CN101798136A - Method for removing organic pollutants from water - Google Patents
Method for removing organic pollutants from water Download PDFInfo
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- CN101798136A CN101798136A CN 201010155103 CN201010155103A CN101798136A CN 101798136 A CN101798136 A CN 101798136A CN 201010155103 CN201010155103 CN 201010155103 CN 201010155103 A CN201010155103 A CN 201010155103A CN 101798136 A CN101798136 A CN 101798136A
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Abstract
The invention discloses a method for removing organic pollutants from water, which relates to a water treatment method and aims to solve the problem that the conventional water treatment method has the disadvantages of poor treatment effect, high treatment cost and complex operation in the removal of trace organic pollutants. The method comprises the following steps: 1, arranging a nonvalent copper material in a reactor in a form of fluidized bed or fixed bed; and 2, adding an acid into incoming water to adjust a pH value to be between 1 and 6, introducing the incoming water of which the pH value is 1 to 6 into the reactor, keeping 1 to 20 mg/L dissolved oxygen concentration in the water in the reactor, keeping 1 to 300 minutes hydraulic detention time and discharging effluent. The method is implemented at the normal temperature and the normal pressure and has the advantages of moderate reaction condition, capacity of effectively removing the trace persistent organic pollutants from the water, and the rate of removal of diethyl phthalate and dibutyl phthalate of 85.9 to 100 percent.
Description
Technical field
The present invention relates to a kind of water treatment method.
Background technology
The discharging of trade effluent, sanitary sewage has caused increasing the weight of of water body organic contamination, enter some organic pollutants of water body, as chemical substances such as agricultural chemicals, softening agent, though concentration is low, but stability is high, difficult degradation, and much have carcinogenic, teratogenesis, mutagenic effect, very big to human health damage.Conventional water treatment process is very limited to the removal effect of these materials, must adopt the advanced treatment technology, as charcoal absorption, membrane filtration, advanced oxidation etc.But in the active carbon absorption technology, gac has saturated extent of adsorption, needs regeneration; And the membrane filtration cost is higher, and film is contaminated easily; Advanced oxidation processes commonly used comprises catalytic ozonation, photochemical catalytic oxidation, Catalytic Wet Oxidation etc., but in the catalysis ozone metallization processes, the ozone preparation cost is higher on the one hand, also has shortcomings such as catalyst efficient is low, easy loss on the other hand; There are problems such as ultraviolet penetration depth is limited, the ultraviolet lamp life-span is short in the photocatalytic-oxidation metallization processes; Catalytic Wet Oxidation must be carried out under High Temperature High Pressure, severe reaction conditions, and the cost height is applicable to the processing of high concentrated organic wastewater.Aforesaid method exists many deficiencies, and the method for therefore seeking the persistence organic pollutant of trace in a kind of economical and efficient, the removal water simple to operate becomes the problem that presses for solution.
Summary of the invention
The objective of the invention is provides a kind of method of removing organic pollutant in the water in order to solve the problem of existing water treatment method to micro quantity organic pollutant poor processing effect, processing cost height, complicated operation.
It is as follows that the present invention removes in the water method of organic pollutant: one, in reactor, zerovalent copper material throwing amount is 10mg/L～10kg/L to the zerovalent copper material with fluidized-bed or fixed bed arranged in form; Two, acid being added water inlet, to regulate pH value be 1～6, is that the interior oxygen in water concentration of reactor remains 1mg/L～20mg/L in 1～6 the water inlet inflow reactor then with the pH value, and hydraulic detention time is 1～300min, discharges water outlet then; Reactor bottom is established aerating apparatus in step 1 and the step 2, with air or pure oxygen aeration; Reactor described in the step 1 is tubular reactor, pond formula reactor or tower reactor; The acid of regulating water inlet pH value in the step 2 is hydrochloric acid or sulfuric acid; Zerovalent copper material described in the step 1 is that particle diameter is shot copper or the copper billet of 1mm～10cm; Zerovalent copper material described in the step 1 is that diameter is the copper wire of 1 μ m～1cm, or the copper mesh that is woven into the copper wire of diameter 1 μ m～1cm; Zerovalent copper material described in the step 1 is the alloy that a kind of or the wherein several and copper in manganese, nickel, chromium, silver, zinc, iron, aluminium, cobalt, lead, titanium, tungsten and the tin is formed; Zerovalent copper material described in the step 1 is plastics, the surperficial molecular sieve of copper, the surperficial quartz sand of copper, the zeolite of surface coating copper, the haydite of surface coating copper or the gac that the surface coats copper of coating of coating that the surface coats copper; Zerovalent copper material described in the step 1 is that particle diameter is the copper powder of 1 μ m～1mm.
The present invention carries out at normal temperatures and pressures, and the reaction conditions gentleness is especially effective to the removal of the persistence organic pollutant of trace in the water.The inventive method can reach 85.9%～100% to the clearance of diethyl phthalate, dibutyl phthalate.
Description of drawings
Fig. 1 is the removal effect figure of diethyl phthalate under the different initial pH value conditions in the embodiment 24, among the figure
The expression initial pH value is the removal curve of diethyl phthalate under 4 the condition,
The expression initial pH value is the removal curve of diethyl phthalate under 3 the condition,
The expression initial pH value is the removal curve of diethyl phthalate under 2 the condition; Fig. 2 is the removal effect figure of dibutyl phthalate under the different throwing amounts of copper powder in the embodiment 25, among the figure
Expression copper powder throwing amount is the removal effect curve of dibutyl phthalate under the condition of 0mg/L,
Expression copper powder throwing amount is the removal effect curve of dibutyl phthalate under the condition of 0.15g/L,
Expression copper powder throwing amount is the removal effect curve of dibutyl phthalate under the condition of 0.45g/L,
Expression copper powder throwing amount is the removal effect curve of dibutyl phthalate under the condition of 1.0g/L.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the method for removing organic pollutant in the water in the present embodiment is as follows: one, in reactor, zerovalent copper material throwing amount is 10mg/L～10kg/L to the zerovalent copper material with fluidized-bed or fixed bed arranged in form; Two, acid being added water inlet, to regulate pH value be 1～6, is that the interior oxygen in water concentration of reactor remains 1mg/L～20mg/L in 1～6 the water inlet inflow reactor then with the pH value, and hydraulic detention time is 1～300min, discharges water outlet then; Reactor bottom is established aerating apparatus in step 1 and the step 2, with air or pure oxygen aeration.
Embodiment two: what present embodiment and embodiment one were different is that the reactor described in the step 1 is tubular reactor, pond formula reactor or tower reactor.Other is identical with embodiment one.
Embodiment three: present embodiment is different with one of embodiment one or two is that the acid of regulating water inlet pH value in the step 2 is hydrochloric acid or sulfuric acid.Other is identical with one of embodiment one or two.
Embodiment four: what present embodiment was different with one of embodiment one to three is that the zerovalent copper material described in the step 1 is that particle diameter is shot copper or the copper billet of 1mm～10cm.Other is identical with one of embodiment one to three.
Embodiment five: what present embodiment was different with one of embodiment one to three is that the zerovalent copper material described in the step 1 is that diameter is the copper wire of 1 μ m～1cm, or the copper mesh that is woven into the copper wire of diameter 1 μ m～1cm.Other is identical with one of embodiment one to three.
Embodiment six: what present embodiment was different with one of embodiment one to three is that the zerovalent copper material described in the step 1 is the alloy that a kind of or the wherein several and copper in manganese, nickel, chromium, silver, zinc, iron, aluminium, cobalt, lead, titanium, tungsten and the tin is formed.Other is identical with one of embodiment one to three.
In the present embodiment zerovalent copper material be several and copper in manganese, nickel, chromium, silver, zinc, iron, aluminium, cobalt, lead, titanium, tungsten and the tin form alloy the time, each composition be any than.
Embodiment seven: what present embodiment was different with one of embodiment one to three is that the zerovalent copper material described in the step 1 is plastics, the surperficial molecular sieve of copper, the surperficial quartz sand of copper, the zeolite of surface coating copper, the haydite of surface coating copper or the gac that the surface coats copper of coating of coating that the surface coats copper.Other is identical with one of embodiment one to three.
Embodiment eight: what present embodiment was different with one of embodiment one to three is that the zerovalent copper material described in the step 1 is that particle diameter is the copper powder of 1 μ m～1mm.Other is identical with one of embodiment one to three.
Embodiment nine: what present embodiment was different with one of embodiment one to three is that the pH value of intaking in the inflow reactor in the step 2 is 2～3.Other is identical with one of embodiment one to three.
Embodiment ten: what present embodiment was different with one of embodiment one to three is that hydraulic detention time is 10min～60min in the step 2.Other is identical with one of embodiment one to three.
Embodiment 11: present embodiment is different with one of embodiment one to ten be in the step 1 particle diameter be the copper powder of 1 μ m～1mm with the fluidized-bed arranged in form in reactor.Other is identical with one of embodiment one to ten.
Embodiment 12: present embodiment is different with one of embodiment one to ten be in the step 1 particle diameter be the shot copper of 1mm～10cm or copper billet with the fixed bed arranged in form in reactor.Other is identical with one of embodiment one to ten.
Embodiment 13: what present embodiment was different with one of embodiment one to ten is that diameter is the copper wire of 1 μ m～1cm in the step 1, or the copper mesh that is woven into the copper wire of diameter 1 μ m～1cm with the fixed bed arranged in form in reactor.Other is identical with one of embodiment one to ten.
Embodiment 14: the gac that the molecular sieve that present embodiment is different with one of embodiment one to ten is the surface coats copper in the step 1 plastics, the surface coats copper, the quartz sand that the surface coats copper, zeolite that the surface coats copper, haydite that the surface coats copper or surface coat copper with the fixed bed arranged in form in reactor.Other is identical with one of embodiment one to ten.
Embodiment 15: what present embodiment was different with one of embodiment one to ten is that the pH value of intaking in the inflow reactor in the step 2 is 2～5.
Embodiment 16: what present embodiment was different with one of embodiment one to ten is that the pH value of intaking in the inflow reactor in the step 2 is 3～4.
Embodiment 17: what present embodiment was different with one of embodiment one to ten is that the pH value of intaking in the inflow reactor in the step 2 is 2.
Embodiment 18: what present embodiment was different with one of embodiment one to ten is aerating apparatus employing core aeration, titanium plate aeration or the standpipe aeration of reactor bottom in the step 1.Other is identical with one of embodiment one to ten.
Embodiment 19: what present embodiment was different with one of embodiment one to 18 is to adopt air aeration in the step 2, and oxygen in water concentration remains 2mg/L～10mg/L in the reactor.Other is identical with one of embodiment one to 18.
Embodiment 20: what present embodiment was different with one of embodiment one to 18 is to adopt pure oxygen aeration in the step 2, and oxygen in water concentration remains 10～20mg/L in the reactor.Other is identical with one of embodiment one to 18.
Embodiment 21: what present embodiment was different with one of embodiment one to 18 is that hydraulic detention time is 2～200min in the step 2.Other is identical with one of embodiment one to 18.
Embodiment 22: what present embodiment was different with one of embodiment one to 18 is that hydraulic detention time is 10～60min in the step 2.Other is identical with one of embodiment one to 18.
Embodiment 23: what present embodiment was different with one of embodiment one to 18 is that hydraulic detention time is 20～30min in the step 2.Other is identical with one of embodiment one to 18.
Embodiment 24: it is target contaminant that present embodiment is selected diethyl phthalate, investigates the removal effect under the different initial pH value conditions.Experiment is carried out in volume is the round-bottomed flask of 1L, adopts magnetic stirrer.Experiment condition is: the diethyl phthalate starting point concentration is 550 μ g/L; Metallic copper material is particle diameter 200 purpose zeroth order copper powders, and dosage is 0.5g/L; The pH value of solution value is regulated with sulfuric acid; Adopt pure oxygen aeration, oxygen flow is 60ml/min.Experimental result as shown in Figure 1, as seen along with the decline of solution initial pH value, diethyl phthalate is removed efficient and is improved gradually, is respectively in initial pH value under 4,3,2 the condition, reacted 30 minutes, the clearance of diethyl phthalate is respectively 20.3%, 61.5%, 85.9%.
Embodiment 25: it is target contaminant that present embodiment is selected dibutyl phthalate, investigates the removal effect under the different metal copper throwing amount condition.Experiment is carried out in volume is the round-bottomed flask of 1L, adopts magnetic stirrer.Experiment condition is: the dibutyl phthalate starting point concentration is 500 μ g/L; Metallic copper material is particle diameter 200 purpose zeroth order copper powders; The solution initial pH value is 2, regulates with hydrochloric acid; Adopt pure oxygen aeration, oxygen flow is 60ml/min.Experimental result as shown in Figure 2, as seen along with the increasing of metallic copper throwing amount, dibutyl phthalate is removed efficient and is improved gradually, be respectively in the throwing amount under the condition of 0mg/L, 0.15g/L, 0.45g/L, 1.0g/L, reacted 30 minutes, the clearance of dibutyl phthalate is respectively 14.8%, 57.7%, 90.4%, 100%.
Claims (10)
1. the method for organic pollutant in the removal water, it is as follows to it is characterized in that removing in the water method of organic pollutant: one, in reactor, zerovalent copper material throwing amount is 10mg/L～10kg/L to the zerovalent copper material with fluidized-bed or fixed bed arranged in form; Two, acid being added water inlet, to regulate pH value be 1～6, is that the interior oxygen in water concentration of reactor remains 1mg/L～20mg/L in 1～6 the water inlet inflow reactor then with the pH value, and hydraulic detention time is 1～300min, discharges water outlet then; Reactor bottom is established aerating apparatus in step 1 and the step 2, with air or pure oxygen aeration.
2. the method for organic pollutant in the removal water according to claim 1 is characterized in that the reactor described in the step 1 is tubular reactor, pond formula reactor or tower reactor.
3. the method for organic pollutant in the removal water according to claim 1 and 2 is characterized in that the acid of adjusting water inlet pH value in the step 2 is hydrochloric acid or sulfuric acid.
4. the method for organic pollutant in the removal water according to claim 3 is characterized in that the zerovalent copper material described in the step 1 is that particle diameter is shot copper or the copper billet of 1mm～10cm.
5. the method for organic pollutant in the removal water according to claim 3 is characterized in that the zerovalent copper material described in the step 1 is that diameter is the copper wire of 1 μ m～1cm, or the copper mesh that is woven into the copper wire of diameter 1 μ m～1cm.
6. the method for organic pollutant in the removal water according to claim 3 is characterized in that the zerovalent copper material described in the step 1 is the alloy that a kind of or the wherein several and copper in manganese, nickel, chromium, silver, zinc, iron, aluminium, cobalt, lead, titanium, tungsten and the tin is formed.
7. the method for organic pollutant in the removal water according to claim 3 is characterized in that the zerovalent copper material described in the step 1 is plastics, the surperficial molecular sieve of copper, the surperficial quartz sand of copper, the zeolite of surface coating copper, the haydite of surface coating copper or the gac that the surface coats copper of coating of coating that the surface coats copper.
8. the method for organic pollutant in the removal water according to claim 3 is characterized in that the zerovalent copper material described in the step 1 is that particle diameter is the copper powder of 1 μ m～1mm.
9. the method for organic pollutant in the removal water according to claim 3 is characterized in that the pH value of intaking in the inflow reactor in the step 2 is 2～3.
10. the method for organic pollutant in the removal water according to claim 3 is characterized in that hydraulic detention time is 10min～60min in the step 2.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010101551037A CN101798136B (en) | 2010-04-26 | 2010-04-26 | Method for removing organic pollutants in water |
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| CN2010101551037A CN101798136B (en) | 2010-04-26 | 2010-04-26 | Method for removing organic pollutants in water |
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| CN101798136A true CN101798136A (en) | 2010-08-11 |
| CN101798136B CN101798136B (en) | 2012-05-30 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249476A (en) * | 2011-05-01 | 2011-11-23 | 南京大学 | Method for removing phthalates out of water by utilizing UV (ultraviolet)/ozone/chlorella degradation composite process |
| CN102464433A (en) * | 2010-11-15 | 2012-05-23 | 新奥科技发展有限公司 | Method and equipment for advanced treatment of refractory wastewater |
| CN104071879A (en) * | 2014-06-27 | 2014-10-01 | 深圳市开天源自动化工程有限公司 | Method for continuously separating out copper ions from copper body under induction of ultraviolet light source |
| CN104743654A (en) * | 2015-04-17 | 2015-07-01 | 南开大学 | Method for efficient treatment of organic wastewater by virtue of pre-magnetized FeO/H2O2 system |
| CN106219915A (en) * | 2016-07-29 | 2016-12-14 | 张凯悦 | A kind of diethyl phthalate Contaminated Sewage Sludge inorganic agent and preparation method thereof |
| CN106493162A (en) * | 2016-12-22 | 2017-03-15 | 常州大学 | A kind of method that PAEs contaminated soils repaired by microwave reinforced calper calcium peroxide |
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| CN86108846A (en) * | 1985-12-03 | 1987-07-29 | 大阪瓦斯株式会社 | Temperature oxidation technique is handled the flow process of waste water |
| CN1569686A (en) * | 2004-04-30 | 2005-01-26 | 杨静 | Vertical sewage treatment device |
| CN101386439A (en) * | 2008-11-05 | 2009-03-18 | 中国海洋石油总公司 | Technique for processing organic wastewater by atmospheric catalytic oxidation at low-temperature |
| CN101693579A (en) * | 2009-10-16 | 2010-04-14 | 同济大学 | Method for processing high-concentration wastewater containing alkaline mud |
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2010
- 2010-04-26 CN CN2010101551037A patent/CN101798136B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86108846A (en) * | 1985-12-03 | 1987-07-29 | 大阪瓦斯株式会社 | Temperature oxidation technique is handled the flow process of waste water |
| CN1569686A (en) * | 2004-04-30 | 2005-01-26 | 杨静 | Vertical sewage treatment device |
| CN101386439A (en) * | 2008-11-05 | 2009-03-18 | 中国海洋石油总公司 | Technique for processing organic wastewater by atmospheric catalytic oxidation at low-temperature |
| CN101693579A (en) * | 2009-10-16 | 2010-04-14 | 同济大学 | Method for processing high-concentration wastewater containing alkaline mud |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464433A (en) * | 2010-11-15 | 2012-05-23 | 新奥科技发展有限公司 | Method and equipment for advanced treatment of refractory wastewater |
| CN102464433B (en) * | 2010-11-15 | 2016-08-17 | 新奥科技发展有限公司 | Method and equipment thereof for advanced treating used water difficult to degradate |
| CN102249476A (en) * | 2011-05-01 | 2011-11-23 | 南京大学 | Method for removing phthalates out of water by utilizing UV (ultraviolet)/ozone/chlorella degradation composite process |
| CN102249476B (en) * | 2011-05-01 | 2012-10-31 | 南京大学 | Method for removing phthalates out of water by utilizing UV (ultraviolet)/ozone/chlorella degradation composite process |
| CN104071879A (en) * | 2014-06-27 | 2014-10-01 | 深圳市开天源自动化工程有限公司 | Method for continuously separating out copper ions from copper body under induction of ultraviolet light source |
| CN104071879B (en) * | 2014-06-27 | 2016-02-24 | 深圳市开天源自动化工程有限公司 | The method utilizing ultraviolet source to bring out cupric ion to separate out continuously from copper body |
| CN104743654A (en) * | 2015-04-17 | 2015-07-01 | 南开大学 | Method for efficient treatment of organic wastewater by virtue of pre-magnetized FeO/H2O2 system |
| CN106219915A (en) * | 2016-07-29 | 2016-12-14 | 张凯悦 | A kind of diethyl phthalate Contaminated Sewage Sludge inorganic agent and preparation method thereof |
| CN106493162A (en) * | 2016-12-22 | 2017-03-15 | 常州大学 | A kind of method that PAEs contaminated soils repaired by microwave reinforced calper calcium peroxide |
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| CN101798136B (en) | 2012-05-30 |
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