CN1223523C - Method for purifying pollutant in water by using biological activity carbon-catalysis or activated carbon and oxidation of ozone - Google Patents
Method for purifying pollutant in water by using biological activity carbon-catalysis or activated carbon and oxidation of ozone Download PDFInfo
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- CN1223523C CN1223523C CNB031233929A CN03123392A CN1223523C CN 1223523 C CN1223523 C CN 1223523C CN B031233929 A CNB031233929 A CN B031233929A CN 03123392 A CN03123392 A CN 03123392A CN 1223523 C CN1223523 C CN 1223523C
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- ozone oxidation
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 174
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 92
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 34
- 230000003647 oxidation Effects 0.000 title claims abstract description 31
- 238000006555 catalytic reaction Methods 0.000 title claims description 36
- 239000003344 environmental pollutant Substances 0.000 title abstract 3
- 231100000719 pollutant Toxicity 0.000 title abstract 3
- 230000004071 biological effect Effects 0.000 title 1
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 239000003403 water pollutant Substances 0.000 claims description 12
- 230000015556 catabolic process Effects 0.000 claims description 3
- 238000006731 degradation reaction Methods 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 12
- 239000011572 manganese Substances 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000011001 backwashing Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- -1 hydroxyl radical free radical Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical class C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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- Treatment Of Water By Oxidation Or Reduction (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The present invention relates to a method for purifying pollutants in water by utilizing an activated carbon catalytic ozone oxidation unit and a biologic active carbon unit, which belongs to the technical field of water treatment. In order to solve the problems that the ozone utilization efficiency of the prior art is low, the removal efficiency of organic substances is low and the treatment cost is high, the present invention discloses a method for purifying pollutants in water, which an activated carbon catalytic ozone oxidation unit and a biologic active carbon unit. Water to be treated enters from the lower part of an activated carbon catalytic ozone oxidation reactor, and ozone is led in from the bottom of the reactor; the ozone is uniformly mixed with water through a gas distributing plate in the reactor. The water and the ozone flow upwards through an activated carbon layer filled in the reactor, the residence time is 5 to 30 min, and organic pollutants in the water can be removed or converted. The water which is primarily treated flows into a reactor in which a biologic active carbon layer si filled, and the residence time is 5 to 90 min; organic pollutants in the water is degraded and removed in a biologic mode. The removal efficiency of the present invention to organic pollutants in water is greatly improved, but the treatment cost is low.
Description
Technical field
The invention belongs to water-treatment technology field, relate to a kind of method of removing water pollutant, relate in particular to a kind of deep-purifying method of the water that is polluted by micro-content organism.
Background technology
The underwater micro-organic matter pollution problems is more and more outstanding, and as the micro-natural organic matter and the poisonous and hazardous artificial synthetic organic materials that exist in the drinking water source, the generation of disinfection byproduct (DBP) has very big relation in organism that these are natural and the tap water.And for example, the secondary effluent of municipal sewage plant also contains the poisonous and hazardous artificial synthetic organic materials and the natural organic matter of many types, also has bigger influence for reusing sewage.The disinfection byproduct (DBP) that may exist in the tap water and the endocrine disrupter of trace, persistent organism also produce adverse influence to HUMAN HEALTH.Traditional tap water production technique, i.e. flocculation-sand filtration-sterilizing and purifying method can not be removed micro quantity organic pollutant in the water effectively.
Ozone oxidation-biological activated carbon technology is the method for micro quantity organic pollutant in the purifying waste water of generally adopting in the world at present, the water that promptly contains micropollutant is earlier through ozone oxidation, organism is tentatively degraded, and then further purifies with the biological activated carbon method.Because ozone and organism react stronger selectivity is arranged, promptly very fast with some substance reaction, and very slow with some substance reaction, all organism of can not degrading very effectively; In addition, in the independent ozone oxidation unit, ozone is also not ideal by the mass transfer of gas phase in water, and ozone can not be absorbed fully by water, and ozone concn is very high in the tail gas, causes the utilising efficiency of ozone not high.Consequently, in the ozone oxidation unit, organism can not well be degraded, influence the treatment effect of follow-up biological activated carbon simultaneously, ozone utilization rate is low, consumption is big, cause whole ozone oxidation-BAC process desirable not to the utmost to the removal efficient of micro-content organism, processing cost is higher.
Summary of the invention
The objective of the invention is in order to solve in the existing ozonation technology ozone utilising efficiency lowly, organic matter removal efficient is low, and the problem that processing cost is high provides the especially method of micro-content organism of a kind of more effective removal water pollutant.
The invention provides the method that a kind of activated carbon catalysis ozone oxidation-biological activated carbon purifies water pollutant, it is characterized in that this method mainly comprises following activated carbon catalysis ozone oxidation and two unit of biological activated carbon:
Pending water enters from the bottom of activated carbon catalysis ozone oxidation reaction device, and ozone gas feeds from the bottom of described reactor, and described ozone gas is through air distribution plate and water uniform mixing in the described reactor; The active carbon layer that water and ozone gas are upwards flowed through and filled in the reactor, the organic pollutant in the water was removed or transformed between 5～30min the residence time; Water after the preliminary treatment flows out from the top of described reactor, and ozone tail gas is discharged from the gas discharge outlet of described reactor;
Through the water of above-mentioned preliminary treatment a side inflow from the biological activated carbon reactor, the biological activated carbon layer that current are filled in reactor, the residence time, organic pollutant was by biological degradation, removal in the water between 5～90min; Water after the processing flows out from described reactor opposite side.
According to the water quality of pending water and to handling the difference of back water quality requirement, water at the unitary ozone dosage of activated carbon catalysis ozone oxidation between 0.5mg/L～20mg/L; Water is long more in the activated carbon catalysis ozone oxidation unit and the unitary residence time of biological activated carbon, and the ozone dosage is high more, and the removal effect of water pollutant is just good more, and the quality of handling back water is good more, but processing cost can increase.
Active carbon layer in the activated carbon catalysis ozone oxidation of the present invention unit can be made up of common gac, or is made up of metal oxide-loaded gac.The metal oxide of load can be the single component oxide compound of nickel, iron, copper, manganese, titanium etc. on the gac, can be the multi-component oxide of nickel, iron, copper, manganese, titanium etc. also, and gac can be gac particle, powder or fibrous.
In activated carbon catalysis ozone oxidation unit, the effect of gac or metal oxide-loaded gac has three:
One: gac can be used as catalyzer, and the O3 catalytic oxidation organic pollutant is more targeted to the degraded of pollutent; Gac can also promote ozone to be converted into the stronger hydroxyl radical free radical isoreactivity group of oxidisability simultaneously, comes the oxidation organic pollutant;
Its two: gac can be used as sorbent material, and the organic pollutant in the planar water is beneficial to ozone oxidation, degraded.After organic pollutant was oxidized, gac obtained regeneration at inside reactor, remains adsorptive power;
Its three: gac can promote the dissolving of gas phase ozone, improves the mass transfer of ozone, improves the utilising efficiency of ozone.
The water that contains micro quantity organic pollutant is through the activated carbon catalysis ozone oxidation, organic pollutant is wherein removed quickly and is transformed, biodegradable also gets a greater increase, easier being degraded by microorganisms, so be more suitable for the processing of follow-up biological activated carbon, the removal effect of micro quantity organic pollutant is better.
The present invention organically combines activated carbon catalysis ozonize and biological activated carbon, and is applied to the purification of micro-polluted water, and the removal efficient of organic pollutant in the water is improved greatly, can reduce the dosage of ozone, reduces cost of water treatment.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Embodiment
Below in conjunction with accompanying drawing in detail embodiments of the invention once are described in detail:
Embodiment one: the activated carbon catalysis ozone oxidation-biological activity carbon purifying of secondary effluent of municipal sewage plant.
As shown in Figure 1, the secondary effluent of municipal sewage plant enters from the bottom of activated carbon catalysis ozone oxidation reaction device 100, and ozone gas feeds from the bottom of described reactor, and ozone gas is through air distribution plate in the described reactor 102 and water uniform mixing; The active carbon layer 101 that water and ozone gas are upwards flowed through and filled in the reactor, the residence time is 16min, the organic pollutant in the water is removed or transforms; Top water outlet 104 from described reactor in the water after the preliminary treatment flows out, and ozone tail gas is discharged from the gas discharge outlet 103 of described reactor;
Flow into through the water of above-mentioned preliminary treatment water-in 205 from biological activated carbon reactor 200 1 sides, the biological activated carbon layer 201 that current are filled in reactor, the residence time is between 15min; Organic pollutant is by biological degradation, removal in the water, and the water after the processing flows out from the water outlet 202 of described reactor opposite side.
According to the concentration and the processing requirements of water pollutant, can also be toward aeration in the biological activated carbon unit.The biological activated carbon unit is after running for some time, carry out back flushing to upgrade the surface of biological activated carbon, backwashing water flows into from the unitary bottom of biological activated carbon water outlet 202, through gravel 203 and biological activated carbon layer 201, discharges from top backwashing water water outlet 204 at last.
In activated carbon catalysis ozone oxidation unit, can add the ozone of various dose according to processing target.When the ozone dosage is respectively 3mg/L and 6mg/L, the removal effect of water pollutant is seen Table 1.
When table 1 ozone dosage is 3mg/L and 6mg/L to removal effect of organic matter in the secondary effluent
| Water-quality guideline | TOC | COD Mn | ||
| Ozone dosage (mg/L) | 3 | 6 | 3 | 6 |
| Influent concentration (mg/L) | 10.1-13.1 | 10.8-14.8 | 9.5-11 | 9.3-12.5 |
| O 3The average removal rate of/AC+BAC (%) | 38.2 | 42.4 | 48.5 | 71.3 |
| O 3The average removal rate of+BAC (%) | 31.3 | 37.8 | 43.4 | 66.4 |
| O 3The average removal rate of/AC (%) | 15.8 | 27.5 | 21.6 | 35.9 |
| O 3Average removal rate (%) | 11.6 | 21.6 | 18.3 | 32.5 |
Annotate: O
3/ AC+BAC is activated carbon catalysis ozone oxidation-biological activated carbon method; O
3+ BAC is ozone oxidation-biological activated carbon method; O
3/ AC is an activated carbon catalysis ozone oxidation method; O
3Be the ozone oxidation method.
When the ozone dosage is 3mg/L, ozone oxidation-biological activated carbon method is 31.3% to total organic carbon in the water (TOC) clearance, and the TOC clearance of activated carbon catalysis ozone oxidation-biological activated carbon method is 38.2%, clearance improves 22%, and the clearance when adding 6mg/L than ozone oxidation-biological activated carbon (37.8%) is also high; And activated carbon catalysis ozone oxidation-biological activated carbon method is to permanganate index (COD
Mn) clearance improve 11.8%.
When the ozone dosage was 6mg/L, activated carbon catalysis ozone oxidation-biological activated carbon method was to permanganate index (COD
Mn) clearance reach 71.3%.
Embodiment two: activated carbon catalysis ozone oxidation-biological activated carbon method purifies the reservoir water that contains micro-content organism.
Adopt activated carbon catalysis ozone oxidation-biological activated carbon method to purify reservoir water, its step and embodiment one are roughly the same, wherein pending reservoir water is 16min in the unitary residence time of activated carbon catalysis ozone oxidation, is 15min in the unitary residence time of biological activated carbon.In activated carbon catalysis ozone oxidation unit, can add the ozone of various dose according to processing target.When the ozone dosage is 3mg/L, the removal effect of water pollutant is seen Table 2.
Ozone oxidation-biological activated carbon method is 32.9% to the clearance of total organic carbon in the water (TOC), and the TOC clearance of activated carbon catalysis ozone oxidation-biological activated carbon method is 36.9%, improves 12%.The activated carbon catalysis ozone oxidation improves 20% than the TOC clearance of independent ozone oxidation.
When table 2 ozone dosage is 3mg/L to removal effect of organic matter in the reservoir water
| Water-quality guideline | TOC | COD Mn | |
| Influent concentration (mg/L) | 5.7-8.6 | 3.1-4.1 | |
| O 3The average removal rate of/AC+BAC method (%) | O 3/AC | 11.4 | 20.2 |
| O 3/AC+BAC | 36.9 | 47.8 | |
| O 3The average removal rate of+BAC method (%) | O 3 | 9.5 | 17.9 |
| O 3+BAC | 32.9 | 43.2 | |
Annotate: O
3/ AC is an activated carbon catalysis ozone oxidation method; O
3/ AC+BAC is activated carbon catalysis ozone oxidation-biological activated carbon method; O
3Be the ozone oxidation method; O
3+ BAC is ozone oxidation-biological activated carbon method.
When the ozone dosage is that 3mg/L, the unitary residence time of activated carbon catalysis ozone oxidation are 16min, the unitary residence time of biological activated carbon, the removal effect of water pollutant saw Table 3 when being respectively 15min, 30min and 60min.When not having follow-up biological activated carbon unit, activated carbon catalysis ozone oxidation unit is to total organic carbon (TOC) and permanganate index (COD
Mn) clearance have only 11.1-11.4% and 17.5-20.2 respectively, after adopting activated carbon catalysis ozone oxidation of the present invention-biological activated carbon method, TOC and COD
MnClearance reach 36.9% and 47.8% (biological activated carbon residence time 15min), 42.5% and 56.7 (biological activated carbon residence time 30min), 45.2% and 64.0% (biological activated carbon residence time 60min), it is very remarkable to improve effect.
The removal effect of the different residence time lower storage reservoir water pollutants in table 3 biological activated carbon unit
| Water-quality guideline | TOC | COD Mn | |||||
| The biological activated carbon unit residence time (min) | 15 | 30 | 60 | 15 | 30 | 60 | |
| Influent concentration (mg/L) | 5.7-8.6 | 5.4-7.0 | 6.4-7.3 | 3.1-4.1 | 3.3-4.3 | 3.8-4.3 | |
| Average removal rate (%) | O 3/AC | 11.4 | 11.1 | 11.2 | 20.2 | 17.7 | 17.5 |
| O 3/AC+BAC | 36.9 | 42.5 | 45.2 | 47.8 | 56.7 | 64.0 | |
Annotate: O
3/ AC is an activated carbon catalysis ozone oxidation method; O
3/ AC+BAC is activated carbon catalysis ozone oxidation-biological activated carbon method.
Claims (2)
1. activated carbon catalysis ozone oxidation-biological activated carbon purifies the method for water pollutant, it is characterized in that this method mainly comprises following activated carbon catalysis ozone oxidation and two unit of biological activated carbon:
Pending water enters from the bottom of activated carbon catalysis ozone oxidation reaction device, and ozone gas feeds from the bottom of described reactor, and described ozone gas is through air distribution plate and water uniform mixing in the described reactor; The active carbon layer that water and ozone gas are upwards flowed through and filled in the reactor, the organic pollutant in the water was removed or transformed between 5～30min the residence time; Water after the preliminary treatment flows out from the top of described reactor, and ozone tail gas is discharged from the gas discharge outlet of described reactor;
Through the water of above-mentioned preliminary treatment a side inflow from the biological activated carbon reactor, the biological activated carbon layer that current are filled in reactor, the residence time, organic pollutant was by biological degradation, removal in the water between 5～90min; Water after the processing flows out from described reactor opposite side.
2. the method for purification water pollutant according to claim 1 is characterized in that: the ozone dosage in the described activated carbon catalysis ozone oxidation unit is 0.5mg/L～20mg/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031233929A CN1223523C (en) | 2003-04-26 | 2003-04-26 | Method for purifying pollutant in water by using biological activity carbon-catalysis or activated carbon and oxidation of ozone |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031233929A CN1223523C (en) | 2003-04-26 | 2003-04-26 | Method for purifying pollutant in water by using biological activity carbon-catalysis or activated carbon and oxidation of ozone |
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| Publication Number | Publication Date |
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| CN1446757A CN1446757A (en) | 2003-10-08 |
| CN1223523C true CN1223523C (en) | 2005-10-19 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103613254A (en) * | 2013-12-18 | 2014-03-05 | 中国市政工程中南设计研究总院有限公司 | Method for deep treatment of refractory organic wastewater of sewage treatment plant in fine chemical industry park |
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| CN101962238A (en) * | 2010-09-07 | 2011-02-02 | 北京林业大学 | Method for removing trace medicine in water by using sludge-based activated carbon to catalyze ozone for oxidation |
| CN102351350B (en) * | 2011-09-15 | 2013-06-05 | 上海大学 | Water treatment experimental device using biological activated carbon and ozone |
| CN102491581B (en) * | 2011-11-14 | 2013-11-27 | 中国海洋石油总公司 | Advanced treatment method for production waste water of acrylic acid and ester device |
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| CN106396073B (en) * | 2016-09-07 | 2019-08-06 | 国网天津市电力公司 | Utilize the water treatment facilities and method of ozone-OH removal pollutant |
| CN106423055B (en) * | 2016-10-09 | 2018-12-25 | 东莞优胜环保科技有限公司 | One kind being easy to regenerated mixed active charcoal and COD degradation system |
| CN109550503A (en) * | 2018-11-01 | 2019-04-02 | 中再生乡村环境服务(武汉)有限公司 | A kind of catalyst and preparation method thereof applied to multiple catalyzing ozone oxidation system |
| CN112408581A (en) * | 2020-11-06 | 2021-02-26 | 天津亚德尔生物质科技股份有限公司 | Wastewater treatment device based on biological activated carbon and wastewater treatment method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103613254A (en) * | 2013-12-18 | 2014-03-05 | 中国市政工程中南设计研究总院有限公司 | Method for deep treatment of refractory organic wastewater of sewage treatment plant in fine chemical industry park |
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