CN103739162B - A kind of ozone-activated carbon adsorption removes the method for PPCPs in tap water - Google Patents
A kind of ozone-activated carbon adsorption removes the method for PPCPs in tap water Download PDFInfo
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- CN103739162B CN103739162B CN201310743789.5A CN201310743789A CN103739162B CN 103739162 B CN103739162 B CN 103739162B CN 201310743789 A CN201310743789 A CN 201310743789A CN 103739162 B CN103739162 B CN 103739162B
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Abstract
The invention discloses a kind of method that ozone-activated carbon adsorption removes PPCPs in tap water.Utilize ozone, adopt the mode of air water continuous reverse contact that ozone is fully contacted with the aqueous solution, then react further through reservation post, then enter biological activated carbon post and process.Method disclosed by the invention effectively can remove the PPCPs in tap water, wherein the clearance of Carbamzepine, oxcarbazepine, progesterone, medroxyprogesterone reaches more than 99.9%, and caffeine, quinizine, pyramidon and Sulfamethoxazole all do not detect in water outlet.Relative to existing drinking water treatment technology, there is higher chemical safety guarantee.Also have good removal effect to the Conventional pollution of Drinking Water, water outlet can be stablized and reached national drinking water sanitary standard (GB5749-2006) and have great practical value and application potential simultaneously.
Description
Technical field
The present invention relates to a kind of method that ozone-activated carbon adsorption removes PPCPs in tap water, belong to purifying water process technical field.
Technical background
PPCPs comprises multiple compounds perhaps, mainly can be divided into two large class, i.e. Pharmaceuticals and personal care products.Its Chinese traditional medicine of a great variety, can comprise widely used all kinds of prescribed and non prescribed medicine, as microbiotic, analgesic antiphlogistic medicine, stimulant, tranquilizer and hormone etc.Personal-care supplies kind also various, can comprise: spices, sun-screening agent, opalizer, disinfection sanitizer etc.The medication of the mankind and animal is that the main of PPCPs in environment is artificially originated.After the mankind or animal body take in medicine, a series of biochemical reaction can be experienced and only have and be utilized on a small quantity, and the drug metabolite of the medicine do not consumed and generation is excreted by the form such as urine, ight soil.Simultaneously in daily life washing process, shampoo, body wash, makeup and washing composition etc. also can be discharged with sewage form, therefore there is a large amount of PPCPs in sanitary sewage, become PPCPs topmost collect one of.Simultaneously, without use or expired medicine, sewage work discharge is rich in the inappropriate disposal of the solid waste containing PPCPs that PPCPs mud and livestock industry produce, such as directly abandon landfill etc. make soil also become PPCPs main collect one of ground.In addition, in the waste water of PPCPs manufacturing industry, hospital wastewater, livestock industry, culture fishery waste water also containing a large amount of PPCPs.
The existence of these PPCPs existed in environment has a negative impact to the mankind or other biological body.The contraceptive bian (progesterone, medroxyprogesterone etc.) that the such as mankind take has endocrine to the fish in environment, Reptilia and invertebrates, estrogens medicine can cause alligator to lay eggs, also can change the endocrine system of alligator embryo simultaneously, have a strong impact on the breeding of alligator.Carbamzepine, O'Casey equality 13 kinds of medicines can make the growth rate of zebra fish liver cell and human embryonic cell reduce under environmental concentration.Caffeine, to heart patient and the toxic effect of women, easily causes the illness such as arrhythmia and women breast cancer.Quinizine and pyramidon have toxicity to lung and mucous membrane, and long-term exposure can cause target organ impaired, works the mischief to HUMAN HEALTH.Therefore, how effectively the PPCPs removed in water surrounding becomes major issue urgently to be resolved hurrily.
At present, the removal pathway of PPCPs mainly can be divided into: conventional processing, biological degradation, physical removal and chemical oxide removal.Select treatment process main it is considered that processing costs and treatment efficiency.Conventional processing connects sedimentation and filtration after comprising cohesion, coagulation, precipitation, can not reach remove completely the removal of PPCPs; Biological method conditional is loaded down with trivial details wayward; Physical is removed PPCPs and is mainly comprised charcoal absorption and membrane technology, charcoal absorption is subject to the impact of organism self character, good removal effect is had for hydrophobicity PPCPs, but to wetting ability and the stronger organism treatment effect of polarity not good, the pollutent that film process concentrates still exists needs process further, and membrane pollution problem is also the major issue that later stage needs are paid close attention to simultaneously; Chemical process cost is higher and can produce a large amount of toxic intermediates.The effective treating method removed PPCPs in water body is varied, sometimes in order to reach the PPCPs that degrades thoroughly, often needs several minimizing technology to join together to use.
Summary of the invention
The invention discloses a kind of method that ozone-activated carbon adsorption removes PPCPs in tap water, the technical scheme of employing is as follows:
A kind of ozone-activated carbon adsorption removes the method for PPCPs in tap water, that pending tap water is pumped into from ozone column top, ozone gas enters ozone post from ozone column bottom aeration board, adopt continuum micromeehanics and add ozone continuously and the reverse mode contacted of air water makes ozone fully contact with the aqueous solution, the water outlet of ozone post enters reservation post, retain pollutent in post to react further with remaining ozone, water outlet enters after biological activated carbon post processes again flows out from bottom.
Described method, is characterized in that, step is as follows:
1) oxygen is passed through ozonizer generates ozone, after ozone detects, enter ozone post by ozone column bottom through aeration board;
2) pending tap water is pumped into ozone post, to be injected continuously by air water and the mode of reverse contact carries out ozonize;
3) by through step 2) water sample that processes pumps into reservation post, and pollutent and residue ozone are reacted further;
4) by through step 3) water sample that retains post process to flow out from bottom after pumping into biological activated carbon post adsorption treatment and collects;
5) last, back flushing is carried out to the biological activated carbon post processing water sample.
Described method steps 2) described in the ozone addition of ozonize be 0.208mM, hydraulic detention time is 20min.
Described method steps 3) described in retain post hydraulic detention time be 25min.
Described method steps 2) and step 3) described in ozone reaction post and to retain post material therefor be synthetic glass, thickness is 5mm, post height 1.2m, internal diameter 100mm.
Described method steps 4) described in biological activated carbon post gac be granulated active carbon, methylene radical blue value is 180mgg
-1, iodine sorption value is 1100mgg
-1, particle diameter is 1.39-3.33mm.
Described method steps 4) described in the air-land combat of biological activated carbon post be 25min.
Described method steps 5) described in back flushing, the cycle is 10d, and back washing strength is 5-10Lm
-2s
-1, back flushing rate of expansion is 10-15%.
The concrete steps of described method are as follows:
1) oxygen is passed through ozonizer generates ozone, after ozone detects, enter ozone post by ozone column bottom through aeration board;
2) pending tap water is pumped into ozone post, to be injected continuously and the mode of reverse contact carries out ozonize by air water, ozone addition is 0.208mM, and hydraulic detention time is 20min;
3) by through step 2) water sample that processes pumps into reservation post, and pollutent and residue ozone are reacted further, and hydraulic detention time is 25min;
4) by through step 3) water sample that retains post process pumps into biological activated carbon post adsorption treatment, and biological activated carbon post air-land combat is 25min, and after process, water sample flows out from bottom and collects;
5) last, carry out back flushing to the biological activated carbon post processing water sample, the cycle is 10d, and back washing strength is 5-10Lm
-2s
-1, back flushing rate of expansion is 10-15%.
PPCPs of the present invention is mainly progesterone, medroxyprogesterone, Carbamzepine, oxcarbazepine, caffeine, quinizine, pyramidon and Sulfamethoxazole.
Beneficial effect of the present invention: by the ozone-activated carbon adsorption technique in the present invention, in tap water, the clearance of Carbamzepine, oxcarbazepine, progesterone, medroxyprogesterone reaches more than 99%, and caffeine, quinizine, pyramidon and Sulfamethoxazole all do not detect in water outlet.In addition, O
3-BAC coupling technique is to the conventional index (COD of Drinking Water
mn, UV
254, NH
4 +-N, turbidity, formaldehyde, bromate and total plate count) all there is good removal effect.
Accompanying drawing explanation
The Experimental equipment of Fig. 1 ozone-biological active carbon coupling technique.
The each index change of Fig. 2 BAC post Inlet and outlet water.
Embodiment
The invention discloses a kind of method that ozone-activated carbon adsorption removes PPCPs in tap water, the device of employing as shown in Figure 1.Below in conjunction with embodiment, the present invention will be further described, but the present invention is not by the restriction of embodiment.
The startup of embodiment 1BAC and biofilm
Biofilm average temperature is more than 20.0 DEG C, and proper temperature microbial growth, is conducive to gac biofilm.BAC post adopts synthetic glass to make, thickness is 5mm, and reactor cubic capacity is about 8.1L, and wherein filtrating area volume is about 6.53L, catchment area volume is about 1.57L, height overall 1.5m, catchment area internal diameter 100mm, filtrating area internal diameter 80mm, gac packing height 1.0m, bottom is provided with supporting layer and is respectively gravel and rubble sand, and packing height is respectively 0.1m, reveals in order to prevent gac.Arrange a thief hole from BAC post bottom every 0.1m, pillar top is provided with overflow port.
Gac Specifeca tion speeification is as follows: gac kind selects granulated active carbon; Methylene radical blue value is 180mgg
-1; Iodine sorption value is 1100mgg
-1; Particle diameter is 1.39-3.33mm.
Primary operating parameter during BAC biofilm: pillar adopts top water inlet, bottom water outlet.Air-land combat EBCT=25min, backwashing period is 10d, and back washing strength is 5 ~ 10Lm
-2s
-1, back flushing rate of expansion is 10 ~ 15%.
Forefathers' research proposal adopts COD
mnand NH
4 +-N clearance is stable is used as microbial film maturity symbol, but in this experiment, biofilm occurs NO mid-term
2 --N Accumulation Phenomenon, the phenomenon that the biofilm later stage reduces to zero gradually shows that nitrobacteria quantity tends towards stability, and also can be used as successfully the mark of biofilm.Meanwhile, biomass and bioactive increase are also judge biofilm successfully another mark.As seen from Figure 2, along with the continuous prolongation of working time, BAC post is to NH
4 +-N, NO
2 --N, COD
mn, UV
254removal all reach stable, at the biofilm initial stage of BAC post, direct observing response device, find that active black colour purity is clean, with the prolongation of working time, find that there is khaki color material gradually and be attached on gac, color is deepened gradually.Before back flushing, below gac top, 0.1m gets BAC sample and measures biomass and dehydrogenase activity, and with the prolongation of working time, in BAC post, biomass and biological activity all raise, and after running 50d, the biomass of BAC post reaches 279.61nmolg
-1, dehydrogenase activity reaches 31.54Ug
-1.
The operation of embodiment 2 ozone-biological active carbon coupling technique
Whole experimental installation is made up of water butt, ozonizer, ozone reaction post, reservation post, biological activated carbon post and ozone destruct device and back-purge system etc.Ozone reaction post and reservation post adopt synthetic glass to make, and thickness is 5mm, post height 1.2m, internal diameter 100mm, and top is provided with production well, and ozone reaction column bottom has additional core micro-pore aeration plate.Wherein for the BAC post after natural membrane, it is saturated that middle lower floor gac has reached absorption, and the microorganism of apposition growth is less simultaneously, and the microorganism mainly in the gac of upper strata is playing a role, the adsorption of gac is very weak, therefore again loads activated carbon column.Bottom loads the new granulated active carbon without use of 0.7m again, and the 0.3m successful particle BAC of biofilm is loaded at top again, makes whole BAC post play better biological degradation and physical adsorption usefulness.
In whole experiment, water inlet pumps into from ozone column top by water pump.Ozone gas is by after ozone detector, and from ozone column bottom, core micro-pore aeration plate enters ozone post, and adopt the reverse contact of air water, ozone is fully contacted with the aqueous solution, and tail gas passes in ozone destruct device.Whole reaction process adopts continuum micromeehanics and adds the mode of ozone.The water outlet of ozone post enters reservation post by bottom water outlet through water pump, and retain pollutent in post and can react further with remaining ozone, water outlet enters BAC column top through water pump again, flows out after BAC process from bottom.
Run duration primary operating parameter: ozone post ozone dosage is 0.208mM, often kind of PPCP dosage is 0.050mM, and hydraulic detention time HRT is 20min, the HRT retaining post is 25min, the empty bed residence time EBCT of BAC post is that the back flushing of 15min, BAC post adopts tap water, and the cycle is 10d.
To water inlet, O in operational process
3conventional index and 8 PPCPs of water outlet and BAC water outlet water sample detect.The detected result of conventional index is in table 1, and the detected result of 8 PPCPs is in table 2.
Table 1 ozone-biological active carbon coupling technique is to the removal of each conventional index
As shown in Table 1, the NH in BAC water outlet water sample
4 +-N and BrO
3 -all do not detect, and other indexs all reach national drinking water sanitary standard (GB5749-2006).
As shown in Table 2, after ozone and the absorption of BAC post, in water outlet water sample, the content of caffeine, quinizine, pyramidon and Sulfamethoxazole is all lower than detectability, and in water sample, the reduction amplitude of Carbamzepine, oxcarbazepine, progesterone and medroxyprogesterone content has all exceeded 99.9%.
Table 2 ozone-biological active carbon coupling technique is to the removal of PPCPs
Claims (1)
1. ozone-activated carbon adsorption removes a method of PPCPs in tap water, and it is characterized in that, concrete steps are as follows:
1) oxygen is passed through ozonizer generates ozone, after ozone detects, enter ozone post by ozone column bottom through aeration board; Described ozone post material therefor is synthetic glass, and thickness is 5mm, post height 1.2m, internal diameter 100mm;
2) pending tap water is pumped into ozone post, to be injected continuously and the mode of reverse contact carries out ozonize by air water, ozone addition is 0.208mM, and hydraulic detention time is 20min;
3) by through step 2) water sample that processes pumps into reservation post, and pollutent and residue ozone are reacted further, and hydraulic detention time is 25min; Described reservation post material therefor is synthetic glass, and thickness is 5mm, post height 1.2m, internal diameter 100mm;
4) by through step 3) water sample that retains post process pumps into biological activated carbon post adsorption treatment, and biological activated carbon post air-land combat is 25min, and after process, water sample flows out from bottom and collects; In described biological activated carbon post, gac is granulated active carbon, and methylene radical blue value is 180mgg
-1, iodine sorption value is 1100mgg
-1, particle diameter is 1.39-3.33mm;
5) last, carry out back flushing to the biological activated carbon post processing water sample, the cycle is 10d, and back washing strength is 5-10Lm
-2s
-1, back flushing rate of expansion is 10-15%.
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| CN104291521A (en) * | 2014-09-01 | 2015-01-21 | 陈小洁 | Water treatment method |
| CN104671361B (en) * | 2015-02-11 | 2017-05-24 | 清华大学 | Method for removing PPCPs micropollutants in secondary sedimentation tank wastewater |
| CN104609532B (en) * | 2015-02-11 | 2017-05-24 | 清华大学 | Method for removing PPCPs in treatment process of drinking water |
| CN104724815B (en) * | 2015-04-02 | 2017-03-15 | 中国科学院城市环境研究所 | Using MnOx15 PMS compound systems of/SBA efficiently quickly remove peace for neighbour method and application |
| CN107324607A (en) * | 2015-12-22 | 2017-11-07 | 潘豪杰 | The system of carbamazepine in a kind of removal waste water |
| CN106477824A (en) * | 2016-11-28 | 2017-03-08 | 清华大学深圳研究生院 | A kind of method and system for removing residual antibiotic in eliminating water |
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