oxidation column of the above is the exclusive equipment of this technology (the upflowing multi-phase oxidation column is applied for utility model patent simultaneously), and oxidizing tower includes: inlet flume, rising pipe, circulation groove, circulation tube, carrier dispensing port, rotation water distributing system and solid-liquid separator.2 circulating water channels that communicate with inlet flume are arranged at the oxidizing tower top, have 2 independently circulation tubes, an end of circulation tube is connected with circulation groove, the other end links to each other with water distribution system, lift pump is housed on the circulation tube, adds the quartz sand carrier in the oxidizing tower, form the heterogeneous oxidation district.
The present invention's beneficial effect compared with the prior art is:
1. the inventive method combines the technology such as reduction of dissolved of homophase chemical oxidation, out-phase chemical oxidation, fluid bed crystallization and ferriferous oxide, traditional technology of utilizing Fenton reagent to handle waste water has been done significantly improvement, therefore can reduce the dosage of Fenton reagent and can reduce chemical sludge output, the ferriferous oxide that forms at carrier surface has the effect of heterocatalysis simultaneously, the mode of multi-phase oxidation column has also promoted chemical oxidation reaction and mass-transfer efficiency, improves and removes efficient.Through test, the clearance of COD, colourity is all greater than 70% after the wastewater treatment.
2. this method is simple to operate, and used starting material are that the technical grade pharmaceutical chemicals is easy to get, expense is cheap, the treatment time is short and to the removal efficient height of pollutent.
Description of drawings
Fig. 1 is the treating bio-refractory waste water by up-flow multi-phase oxidation column process flow diagram.
Fig. 2 is a upflowing multi-phase oxidation column structural representation.
Among the figure: water inlet pipe 1, inlet flume 2, circulation groove 3, circulation tube 4, recycle pump 5, water distributor 6, water distributor posticum 7, cyclone water distributor 8, water distributor posticum 9, heterogeneous oxidation district 10, solid-liquid separator 11, annular steelframe 12 overflows tank 13, rising pipe 14, quartz sand dispensing port 15.
Embodiment
The present invention is further detailed explanation below in conjunction with embodiment.
The used pharmaceutical chemicals of the present invention is the technical grade pharmaceutical chemicals.
Embodiment 1
Adopt treating bio-refractory waste water by up-flow multi-phase oxidation column technology that paper mill, Guangxi middle-stage wastewater bio-chemical effluent is handled.The wastewater treatment water yield is 250t/h, the COD value 265mg/L of waste water, 64 times of colourities.Waste water with being pumped into oxidizing tower top inlet flume, is dispensed to 2 circulation grooves by inlet flume, in circulation groove, adds H respectively
2O
2And FeSO
47H
2O.Two kinds of adding amount of medicines are: the COD mass ratio is 2: 1 in hydrogen peroxide and the pending water, i.e. H
2O
2Dosage 530mg/L; H
2O
2With Fe
2+Mol ratio be 5: 1, i.e. FeSO
47H
2O dosage 867mg/L.
Waste water reacts in oxidizing tower, reaction times 30min.Enter neutralization tank through the oxidizing tower processed waste water, in neutralization tank, add sodium hydroxide, regulate pH value to 7～8; Waste water enters degassing pond after neutralizing, air blast degassing 10min; Degassing back waste water enters flocculation sedimentation tank, adds polyacrylamide according to 2mg/L in settling tank, forms flco, settling tank surface load 1m
3/ m
2H, residence time 2h removes the suspended substance in anhydrating.The COD of the water outlet after the processing reduces to 75mg/L, and colourity is reduced to 8 times, reaches GB3544-2008 pulp and paper industry water emission standard.
Adopt treating bio-refractory waste water by up-flow multi-phase oxidation column technology that Guangxi refuse landfill percolate waste water is handled.The wastewater treatment water yield is 4t/h, the COD value 565mg/L of waste water, 112 times of colourities.Waste water with being pumped into oxidizing tower top inlet flume, is dispensed to 2 circulation grooves by inlet flume, in circulation groove, adds H respectively
2O
2And FeSO
47H
2O.Two kinds of adding amount of medicines are: the COD mass ratio is 2.6: 1 in hydrogen peroxide and the pending water, i.e. H
2O
2Dosage 1469mg/L; H
2O
2With Fe
2+Mol ratio be 13: 1, i.e. FeSO
47H
2O dosage 924mg/L.
Waste water reacts in oxidizing tower, reaction times 40min.Enter neutralization tank through the oxidizing tower processed waste water, in neutralization tank, add sodium hydroxide, regulate pH value to 7～8; Waste water enters degassing pond after neutralizing, air blast degassing 20min; Degassing back waste water enters flocculation sedimentation tank, adds polyacrylamide according to 3mg/L in settling tank, forms flco, settling tank surface load 2m
3/ m
2H, residence time 3h removes the suspended substance in anhydrating.The COD of the water outlet after the processing reduces to below the 100mg/L, and colourity is reduced to 30 times, reaches the GB16889-2008 household refuse landfill sites and pollutes control criterion.
Embodiment 3
Adopt treating bio-refractory waste water by up-flow multi-phase oxidation column technology that the wastewater biochemical water outlet of Guangxi molasses-spirit factory is handled.The wastewater treatment water yield is 1t/h, the COD value 347mg/L of waste water, 80 times of colourities.Waste water with being pumped into oxidizing tower top inlet flume, is dispensed to 2 circulation grooves by inlet flume, in circulation groove, adds H respectively
2O
2And FeSO
47H
2O.Two kinds of adding amount of medicines are: the COD mass ratio is 3: 1 in hydrogen peroxide and the pending water, i.e. H
2O
2Dosage 1041mg/L; H
2O
2With Fe
2+Mol ratio be 20: 1, i.e. FeSO
47H
2O dosage 426mg/L.
Waste water reacts in oxidizing tower, reaction times 60min.Enter neutralization tank through the oxidizing tower processed waste water, in neutralization tank, add sodium hydroxide, regulate pH value to 7～8; Waste water enters degassing pond after neutralizing, air blast degassing 20min; Degassing back waste water enters flocculation sedimentation tank, adds polyacrylamide according to 4mg/L in settling tank, forms flco, settling tank surface load 1m
3/ m
2H, residence time 2h removes the suspended substance in anhydrating.The COD of the water outlet after the processing reduces to 75mg/L, and colourity is reduced to 8 times, reaches the GB8978-1996 integrated wastewater discharge standard.
Claims (4)
1. the processing method of a treating bio-refractory waste water by up-flow multi-phase oxidation column is characterized in that may further comprise the steps and processing condition:
1) waste water is sent into the inlet flume of upflowing heterogeneous oxidation top of tower with pump by water inlet pipe, be assigned to 2 circulating water channels, in 2 circulating water channels, add H respectively by inlet flume
2O
2And FeSO
47H
2O, wherein H
2O
2With Fe
2+Mol ratio be 5～20: 1, the COD mass ratio is 2～3: 1 in hydrogen peroxide and the pending water; Waste water, Fenton reagent, waste water is delivered to oxidizing tower bottom rotation water distributing system by water circulating pump after circulation groove mixes after treatment, and waste water is the eddy flow fluidised form and enters in the heterogeneous oxygen district and react, and waste water is at oxidizing tower internal reaction time 0.5～1h;
Simultaneously add small-particle carrier quartz sand, make oxidation zone form the heterogeneous oxidation district in oxidizing tower carrier input port; Recirculated water keeps certain upflow velocity 50～80m/h, makes carrier granule be fluidization; Fe in the oxidizing reaction
2+With H
2O
2The Fe that generates
3+Be adsorbed onto on the surface of carrier this part Fe with crystallization or sedimentary form
3+Thereby, the heterocatalysis oxidizing reaction reduces the add-on of Fenton reagent and the chemical sludge of generation because taking place;
After the solid-liquid separator of quartz sand and waste water process oxidizing tower separated, waste water overflowed through overflow weir, and the water that reaches emission standard is discharged by rising pipe;
An oxidizing tower water outlet part flow into neutralization tank and carries out subsequent disposal; A part is back to oxidizing tower to guarantee certain upflow velocity.
2) through 1) waste water after handling enters neutralization tank, degassing pond and coagulative precipitation tank successively: in neutralization tank, regulate waste water ph 7～8, water outlet enters degassing pond, the air blast degassing 10～20min in degassing pond, waste water after the degassing adds polyacrylamide 2～4mg/L and enters coagulating sedimentation, carry out coagulating sedimentation, the residence time 2～3h sloughs the suspended substance in the water, the supernatant liquor qualified discharge.
2. treating bio-refractory waste water by up-flow multi-phase oxidation column processing method according to claim 1 is characterized in that, the equipment that described technical process relates to has upflowing multi-phase oxidation column, neutralization tank, degassing pond and coagulative precipitation tank.
3. treating bio-refractory waste water by up-flow multi-phase oxidation column processing method according to claim 2 is characterized in that, described coagulative precipitation tank, its surface load are 1～2m
3/ m
2H.
4. treating bio-refractory waste water by up-flow multi-phase oxidation column processing method according to claim 2, it is characterized in that, described upflowing multi-phase oxidation column is the exclusive equipment of this technology, and oxidizing tower includes: inlet flume, rising pipe, circulation groove, circulation tube, carrier dispensing port, rotation water distributing system and solid-liquid separator.2 circulating water channels that communicate with inlet flume are arranged at the oxidizing tower top, have 2 independently circulation tubes, an end of circulation tube is connected with circulation groove, the other end links to each other with water distribution system, lift pump is housed on the circulation tube, adds the quartz sand carrier in the oxidizing tower, form the heterogeneous oxidation district.
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| CN101955305A (en) * | 2010-10-19 | 2011-01-26 | 江苏省环境科学研究院 | A kind of paper waste combined treatment process |
| CN102642911A (en) * | 2012-05-02 | 2012-08-22 | 山东绿泉环保工程有限公司 | Advanced oxidation treatment device and advanced oxidation treatment process of refractory organic wastewater |
| CN102701392A (en) * | 2012-05-24 | 2012-10-03 | 苏州顶裕水务科技有限公司 | Fenton fluidized bed with monitoring device |
| CN102765799A (en) * | 2012-07-10 | 2012-11-07 | 广州市环境保护工程设计院有限公司 | Method of chain scission for high concentration persistent organic pollutants in wastewater |
| CN102774953A (en) * | 2012-05-24 | 2012-11-14 | 苏州顶裕水务科技有限公司 | Fenton fluidized bed and operating method thereof |
| CN102838229A (en) * | 2012-08-22 | 2012-12-26 | 青岛海安生物环保有限公司 | Method for treating alkali high-concentration organic waste water by using Fenton process |
| CN102897942A (en) * | 2012-06-21 | 2013-01-30 | 浙江水美环保工程有限公司 | Integrated Fenton advanced oxidation system |
| CN103121771A (en) * | 2011-11-21 | 2013-05-29 | 上海巴安水务股份有限公司 | Advanced treatment process for high concentration organic wastewater |
| CN103342424A (en) * | 2013-07-15 | 2013-10-09 | 枣庄市申龙水务有限公司 | Advanced treatment process and equipment for refractory wastewater |
| CN105236625A (en) * | 2015-11-11 | 2016-01-13 | 苏州市环境保护有限公司 | Fenton printing-dyeing-wastewater deep treatment method |
| CN106673302A (en) * | 2016-12-16 | 2017-05-17 | 北京桑德环境工程有限公司 | Advanced wastewater treatment system for leather industry park |
| CN108117196A (en) * | 2018-02-01 | 2018-06-05 | 北京桑德环境工程有限公司 | Leather waste water advanced treatment system and method |
| CN108128970A (en) * | 2017-12-22 | 2018-06-08 | 南京工大环境科技南通有限公司 | A kind of strenuous primary treatment device for the processing of Mediben high slat-containing wastewater |
| CN108622994A (en) * | 2018-05-18 | 2018-10-09 | 北京鑫佰利科技发展有限公司 | A kind of advanced oxidation multistage suspension bed reaction device and technique |
| CN110240313A (en) * | 2019-06-17 | 2019-09-17 | 自然资源部第三海洋研究所 | The devices and methods therefor of Fenton processing refractory organic |
| CN110316861A (en) * | 2019-06-24 | 2019-10-11 | 广西博世科环保科技股份有限公司 | Strengthen up flow type multiphase wastewater oxidation treatment process and processing system |
| CN111018187A (en) * | 2019-12-25 | 2020-04-17 | 苏州希图环保科技有限公司 | Wastewater treatment process based on Fenton oxidation reaction |
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| CN101955305A (en) * | 2010-10-19 | 2011-01-26 | 江苏省环境科学研究院 | A kind of paper waste combined treatment process |
| CN103121771A (en) * | 2011-11-21 | 2013-05-29 | 上海巴安水务股份有限公司 | Advanced treatment process for high concentration organic wastewater |
| CN103121771B (en) * | 2011-11-21 | 2016-08-03 | 上海巴安水务股份有限公司 | The technique of high concentrated organic wastewater advanced treating |
| CN102642911A (en) * | 2012-05-02 | 2012-08-22 | 山东绿泉环保工程有限公司 | Advanced oxidation treatment device and advanced oxidation treatment process of refractory organic wastewater |
| CN102701392A (en) * | 2012-05-24 | 2012-10-03 | 苏州顶裕水务科技有限公司 | Fenton fluidized bed with monitoring device |
| CN102774953A (en) * | 2012-05-24 | 2012-11-14 | 苏州顶裕水务科技有限公司 | Fenton fluidized bed and operating method thereof |
| CN102897942A (en) * | 2012-06-21 | 2013-01-30 | 浙江水美环保工程有限公司 | Integrated Fenton advanced oxidation system |
| CN102765799A (en) * | 2012-07-10 | 2012-11-07 | 广州市环境保护工程设计院有限公司 | Method of chain scission for high concentration persistent organic pollutants in wastewater |
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| CN102838229A (en) * | 2012-08-22 | 2012-12-26 | 青岛海安生物环保有限公司 | Method for treating alkali high-concentration organic waste water by using Fenton process |
| CN103342424A (en) * | 2013-07-15 | 2013-10-09 | 枣庄市申龙水务有限公司 | Advanced treatment process and equipment for refractory wastewater |
| CN105236625A (en) * | 2015-11-11 | 2016-01-13 | 苏州市环境保护有限公司 | Fenton printing-dyeing-wastewater deep treatment method |
| CN106673302A (en) * | 2016-12-16 | 2017-05-17 | 北京桑德环境工程有限公司 | Advanced wastewater treatment system for leather industry park |
| CN108128970A (en) * | 2017-12-22 | 2018-06-08 | 南京工大环境科技南通有限公司 | A kind of strenuous primary treatment device for the processing of Mediben high slat-containing wastewater |
| CN108117196A (en) * | 2018-02-01 | 2018-06-05 | 北京桑德环境工程有限公司 | Leather waste water advanced treatment system and method |
| CN108622994A (en) * | 2018-05-18 | 2018-10-09 | 北京鑫佰利科技发展有限公司 | A kind of advanced oxidation multistage suspension bed reaction device and technique |
| CN110240313A (en) * | 2019-06-17 | 2019-09-17 | 自然资源部第三海洋研究所 | The devices and methods therefor of Fenton processing refractory organic |
| US20210078887A1 (en) * | 2019-06-21 | 2021-03-18 | Guangxi Bossco Environmental Protection Technology | Treatment process and treatment system of enhanced up-flow multiphase wastewater oxidation |
| US11926549B2 (en) * | 2019-06-21 | 2024-03-12 | Guangxi Bossco Environmental Protection Agency | Treatment process and treatment system of enhanced up-flow multiphase wastewater oxidation |
| CN110316861A (en) * | 2019-06-24 | 2019-10-11 | 广西博世科环保科技股份有限公司 | Strengthen up flow type multiphase wastewater oxidation treatment process and processing system |
| WO2020258359A1 (en) * | 2019-06-24 | 2020-12-30 | 广西博世科环保科技股份有限公司 | Improved upflow multi-phase wastewater oxidation treatment process and system |
| CN111018187A (en) * | 2019-12-25 | 2020-04-17 | 苏州希图环保科技有限公司 | Wastewater treatment process based on Fenton oxidation reaction |
| CN114538596A (en) * | 2022-03-22 | 2022-05-27 | 中建环能科技股份有限公司 | Heterogeneous fenton effluent treatment plant |
| CN115888712A (en) * | 2022-07-27 | 2023-04-04 | 广西大学 | Preparation method and application of Fenton sludge-based magnetic biochar catalytic material |
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