CN104108783A - Method for rapid, high-efficiency and selective degradation of trace benzopyrene in water - Google Patents
Method for rapid, high-efficiency and selective degradation of trace benzopyrene in water Download PDFInfo
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- CN104108783A CN104108783A CN201410312754.0A CN201410312754A CN104108783A CN 104108783 A CN104108783 A CN 104108783A CN 201410312754 A CN201410312754 A CN 201410312754A CN 104108783 A CN104108783 A CN 104108783A
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Abstract
The invention relates to a method for rapid, high-efficiency and selective degradation of trace benzopyrene in water. The method comprises the following steps: cutting trace-benzopyrene-containing wastewater having undergone biochemical treatment into water films with a filling material in a catalytic ozonation reactor; allowing the water films to contact with ozone or ozonized air flowing along a reverse direction and to be dissolved; and selectively degrading trace benzopyrene in the wastewater under the preferential adsorption and catalytic oxidation coupling effects of a molecular imprinting filling material. According to the invention, molecular imprinting technology and catalytic ozonation technology are combined, and trace benzopyrene in the wastewater is rapidly, highly efficiently and selectively treated; the absorption rate of ozone is more than 90% in 10 min in the catalytic ozonation reactor, so the removal rate of trace benzopyrene is more than 99%. The method can be widely applied to deep and recycling treatment of a variety of sewage and wastewater containing benzopyrene.
Description
Technical field
The present invention relates to a kind of fast, the method for micro-benzopyrene in efficient, degradation selectivity water.The method can fast, efficiently, optionally be removed the micro-benzopyrene pollutent in water, is applicable to the degree of depth and the regeneration processing technology field of the trade effluents such as coking, oil refining, pitch, plastics.
Background technology
In recent years, the chemical industry developments such as Coal Chemical Industry, oil, plastics, coking, the Persistent organic pollutants (as polycyclic aromatic hydrocarbons) such as a large amount of many rings, heterocycle, long-chain also produce thereupon.Wherein, benzopyrene is a kind of strong carcinogens of polycyclic aromatic hydrocarbons toxic maximum, can cause prokaryotic organism, mammalian cell to produce genotoxicity.It enters human environment especially in water surrounding by different approach, and its molecular weight is large, the feature of Stability Analysis of Structures, low water solubility becomes a large difficulty in treatment of environmental area.On the other hand, national reusing sewage rate continues to improve in recent years, the important channel that the regeneration of municipal effluent has become and improved water resources comprehensive utilization rate, alleviated shortage of water resources.Even if benzopyrene can reach discharge or reuse standard after conventional biochemical treatment, but because of its strong carinogenicity, the micro-benzopyrene containing in water outlet brings risk in various degree still can to the regeneration of sewage.Therefore, for the removal of micro-benzopyrene in waste water, become the study hotspot of environmental area.
Absorption method, as a kind of common method of removing low water solubility in water, neutral charge, high-molecular-weight organic material, has higher clearance to benzopyrene.But the benzopyrene pollution thing that adsorption is removed is just transferred to solid phase from water, and along with disposal and the reuse of sorbent material, benzopyrene can come back in environment, it does not have from being weakened in fact the harm of environment.
On the one hand, abroad to having done a lot of research with ozonation technology oxide treatment benzopyrene.But investigator's adopt in research process is scattered in the pattern in water by ozone by bubble diffuser more, and this makes ozone utilization rate not high, produces a large amount of ozone tail gas.In addition, the degradation effect to benzopyrene that investigator makes mostly is: 50% left and right of degrading within a few hours, and because ozone oxidation is limited in one's ability, in reaction process, produce by product.On the other hand, catalytic ozonation technology is applied to dirty wastewater treatment, mainly utilize ozone or ozonized air under the effect of catalyzer, produce the extremely strong free radical of oxidation capacity realize water in organic degraded.Its unique advantage is: (1) can be oxidized the most organism except a few organism.(2) can be CO by organism permineralization
2and H
2o etc. are simple, the inorganics of environmental sound.But still there are some problems in catalytic ozonation technology when practical application: (1) traditional catalytic ozonation reactor adopts the pattern of " gas is scattered in water ", utilizes gaseous diffuser to make ozone form small bubbles, with liquid phase contact lysis.But its mass-transfer efficiency and speed of reaction are usually not fully up to expectations.(2) making method of the ozone solid catalyst of known technology is generally to adopt activated alumina, gac, pottery etc. as carrier at present, using the oxide compound of transition metal or transition metal as the activeconstituents of catalyzer, by steps such as dipping, oven dry, roastings, obtain catalyst prod.The problem that these solid catalyst product existence and stabilities of making are not high, its activeconstituents easily flows away with current and cause ozone catalytic effect to reduce.(3) tail gas producing after catalytic ozonation reaction can not get appropriate disposal, causes ecological environment problem.(4) catalytic ozonation degradation of organic substances is a reaction process based on free radical, and it does not have selectivity to pollution substance, in the Complex water body that is difficult to coexist at multiple pollutant by target compound selective removal.For lower concentration, highly toxic benzopyrene in dirty waste water, due to the interference of the pollutent that coexists, catalytic ozonation technology especially strong difficulty makes, and is difficult to obtain better degradation effect.Chinese patent (CN202924812U) discloses a kind of " organic waste water catalytic ozonation treatment unit ", its principal character is exactly by the counter current contact of organic waste water and ozone, reach and remove organic object, and process ozone tail gas by ozone layer destroying device.But its defect is also apparent: ozone is easily overflowed from reactor bottom with water outlet, though destroyed ozone tail gas, still there is ecological safety risk.In addition, it can not optionally process organism, not good for low-concentration organic or the specific organic removal effect of target, does not reach the object of the micro-benzopyrene of effective degraded.
Summary of the invention
The object of the invention is for above problem, provide a kind of catalytic ozonation reaction to remove the method for the catalytic ozonation of micro-benzopyrene in water, the method is easy to engineering practice, Ozone Absorption efficiency is high, speed of response fast, non-secondary pollution risk.
For reaching above-mentioned purpose, one aspect of the present invention builds catalytic ozonation reactor and adopts homemade molecular imprinting modification catalyzer, make catalytic ozonation reactor thoroughly abandon the ozone mass transfer pattern of " gas is scattered in water ", but the pattern of employing " water-dispersion is in gas ": current form liquid film by the spray of water distribution board in catalytic ozonation reactor and the cutting of filler (catalyzer), liquid film constantly collides with filler in decline process, thickness of liquid film reduced and constantly updated, having increased considerably the effective contact area of gas-liquid two-phase.Therefore, the pattern of " water-dispersion is in gas " increased substantially ozone mass-transfer efficiency, shortened the ozone solution time, can fast, efficiently remove micro-benzopyrene in water, in addition on the one hand, increase ozone tail gas breaking plant or adopted series and parallel technique, carry out ozone tail gas recycling, eliminate secondary pollution risk.
Concrete technology is as follows:
The first step, first build catalytic ozonation reactor, catalytic ozonation inside reactor sets gradually water distribution layer, molecular imprinting modification catalytic filler layer and reservoir bed totally three functional zone from top to bottom, water distribution layer is by the suspension that is fixed on catalytic ozonation reactor top, with the aperture that is fixed on suspension bottom be 2-4mm, the water distribution board of the perforation that percentage of open area is 50% forms; Molecular imprinting modification catalytic filler layer is fixed by bottom and catalytic ozonation reactor bottom, the support that top and filler supporting plate are fixing, and the molecular imprinting modification catalytic filler on filler supporting plate forms; The reservoir bed water seal that to be prevention ozone between catalytic ozonation reactor bottom and filler supporting plate directly flow away from the bottom of catalytic ozonation reactor with current; The bottom center of catalytic ozonation reactor shell is provided with water outlet, is provided with the inlet mouth of liquid level meter and ozonize gas between reservoir bed and molecular imprinting modification catalytic filler layer, and molecular imprinting modification catalytic filler layer place is provided with manhole and filler discharge opening; Catalytic ozonation reactor top is provided with water-in and tail gas air outlet;
The preparation method of above-mentioned molecular imprinting modification filler is:
I, material choice and metering, measure in mass ratio iron nitrate: manganous phosphate: single nickel salt: Vanadium Pentoxide in FLAKES: potassium oxide: copper sulfate: methacrylic acid: aluminum oxide=6-12:4-6:2-5:2-6:2-6:3-5:1-3:100 part, above-mentioned raw materials is commercially available analytical pure commodity;
II, iron modified aluminium oxide supports is mixed in preparation, first the iron nitrate of the first step metering is added to water preparation and become the iron nitrate solution that mass percentage concentration is 5-10%, using aluminum oxide as carrier, put into iron nitrate solution again and carry out ion-exchange, standing 4-6 hour, the iron content alumina supporter obtaining after filtration is through 60-120 ℃ of dry 10-12h, and roasting 3-4 hour obtains mixing iron modified aluminium oxide supports at 500-600 ℃; Filtered liquid is recycled;
III, support of the catalyst preparation, the manganous phosphate first respectively the first step being measured, Vanadium Pentoxide in FLAKES and potassium oxide add water preparation becomes the manganous phosphate solution that mass percentage concentration is 6%-8%, the Vanadium Pentoxide in FLAKES solution of 5%-10% and the potassium oxide solution of 8%-10%, three kinds of solution are mixed into precursor solution A, the single nickel salt respectively the first step being measured again and copper sulfate add water preparation, and to become mass percentage concentration be the nickel sulfate solution of 4%-6% and the copper-bath of 4%-8%, these two kinds of solution are mixed into precursor solution B, then, the iron modified aluminium oxide supports of mixing that second step is obtained is dipped in each 3h in precursor solution A and precursor solution B successively, after each dipping, all need through 80-100 ℃ of dry 10-12h, modification after final drying is mixed to iron alumina supporter roasting 2-3 hour under the inert gas atmosphere of 600-900 ℃ and obtain granules of catalyst, the granules of catalyst making is added to methacrylic acid: in the mixing solutions of chloroform=1:1 volume ratio, after standing 24h, filtration, vacuum-drying make support of the catalyst,
IV, the preparation of molecular imprinting modification filler, the pure benzopyrene of commercially available top grade of take is template, support of the catalyst is function base material, ethylene glycol dimethacrylate is linking agent, dehydrated alcohol is solvent, take azo-bis-isobutyl cyanide as initiator, measure benzopyrene: support of the catalyst=1:10 mass ratio, measure again dehydrated alcohol: 98% ethylene glycol dimethacrylate: analytical pure azo-bis-isobutyl cyanide: support of the catalyst=5:1:15:1 mass ratio, then, first benzopyrene and support of the catalyst are joined in dehydrated alcohol, under room temperature, fully stir 6h, respectively ethylene glycol dimethacrylate and azo-bis-isobutyl cyanide are added again, in sealing, temperature is 35 ℃, polyreaction 15h under agitation condition.Gained particle first cleans 3 times with distilled water, then cleans 3 times with ethanol, then puts into baking oven dry 1h at 55 ℃, finally puts into retort furnace at 400 ℃ of temperature lower calcination 3h, makes molecular imprinting modification filler.After testing, this molecular imprinting modification filler diameter is 3～6mm, and specific surface area is greater than 500m
2/ m
3;
Second step, adopt one or more catalytic ozonation reactors to remove micro-benzopyrene in water, first the water-in of catalytic ozonation reactor will be pumped into containing waste water after the biochemical treatment of 50ug/L-100mg/L benzopyrene, through water distribution board, be sprayed onto molecular imprinting modification catalytic filler layer, enter the ozone of catalytic ozonation reactor with lower end inlet mouth, in the cutting of molecular imprinting modification catalytic filler layer, form liquid film, liquid film pushes away under pincer attack in decline process and on the continuous collision of molecular imprinting modification catalytic filler layer and ozone, thickness of liquid film is reduced and constantly updated, increased considerably the effective contact area of gas-liquid two-phase, realized the pattern of " water-dispersion is in gas ", improved gas-liquid two-phase interface renewal rate, accelerated molten gas process, liquid film contacts with ozonize gas and selective adsorption, catalyzed oxidation is removed benzopyrene in water, last water flows out through lower end water outlet, ozone dosage is 50-100mg/L, in ozonized air, ozone concn is 1-3mg/L, the reactor waterpower residence time is 10-15min, more than can realizing the specific absorption to 90% of ozone, the removal efficiency of benzopyrene reaches 99.99%.
In described second step, adopt micro-benzopyrene in a catalytic ozonation reactor removal water to be, first set up the ozone tail gas breaking plant that a bottom is provided with steam heating tube, ozone tail gas breaking plant inside is loaded active carbon layer and catalytic filler layer from top to bottom successively, this catalytic filler layer is the molecular imprinting modification filler of preparing as the first step method, by pipeline, the air outlet of catalytic ozonation reactor is connected with ozone tail gas breaking plant bottom ozone tail gas inlet mouth, then will enter catalytic ozonation reactor containing waste water after the biochemical treatment of 50ug/L benzopyrene, wherein ozone dosage is 50-100mg/L, in ozonized air, ozone concn is 1-3mg/L, the reactor waterpower residence time is 10min, to the assimilated efficiency of ozone up to more than 90%, in water outlet, benzopyrene concentration is 0.0027ug/L, removal efficiency to benzopyrene reaches 99.99%, entering ozone concn in the tail gas in ozone tail gas breaking plant is 0.08-0.24mg/L, stop 10-20min, the catalytic filler layer catalytic decomposition that dependence consists of homemade molecular imprinting modification filler destroyed and charcoal absorption, ozone is destroyed substantially completely, in emission gases, ozone concn is less than 0.0001mg/L, meets the requirement of discharge.
In described second step, adopt micro-benzopyrene in a plurality of catalytic ozonation reactors removal water to be, according to the requirement of benzopyrene concentration <0.0029ug/L in water outlet, adopt three grades of series connection forms, be about to three catalytic ozonation reactors in series, to first pump into first catalytic ozonation reactor head water-in containing waste water after the biochemical treatment of 50ug/L-100mg/L benzopyrene, after reaction, by lower end water outlet, flowed out, pump into again second, by that analogy, and first reactor ozone tail gas out enters second reactor through pipeline, by that analogy, other conditions are identical, benzopyrene concentration <0.0029ug/L from the 3rd reactor water out, from the 3rd reactor gas out, ozone concn is less than 0.0001mg/L, meet the requirement of discharge, avoid the secondary pollution of ozone.
In described second step, adopt micro-benzopyrene in a plurality of catalytic ozonation reactors removal water to be, according to the requirement of benzopyrene concentration <0.01ug/L in water outlet, adopt three grades of parallel forms, be about to three catalytic ozonation reactors in parallel, to through different pipelines, enter the top water-in of three catalytic ozonation reactors containing waste water after the biochemical treatment of 50ug/L-100mg/L benzopyrene simultaneously, by lower end water outlet, flow out and converge by pipeline, unified discharge, benzopyrene concentration <0.01ug/L in water; And first reactor ozone tail gas out enters second reactor through pipeline, by that analogy, other conditions are identical, and from the 3rd reactor gas out, ozone concn is less than 0.0001mg/L, meets the requirement of discharge, avoids the secondary pollution of ozone.
The present invention has the following advantages:
1. because the present invention has designed water distribution layer, molecular imprinting modification catalytic filler layer and the reservoir bed matching each other in catalytic ozonation reactor, and the specific surface area of molecular imprinting modification catalytic filler is greater than 500m
2/ m
3, realize the pattern of " water-dispersion is in gas ", thereby improved gas-liquid two-phase interface renewal rate, accelerate molten gas process.Therefore,, in catalytic ozonation reactor, retention time of sewage only needs more than 1-10min can realize the specific absorption to 90% of ozone, efficiently the micro-benzopyrene in fast degradation water.
2. with respect to the catalyzer using in traditional catalytic ozonation reaction, the present invention adopts a kind ofly homemadely to be had very high specific surface area and is comprised of multiple catalytic active component, catalytic activity is high, and the molecular imprinting modification filler of stability, uniformity and good dispersion degree, therefore make the cut liquid film that forms of waste water in catalytic ozonation reactor, and selective adsorption, catalyzed degradation trace benzopyrene remains that higher degradation capability and its stability is constant, this has reduced the cost of catalyst change, operation.
3. because the present invention has adopted homemade molecular imprinting modification catalyst filling, under selective adsorption, catalyzing oxidizing degrading coupling, the efficient removal of realization to target trace benzopyrene in waste water, can eliminate other the organic interference existing in waste water, removal efficiency is high, reaction is thorough, simultaneously, according to the different requirements of benzopyrene concentration in water outlet, adopt three grades of serial or parallel connection forms, both met the efficient removal of target trace benzopyrene, realize again ozone recycling, reached the object of resource reutilization.
4. when the present invention removes in water micro-benzopyrene with catalytic ozonation reactor, first set up the ozone tail gas breaking plant that a bottom is provided with steam heating tube, by the method that adopts ozone tail gas to destroy, the residual ozone of catalytic decomposition, absorption catalytic ozonation reactor unreacted, has realized thorough processing, the non-secondary pollution of tail gas.
Accompanying drawing explanation
Fig. 1 is the structural representation of catalytic ozonation reactor of the present invention
Fig. 2 is the vertical view of catalytic ozonation reactor of the present invention
Fig. 3 is the water distribution board schematic diagram of catalytic ozonation reactor of the present invention
Fig. 4 is the filler supporting plate schematic diagram of catalytic ozonation reactor of the present invention
Fig. 5 is a kind of micro-benzopyrene process flow sheet in the removal water that destroys ozone tail gas that has of the present invention
Fig. 6 is a kind of water outlet benzopyrene concentration <0.0029ug/L ozone tail gas recovery process schema of the present invention
Fig. 7 is a kind of water outlet benzopyrene concentration <0.01ug/L ozone tail gas recovery process schema of the present invention
In figure, 1-catalytic ozonation reactor; 2-filler discharge opening; 3-liquid level meter; 4-reservoir bed; 5-water outlet; 6-supporting leg; 4-support; 8-inlet mouth; 9-filler supporting plate; 10-molecular imprinting modification filler; 11-molecular imprinting modification catalytic filler layer; 12-water distribution layer; 13-tail gas air outlet; 14-suspension; 15-water-in; 16-water distribution board; 17-manhole.
Embodiment
Refer to Fig. 1-4.
First build catalytic ozonation reactor 1.Catalytic ozonation reactor 1 bottom is supported by supporting leg 6.The housing of catalytic ozonation reactor 1 can adopt the material of the resistance to ozone such as stainless steel, glass reinforced plastic, polyvinyl chloride plate corrosion, or the set up defences material manufacture of ozone corrosion treatment of concrete structure and other internal surface.Housing front is provided with manhole 17 and filler discharge opening 2, and housing one side lower end (reservoir bed 7) is provided with the inlet mouth 8 of liquid level meter 3 and ozonize gas.Center, housing top is provided with water-in 15, and top one side is provided with tail gas air outlet 13, and housing bottom center is provided with water outlet 5.
In catalytic ozonation reactor 1 of the present invention, set gradually water distribution layer 12, molecular imprinting modification catalytic filler layer 11 and 7 three functional zone of reservoir bed from top to bottom.
Wherein, the height of water distribution layer 12 is 300-600mm, three suspensions 14 that are fixed on catalytic ozonation reactor 1 top, consists of with the water distribution board 16 that is fixed on suspension 14 bottoms.Wherein, the perforation filter plate that water distribution board 16 is 50% for aperture 2-4mm, percentage of open area, water distribution board 16 is positioned at the middle of water distribution layer 12, and water distribution board 16 diameters are that 2/3, three suspension 14 of catalytic ozonation reactor 1 diameter of the housing is uniformly distributed.Waste water enters reactor by water-in 15, and a part disperses to fall by the backward surrounding radiation of water distribution board 16 reflection, and another part waste water can directly fall by aperture, thereby improves the homogeneity of water distribution.Water distribution board adopts stainless steel plate, polyvinyl chloride plate, pottery and other surperficial material that is provided with deodorization oxygen corrosion processing of resistance to ozone corrosion.
The height of molecular imprinting modification catalytic filler layer 11 is 1000～2000mm, is waste water formation liquid film the region that contacts also selective adsorption, catalyzed oxidation with ozonize gas (in this region, filling high-specific surface area filler molecular imprinting modification filler 10).Molecular imprinting modification catalytic filler layer 11 is comprised of molecular imprinting modification filler 10, filler supporting plate 9 and support 4 successively.Filler supporting plate 9 is fixedly connected with three supports 4, on filler supporting plate 9 distributed aperture be 1-2mm, percentage of open area to be 62% cross water aperture, can carry, support filler on the one hand, can make on the other hand that current are smooth and easy to be passed through.Support 4 bottoms and catalytic ozonation reactor 1 bottom are fixed, and top and filler supporting plate 9 are fixing.The diameter of molecular imprinting modification filler 10 is 3～6mm, and specific surface area is greater than 500m
2/ m
3.Molecular imprinting modification filler 10 is by the micro-benzopyrene pollutent in selective adsorption, catalyzed oxidation coupling degrading waste water.Molecular imprinting modification filler is 10 preparation methods comprise:
First in parts by weight, Jiang Cong traditional Chinese medicines group buy material weigh as follows: the analytical pure iron nitrate of 6-12 part; The analytical pure manganous phosphate of 4-6 part; The analytical pure sulfuric acid nickel of 2-5 part; The analytical pure Vanadium Pentoxide in FLAKES of 2-6 part; The analytical pure potassium oxide of 2-6 part; The analytical pure sulfuric acid copper of 3-5 part; The analytical pure methacrylic acid of 1-3 part; The aluminum oxide of 100 parts.
Again the iron nitrate of above-mentioned weighing is added to water configuration and obtain the iron nitrate solution that weight percent content is 5-10%, using aluminum oxide as carrier, put into iron nitrate solution and carry out ion-exchange, standing 4-6 hour, after filtration, obtain iron content alumina supporter, this iron content alumina supporter is through 60-120 ℃ of dry 10-12h, and roasting 3-4 hour obtains mixing iron modified aluminium oxide supports at 500-600 ℃.Filtered liquid is recycled.
Then, respectively weighing being obtained to manganous phosphate, Vanadium Pentoxide in FLAKES and potassium oxide adds water configuration to obtain weight percent content is the manganous phosphate solution of 6%-8%, the Vanadium Pentoxide in FLAKES solution of 5%-10%, the potassium oxide solution of 8%-10%, then three kinds of solution are mixed, become precursor solution A; Equally single nickel salt and copper sulfate being added to water configuration, to obtain weight percent content be the nickel sulfate solution of 4%-6% and the copper-bath of 4%-8%, and two kinds of solution are mixed, and becomes precursor solution B.To mix iron modified aluminium oxide supports and first impregnated in precursor solution A 3h by 80-100 ℃ of dry 10-12h, after taking-up, impregnated in 3h in precursor solution B, again through 80-100 ℃ of dry 10-12h, finally, under the inert gas atmosphere of 600-900 ℃, roasting 2-3 hour obtains granules of catalyst, the granules of catalyst making is added to methacrylic acid: in the mixing solutions of chloroform=1:1 volume ratio, after standing 24h, filtration, vacuum-drying, make support of the catalyst.
Finally, measure traditional Chinese medicines group buy the pure benzopyrene of top grade: support of the catalyst=1:10 mass ratio, measure again dehydrated alcohol: 98% ethylene glycol dimethacrylate: analytical pure azo-bis-isobutyl cyanide: support of the catalyst=5:1:15:1 mass ratio, then, first benzopyrene and support of the catalyst are joined in dehydrated alcohol, under room temperature, fully stirring 6h, more respectively ethylene glycol dimethacrylate and azo-bis-isobutyl cyanide are added, is polyreaction 15h under 35 ℃, agitation condition in sealing, temperature.Gained particle first cleans 3 times with distilled water, then cleans 3 times with ethanol, then puts into baking oven dry 1h at 55 ℃, finally puts into retort furnace at 400 ℃ of temperature lower calcination 3h, makes molecular imprinting modification filler 10.
The function of reservoir bed 7 is to play water seal effect, prevents that ozonize gas from directly flowing away from the bottom of catalytic ozonation reactor 1 with current.The ozone that height enters with inlet mouth 8 can only up be as the criterion by molecular imprinting modification catalytic filler layer 11, is specifically highly 400-600mm.
Refer to Fig. 5.The present invention adopts catalytic ozonation reactor to remove micro-benzopyrene in water and has the technical process that destroys ozone tail gas: first set up the ozone tail gas breaking plant that a bottom is provided with steam heating tube, ozone tail gas breaking plant inside is loaded active carbon layer and catalytic filler layer from top to bottom successively, by pipeline (material that pipeline can be processed with material or the oxygen corrosion of other internal surface process deodorization of the resistance to ozone corrosion such as silicone tube), the air outlet of catalytic ozonation reactor is connected with ozone tail gas breaking plant bottom ozone tail gas inlet mouth, then will enter catalytic ozonation reactor containing waste water after the biochemical treatment of 50ug/L benzopyrene, wherein ozone dosage is 50-100mg/L, in ozonized air, ozone concn is 1-3mg/L, the catalytic ozonation reactor waterpower residence time is 10min, to the assimilated efficiency of ozone up to more than 90%, in water outlet, benzopyrene concentration is 0.0027ug/L, removal efficiency to benzopyrene reaches 99.99%, entering ozone concn in the tail gas in ozone tail gas breaking plant is 0.08-0.24mg/L, stop 10-20min, the catalytic filler layer catalytic decomposition, destruction and the charcoal absorption that by homemade molecular imprinting modification filler, are being formed, ozone is destroyed substantially completely, in emission gases, ozone concn is less than 0.0001mg/L, meets the requirement of discharge.
If effluent quality is had relatively high expectations (benzopyrene concentration <0.0029ug/L in water outlet), adopt three grades of series connection forms, be about to 1 series connection of three catalytic ozonation reactors and remove micro-benzopyrene in water, refer to Fig. 6.Containing waste water after the biochemical treatment of 50ug/L benzopyrene, by first catalytic ozonation reactor 1 top water-in 15, enter one-level catalytic ozonation reactor, by lower end water outlet 5, flowed out, rely on lift pump or self gravitation to flow to into second reactor water-in 15, by that analogy, wherein the reactor waterpower residence time is 10-15min, ozone enters A reactor with 50-100mg/L dosage, in ozonized air, ozone concn is 1-3mg/L, the ozone tail gas of A reactor is by free diffusing effect, via pipeline, enter the inlet mouth 8 of second reactor, other conditions are identical, benzopyrene concentration <0.0029ug/L from the 3rd reactor water out, from the 3rd reactor gas out, ozone concn is less than 0.0001mg/L, meet the requirement of discharge, avoid the secondary pollution of ozone the cost of reducing investment outlay.The present invention in 10min to the assimilated efficiency of ozone up to more than 90%, the removal efficiency of benzopyrene is reached to 99.99%.
If reactor effluent quality is required to lower (benzopyrene concentration <0.01ug/L), can adopt following air water arrangement form, refer to Fig. 7.To via different pipelines, enter one, two, three catalytic ozonation reactor top water-in 15 containing waste water after the biochemical treatment of 50ug/L benzopyrene simultaneously, by lower end water outlet 5, flow out and converge by pipeline, unified discharge, benzopyrene concentration <0.01ug/L in water.Wherein the volume of secondary, three reactor is respectively 2/3,1/4 of A reactor.The ozone tail gas of A reactor is by free diffusing effect, via pipeline, enter the inlet mouth 8 of second reactor, by that analogy, other conditions are identical, from the 3rd reactor gas out, ozone concn is less than 0.0001mg/L, meet the requirement of discharge, avoid the secondary pollution of ozone the cost of reducing investment outlay.The present invention in 10min to the assimilated efficiency of ozone up to more than 90%, the removal efficiency of benzopyrene is reached to 99.99%.
Claims (4)
1. fast, the method for micro-benzopyrene in efficient, degradation selectivity water, it is characterized in that:
The first step, first build catalytic ozonation reactor (1), catalytic ozonation reactor (1) inside sets gradually water distribution layer (12), molecular imprinting modification catalytic filler layer (11) and reservoir bed (7) totally three functional zone from top to bottom, water distribution layer (12) is 2-4mm by the aperture that is fixed on the suspension (14) on catalytic ozonation reactor (1) top and is fixed on suspension (14) bottom, and the perforation water distribution board (16) that percentage of open area is 50% forms; Molecular imprinting modification catalytic filler layer (11) is fixing by bottom and catalytic ozonation reactor (1) bottom, the support (4) that top and filler supporting plate (9) are fixing, and the molecular imprinting modification filler (10) on filler supporting plate (9) forms; Reservoir bed (7) water seal that to be prevention ozone between catalytic ozonation reactor (1) bottom and filler supporting plate (9) directly flow away from the bottom of catalytic ozonation reactor (1) with current; The bottom center of catalytic ozonation reactor (1) housing is provided with water outlet (5), between reservoir bed (7) and molecular imprinting modification catalytic filler layer (11), be provided with the inlet mouth (8) of liquid level meter (3) and ozonize gas, molecular imprinting modification catalytic filler layer (11) locates to be provided with manhole (17) and filler discharge opening (2); Catalytic ozonation reactor (1) top is provided with water-in (15) and tail gas air outlet (13);
The preparation method of above-mentioned molecular imprinting modification filler (10) is:
I, material choice and metering, measure in mass ratio iron nitrate: manganous phosphate: single nickel salt: Vanadium Pentoxide in FLAKES: potassium oxide: copper sulfate: methacrylic acid: aluminum oxide=6-12:4-6:2-5:2-6:2-6:3-5:1-3:100 part, above-mentioned raw materials is commercially available analytical pure commodity;
II, iron modified aluminium oxide supports is mixed in preparation, first the iron nitrate of the first step metering is added to water preparation and become the iron nitrate solution that mass percentage concentration is 5-10%, using aluminum oxide as carrier, put into iron nitrate solution again and carry out ion-exchange, standing 4-6 hour, filter, by the iron content alumina supporter obtaining after filtering, through 60-120 ℃ of dry 10-12h, roasting 3-4 hour obtains mixing iron modified aluminium oxide supports at 500-600 ℃; Filtered liquid is recycled;
III, support of the catalyst preparation, the manganous phosphate first respectively the first step being measured, Vanadium Pentoxide in FLAKES and potassium oxide add water preparation becomes the manganous phosphate solution that mass percentage concentration is 6%-8%, the Vanadium Pentoxide in FLAKES solution of 5%-10% and the potassium oxide solution of 8%-10%, three kinds of solution are mixed into precursor solution A, the single nickel salt respectively the first step being measured again and copper sulfate add water preparation, and to become mass percentage concentration be the nickel sulfate solution of 4%-6% and the copper-bath of 4%-8%, these two kinds of solution are mixed into precursor solution B, then, the iron modified aluminium oxide supports of mixing that second step is obtained is dipped in each 3h in precursor solution A and precursor solution B successively, after each dipping, all need through 80-100 ℃ of dry 10-12h, modification after final drying is mixed to iron alumina supporter roasting 2-3 hour under the inert gas atmosphere of 600-900 ℃ and obtain granules of catalyst, the granules of catalyst making is added to methacrylic acid: in the mixing solutions of chloroform=1:1 volume ratio, after standing 24h, filtration, vacuum-drying make support of the catalyst,
IV, the preparation of molecular imprinting modification filler (10), the pure benzopyrene of commercially available top grade of take is template, support of the catalyst is function base material, ethylene glycol dimethacrylate is linking agent, dehydrated alcohol is solvent, take azo-bis-isobutyl cyanide as initiator, measure benzopyrene: support of the catalyst=1:10 mass ratio, measure again dehydrated alcohol: the ethylene glycol dimethacrylate that mass percentage concentration is 98%: analytical pure azo-bis-isobutyl cyanide: support of the catalyst=5:1:15:1 mass ratio, then, first benzopyrene and support of the catalyst are joined in dehydrated alcohol, under room temperature, fully stir 6h, respectively ethylene glycol dimethacrylate and azo-bis-isobutyl cyanide are added again, in sealing, temperature is polyreaction 15h under 35 ℃ and agitation condition, gained particle first cleans 3 times with distilled water, with ethanol, clean 3 times again, then put into baking oven dry 1h at 55 ℃, finally put into retort furnace at 400 ℃ of temperature lower calcination 3h, make molecular imprinting modification filler (10), after testing, this molecular imprinting modification filler (10) diameter is 3～6mm, specific surface area is greater than 500m
2/ m
3,
Second step, adopt one or more catalytic ozonation reactors (1) to remove micro-benzopyrene in water, first the water-in (15) of catalytic ozonation reactor (1) will be pumped into containing waste water after the biochemical treatment of 50ug/L-100mg/L benzopyrene, through water distribution board (16), be sprayed onto molecular imprinting modification catalytic filler layer (11), enter the ozone of catalytic ozonation reactor (1) with lower end inlet mouth (8), under molecular imprinting modification catalytic filler layer (11) cutting, form liquid film, liquid film in decline process and molecular imprinting modification catalytic filler layer (11) constantly collide and ozone on push away under pincer attack, thickness of liquid film is reduced and constantly updated, increased considerably the effective contact area of gas-liquid two-phase, realized water-dispersion in the pattern of gas, improved gas, liquid two-phase interface renewal rate, accelerated molten gas process, liquid film contacts with ozonize gas and selective adsorption, catalyzed oxidation has been removed benzopyrene in water, last water flows out through lower end water outlet (5), ozone dosage is 50-100mg/L, in ozonized air, ozone concn is 1-3mg/L, the reactor waterpower residence time is 10-15min, more than can realizing the specific absorption to 90% of ozone, the clearance of benzopyrene reaches 99.99%.
2. according to claim 1 a kind of quick, efficiently, the method of micro-benzopyrene in degradation selectivity water, it is characterized in that: in described second step, adopt micro-benzopyrene in a catalytic ozonation reactor (1) removal water to be, first set up the ozone tail gas breaking plant that a bottom is provided with steam heating tube, ozone tail gas breaking plant inside is loaded active carbon layer and catalytic filler layer from top to bottom successively, by pipeline, the air outlet of catalytic ozonation reactor (1) (13) are connected with ozone tail gas breaking plant bottom ozone tail gas inlet mouth, then will enter catalytic ozonation reactor (1) containing waste water after the biochemical treatment of 50ug/L benzopyrene, wherein ozone dosage is 50-100mg/L, in ozonized air, ozone concn is 1-3mg/L, the reactor waterpower residence time is 10min, to the assimilated efficiency of ozone up to more than 90%, in water outlet, benzopyrene concentration is 0.0027ug/L, clearance to benzopyrene reaches 99.99%, entering ozone concn in the tail gas in ozone tail gas breaking plant is 0.08-0.24mg/L, stop 10-20min, the catalytic filler layer catalytic decomposition that dependence consists of homemade molecular imprinting modification filler (10) destroyed and charcoal absorption, ozone is destroyed substantially completely, in emission gases, ozone concn is less than 0.0001mg/L, meets the requirement of discharge.
3. according to claim 1 a kind of quick, efficiently, the method of micro-benzopyrene in degradation selectivity water, it is characterized in that: in described second step, adopt micro-benzopyrene in a plurality of catalytic ozonation reactors (1) removal water to be, for meeting the requirement of benzopyrene concentration <0.0029ug/L in water outlet, adopt three grades of series connection forms, be about to three catalytic ozonation reactors (1) series connection, to pump into successively first catalytic ozonation reactor (1) top water-in (15) containing waste water after the biochemical treatment of 50ug/L-100mg/L benzopyrene, after reaction, by lower end water outlet (5), flowed out, enter again second catalytic ozonation reactor (1), by that analogy, and first reactor ozone tail gas out enters second reactor through pipeline, by that analogy, other conditions are identical, benzopyrene concentration <0.0029ug/L from the 3rd reactor water out, from the 3rd reactor gas out, ozone concn is less than 0.0001mg/L, meet the requirement of discharge, avoid the secondary pollution of ozone.
4. according to claim 1 a kind of quick, efficiently, the method of micro-benzopyrene in degradation selectivity water, it is characterized in that: in described second step, adopt micro-benzopyrene in a plurality of catalytic ozonation reactors (1) removal water to be, for meeting the requirement of benzopyrene concentration <0.01ug/L in water outlet, adopt three grades of parallel forms, be about to three catalytic ozonation reactors (1) parallel connection, to through different pipelines, pump into the top water-in (15) of three catalytic ozonation reactors (1) containing waste water after the biochemical treatment of 50ug/L-100mg/L benzopyrene simultaneously, by lower end water outlet (5), flow out and converge by pipeline, unified discharge, benzopyrene concentration <0.01ug/L in water, and first reactor ozone tail gas out enters second reactor through pipeline, by that analogy, other conditions are identical, and from the 3rd reactor gas out, ozone concn is less than 0.0001mg/L, meets the requirement of discharge, avoids the secondary pollution of ozone.
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