CN103143360B - Preparation method of multi-element polyhydroxy pumice ozone catalyst - Google Patents
Preparation method of multi-element polyhydroxy pumice ozone catalyst Download PDFInfo
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Abstract
The invention discloses a preparation method of a multi-element polyhydroxy pumice ozone catalyst and relates to a preparation method of a heterogeneous catalyst for water treatment. The preparation method disclosed by the invention aims to solve the problems that conventional nanometer transition metal hydroxylate catalysts are difficult to recover and the secondary pollution is easy to generate in the process of catalyzing organic matters in ozonized water. The preparation method comprises the steps of: 1, ultrasonically cleaning; 2, acid solution soaking; 3, filtering, washing and drying; 4, aluminium salt solution dipping; 5, filtering, washing and roasting; 6, metal salt solution dipping; 7, activating treatment; and 8, filtering, washing and drying to obtain the multi-element polyhydroxy pumice ozone catalyst. The preparation method disclosed by the invention can be used for preparing the multi-element polyhydroxy pumice ozone catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of water treatment heterogeneous catalysis.
Background technology
Along with industrial fast development and human substance life horizontal's raising, water environment pollution has become current ubiquitous problem.Some difficult degradation hazardous contaminants in water, although concentration is low, harm is large, removal is difficult, conventional processes can not be removed these poisonous and harmful micropollutants effectively, directly threatens urban water supply water quality safety.In water treatment field, metal catalytic ozonation technology, because of the feature such as its efficient oxidation performance, catalyst be easily separated, has become current research focus.In recent years, be accompanied by the development of nanometer technology, researcher utilizes nano-metal-oxide to be applied to ozone catalytic system as catalyst and removes organic pollutants, has obtained good catalytic effect.Researcher is to finding in organic matter work in nano transition metal hydroxylate O3 catalytic oxidation water, compare nano transition metal hydroxylate (wherein iron, zinc and cobalt oxyhydroxide activity are best) with nano transition metal oxides and show stronger catalytic activity to removing micro-hardly degraded organic substance in water, mechanism research finds that the adsorbed hydroxyl content is its highly active key factor, but in reaction system, catalyst is difficult to reclaim, easily cause secondary pollution, limits its large-scale promotion application in actual water treatment.
Float stone is the acid volcano of the nature of glass effusive rock of a kind of porous, lightweight, chemical composition is silica and metal oxide, abundant at China's reserves, have that specific area is large, quality is light, intensity is high, acid and alkali-resistance, anticorrosive, and the feature such as pollution-free, "dead", be widely used in building, field of printing and dyeing, at catalytic field, also represent broad prospect of application.Researcher finds that float stone can adsorb ozone in water and promote it to decompose, and strengthens organic matter ability in ozone oxidation water.Therefore, find a kind of effectively catalyst of high stability micro-content organism in degradation water of ozone system that is applied to, develop a kind of economical and practical, catalytic ozonation new technology safely and effectively, effectively remove micro quantity organic pollutant in water and there is important theory significance and actual application value.
Summary of the invention
The present invention will solve existing nano transition metal hydroxylate catalyst in O3 catalytic oxidation water, in organic process, to have the difficult recovery of catalyst, easily cause the problem of secondary pollution, and the preparation method of a kind of polynary poly-hydroxyl float stone ozone catalytic agent is provided.
The preparation method of a kind of polynary poly-hydroxyl float stone ozone catalytic of the present invention agent, carries out according to the following steps:
One, ultrasonic cleaning: under the condition that is 40KHz with distilled water in frequency by float stone, ultrasonic cleaning is 2 times～4 times, and single scavenging period is 5min～10min; Two, acid solution soaks: it is that the acid solution environment of 0.5mol/L～1.0mol/L soaks 3h～6h that the float stone after step 1 ultrasonic cleaning is put into concentration, obtains mixed liquor A; Three, filter, washing and dry: the mixed liquor A that step 2 is obtained is filtered, and by distilled water flushing 5 times～7 times for the solid obtaining after filtering, in temperature, is then dry 12h～24h under the condition of 60 ℃～120 ℃, obtains solid B; Four, aluminum salt solution dipping: the solid B that step 3 is obtained immerses in the aluminum salt solution that concentration is 0.5mol/L～5.0mol/L, and dip time is 24h～48h, obtains suspension C; Five, filtration, washing and roasting: the suspension C that step 4 is obtained filters, by distilled water flushing 5 times～7 times for the solid obtaining after filtering, be then roasting 4h～6h under the condition of 450 ℃～650 ℃ in temperature, obtains solid D; Six, metal salt solution dipping: the solid D that step 5 is obtained immerses in the metal salt solution that concentration is 0.5mol/L～5.0mol/L, and dip time is 48h～72h, obtains suspension E; Seven, activation processing: it is 9～12 that suspension E step 6 being obtained with alkaline solution regulates pH value, then staticly settles 30min～60min, is finally activation processing 24h～48h under 40 ℃～80 ℃ conditions in temperature, obtains mixed liquor F; Eight, filter, wash and be dried: after the mixed liquor F that step 7 is obtained filters, obtaining solid formation, then the pH that solid formation is washed with distilled water to cleaning solution is invariable, in temperature, be finally dry 24h～48h under 40 ℃～80 ℃ conditions, obtain the agent of polynary poly-hydroxyl float stone ozone catalytic.
The effect of the ultrasonic cleaning described in step 1 of the present invention is in order to clean the float stone surfaces externally and internally gas in hole of draining simultaneously.
Advantage of the present invention: the catalyst that the polynary poly-hydroxyl float stone ozone catalytic agent that, prepared by the present invention is decomposed generation hydroxyl radical free radical as catalysis ozone has advantages of that catalytic elimination organic pollution is active by force, self stability is high, is easy to recycle and do not produce secondary pollution; Two, the polynary poly-hydroxyl float stone ozone catalytic agent particle crystalline form that prepared by the present invention is complete, even compact and particle diameter are evenly distributed, and has specific area large, and settling property is good, and active component is combined with carrier closely, very easily separated with water, the advantage being evenly distributed; Three, the polynary poly-hydroxyl float stone ozone catalytic agent that prepared by the present invention can promote ozone decomposed to generate hydroxyl radical free radical, increase generating rate and the quantity of free radical in water body, can make the utilization rate of ozone improve 20～30 percentage points, O3 catalytic oxidation has improved 30～50 percentage points than independent ozone oxidation to the clearance of organic pollutants; Four, preparation method's technique of the present invention simply, easily synthetic, with low cost, can be applied in engineering of water treatment on a large scale.
Accompanying drawing explanation
Fig. 1 is the clearance of parachloronitrobenzene and the graph of relation in reaction time, when the △ in Fig. 1 represents to test the polynary poly-hydroxyl float stone of two employings and is ozone catalytic agent, the clearance of ozone oxidation parachloronitrobenzene and the graph of relation in reaction time, when zero in Fig. 1 represents that the contrast test I of test two adopts float stone to be ozone catalytic agent, the clearance of ozone oxidation parachloronitrobenzene and the graph of relation in reaction time, the clearance of parachloronitrobenzene and the graph of relation in reaction time when the in Fig. 1 represents to test two the independent ozone oxidation of contrast test II;
Fig. 2 is the EPR spectrogram of DMPO-OH in O3 catalytic oxidation process, when the A in Fig. 2 represents to test the polynary poly-hydroxyl float stone of two employings and is ozone catalytic agent, the EPR spectrogram of DMPO-OH in O3 catalytic oxidation process, when the B in Fig. 2 represents to test two contrast test I and adopts float stone to be ozone catalytic agent, the EPR spectrogram of DMPO-OH in O3 catalytic oxidation process, when the C in Fig. 2 represents to test two the independent ozone oxidation of contrast test II, the EPR spectrogram of DMPO-OH in O3 catalytic oxidation process.
The specific embodiment
The specific embodiment one: the preparation method of a kind of polynary poly-hydroxyl float stone ozone catalytic of present embodiment agent, carries out according to the following steps:
One, ultrasonic cleaning: under the condition that is 40KHz with distilled water in frequency by float stone, ultrasonic cleaning is 2 times～4 times, and single scavenging period is 5min～10min; Two, acid solution soaks: it is that the acid solution environment of 0.5mol/L～1.0mol/L soaks 3h～6h that the float stone after step 1 ultrasonic cleaning is put into concentration, obtains mixed liquor A; Three, filter, washing and dry: the mixed liquor A that step 2 is obtained is filtered, and by distilled water flushing 5 times～7 times for the solid obtaining after filtering, in temperature, is then dry 12h～24h under the condition of 60 ℃～120 ℃, obtains solid B; Four, aluminum salt solution dipping: the solid B that step 3 is obtained immerses in the aluminum salt solution that concentration is 0.5mol/L～5.0mol/L, and dip time is 24h～48h, obtains suspension C; Five, filtration, washing and roasting: the suspension C that step 4 is obtained filters, by distilled water flushing 5 times～7 times for the solid obtaining after filtering, be then roasting 4h～6h under the condition of 450 ℃～650 ℃ in temperature, obtains solid D; Six, metal salt solution dipping: the solid D that step 5 is obtained immerses in the metal salt solution that concentration is 0.5mol/L～5.0mol/L, and dip time is 48h～72h, obtains suspension E; Seven, activation processing: it is 9～12 that suspension E step 6 being obtained with alkaline solution regulates pH value, then staticly settles 30min～60min, is finally activation processing 24h～48h under 40 ℃～80 ℃ conditions in temperature, obtains mixed liquor F; Eight, filter, wash and be dried: after the mixed liquor F that step 7 is obtained filters, obtaining solid formation, then the pH that solid formation is washed with distilled water to cleaning solution is invariable, in temperature, be finally dry 24h～48h under 40 ℃～80 ℃ conditions, obtain the agent of polynary poly-hydroxyl float stone ozone catalytic.
The effect of the ultrasonic cleaning described in present embodiment step 1 is in order to clean the float stone surfaces externally and internally gas in hole of draining simultaneously.
The catalyst that polynary poly-hydroxyl float stone ozone catalytic agent prepared by present embodiment is decomposed generation hydroxyl radical free radical as catalysis ozone has advantages of that catalytic elimination organic pollution is active by force, self stability is high, is easy to recycle and do not produce secondary pollution.
Polynary poly-hydroxyl float stone ozone catalytic agent particle crystalline form prepared by present embodiment is complete, even compact and particle diameter are evenly distributed, and has specific area large, and settling property is good, and active component is combined with carrier closely, very easily separated with water, the advantage being evenly distributed.
Polynary poly-hydroxyl float stone ozone catalytic agent prepared by present embodiment can promote ozone decomposed to generate hydroxyl radical free radical, increase generating rate and the quantity of free radical in water body, can make the utilization rate of ozone improve 20～30 percentage points, O3 catalytic oxidation has improved 30～50 percentage points than independent ozone oxidation to the clearance of organic pollutants.
Preparation method's technique of present embodiment simply, easily synthetic, with low cost, can be applied in engineering of water treatment on a large scale.
The specific embodiment two: present embodiment is different from the specific embodiment one: the particle diameter of float stone described in step 1 is 0.1mm～10cm.Other is identical with the specific embodiment one.
The specific embodiment three: present embodiment is different from the specific embodiment one or two: described in step 2, acid solution is salpeter solution, hydrochloric acid solution or sulfuric acid solution.Other is identical with the specific embodiment one or two.
The specific embodiment four: present embodiment is different from one of specific embodiment one to three: aluminum salt solution described in step 4 is aluminum nitrate solution, aluminum sulfate solution, liquor alumini chloridi or aluminium carbonate solution.Other is identical with one of specific embodiment one to three.
The specific embodiment five: present embodiment is different from one of specific embodiment one to four: metal salt solution described in step 6 is a kind of in iron nitrate solution, ferrum sulfuricum oxydatum solutum, ferric chloride solution, ferric carbonate solution, zinc nitrate solution, solution of zinc sulfate, liquor zinci chloridi, zinc carbonate solution, cobalt nitrate solution, cobalt sulfate solution, cobalt chloride solution and cobalt carbonate solution or several mixture wherein.Other is identical with one of specific embodiment one to four.
When described in present embodiment, metal salt solution is mixed solution, between each component, be mixed by any ratio.
The specific embodiment six: present embodiment is different from one of specific embodiment one to five: alkaline solution described in step 7 is sodium hydroxide solution, potassium hydroxide solution or ammonia spirit.Other is identical with one of specific embodiment one to five.
The specific embodiment seven: present embodiment is different from one of specific embodiment one to six: the acid solution environment of described in step 2, the float stone after step 1 ultrasonic cleaning being put into concentration and be 0.6mol/L～0.9mol/L soaks 4h～5h, obtains mixed liquor A.Other is identical with one of specific embodiment one to six.
The specific embodiment eight: present embodiment is different from one of specific embodiment one to seven: the solid B described in step 4, step 3 being obtained immerses in the aluminum salt solution that concentration is 1.0mol/L～4.0mol/L, dip time is 30h～46h, obtains suspension C.Other is identical with one of specific embodiment one to seven.
The specific embodiment nine: present embodiment is different from one of specific embodiment one to eight: the solid D described in step 6, step 5 being obtained immerses in the metal salt solution that concentration is 1.0mol/L～4.0mol/L, dip time is 50h～70h, obtains suspension E.Other is identical with one of specific embodiment one to eight.
Adopt following verification experimental verification effect of the present invention:
Test one: the preparation method of a kind of polynary poly-hydroxyl float stone ozone catalytic agent, carries out according to the following steps:
One, ultrasonic cleaning: under the condition that is 40KHz with distilled water in frequency by float stone (particle diameter 0.6mm), ultrasonic cleaning is 2 times, and single scavenging period is 5min; Two, salpeter solution soaks: it is that the salpeter solution environment of 0.5mol/L soaks 6h that the float stone after step 1 ultrasonic cleaning is put into concentration, obtains mixed liquor A; Three, filter, washing and dry: the mixed liquor A that step 2 is obtained is filtered, and by distilled water flushing 5 times for the solid obtaining after filtering, in temperature, is then dry 12h under the condition of 80 ℃, obtains solid B; Four, aluminum nitrate solution dipping: the solid B that step 3 is obtained immerses in the aluminum nitrate solution that concentration is 3.0mol/L, and dip time 48h, obtains suspension C; Five, filtration, washing and roasting: the suspension C that step 4 is obtained filters, by distilled water flushing 6 times for the solid obtaining after filtering, be then roasting 5h under the condition of 550 ℃ in temperature, obtains solid D; Six, iron and cobalt nitrate solution dipping: the solid D that step 5 is obtained immerses in the iron and cobalt nitrate solution that concentration is 3.0mol/L, and dip time is 72h, obtains suspension E; Seven, activation processing: it is 12 that suspension E step 6 being obtained with sodium hydroxide solution regulates pH value, then staticly settles 60min, is finally activation processing 48h under 60 ℃ of conditions in temperature, obtains mixed liquor F; Eight, filter, wash and be dried: after the mixed liquor F that step 7 is obtained filters, obtaining solid formation, then the pH that solid formation is washed with distilled water to cleaning solution is invariable, in temperature, be finally dry 24h under 60 ℃ of conditions, obtain the agent of polynary poly-hydroxyl float stone ozone catalytic.
Test two: utilize while testing a polynary poly-hydroxyl float stone of preparing for ozone catalytic agent the removal usefulness of ozone oxidation parachloronitrobenzene:
The reactor that contains 1L distilled water (pH of presetting distilled water is 6.86) is placed in bain-marie, and by thermostat, controlling reaction solution temperature constant is 23 ℃, in reactor, passes into O
3/ O
2mist, when the concentration of ozone is 0.6mg/L in the aqueous solution, stop aeration, then in reactor, add pCNB(parachloronitrobenzene at once) and the agent of polynary poly-hydroxyl float stone ozone catalytic, and concentration pCNB(parachloronitrobenzene in the reactor after adding) is that the concentration of 100 μ g/L, the agent of polynary poly-hydroxyl float stone ozone catalytic is 0.5g/L, open magnetic stirring apparatus, low whipping speed is to carry out stirring reaction under the condition of 200r/min, at 0min, 1min, 5min, 10min and 20min, from sample tap, sample, institute's water sampling need be immediately with the Na of 100 μ L
2s
2o
3solution (0.1mol/L) stops ozone oxidation reaction, then adopts the acetate fiber ultrafiltration membrance filter 50mL water sample of 0.45 μ m, liquid-phase chromatographic analysis; Ozone tail gas is used 2% liquor kalii iodide absorption.
This tests described reactor is flat class flask formula closed reactor, and its dischargeable capacity is 1.2L.
The contrast test I of test two: while adopting float stone to be ozone catalytic agent, the removal usefulness of ozone oxidation parachloronitrobenzene:
The reactor that contains 1L distilled water (pH of presetting distilled water is 6.86) is placed in bain-marie, and by thermostat, controlling reaction solution temperature constant is 23 ℃, in reactor, passes into O
3/ O
2mist, when the concentration of ozone is 0.6mg/L in the aqueous solution, stop aeration, then in reactor, add pCNB(parachloronitrobenzene at once) and the agent of float stone ozone catalytic, and concentration pCNB(parachloronitrobenzene in the reactor after adding) is that the concentration of 100 μ g/L, the agent of float stone ozone catalytic is 0.5g/L, open magnetic stirring apparatus, low whipping speed is to carry out stirring reaction under the condition of 200r/min, at 0min, 1min, 5min, 10min and 20min, from sample tap, sample, institute's water sampling need be immediately with the Na of 100 μ L
2s
2o
3solution (0.1mol/L) stops ozone oxidation reaction, then adopts the acetate fiber ultrafiltration membrance filter 50mL water sample of 0.45 μ m, liquid-phase chromatographic analysis, and ozone tail gas is used 2% liquor kalii iodide absorption.
This tests described reactor is flat class flask formula closed reactor, and its dischargeable capacity is 1.2L.
The contrast test II of test two: the removal usefulness of independent ozone oxidation parachloronitrobenzene:
The reactor that contains 1L distilled water (pH of presetting distilled water is 6.86) is placed in bain-marie, and by thermostat, controlling reaction solution temperature constant is 23 ℃, in reactor, passes into O
3/ O
2mist, when the concentration of ozone is 0.6mg/L in the aqueous solution, stop aeration, then in reactor, add pCNB(parachloronitrobenzene at once), and concentration pCNB(parachloronitrobenzene in the reactor after adding) is 100 μ g/L, open magnetic stirring apparatus, low whipping speed is to carry out stirring reaction under the condition of 200r/min, at 0min, 1min, 5min, 10min and 20min, from sample tap, sample, institute's water sampling need be immediately with the Na of 100 μ L
2s
2o
3solution (0.1mol/L) stops ozone oxidation reaction, then adopts the acetate fiber ultrafiltration membrance filter 50mL water sample of 0.45 μ m, liquid-phase chromatographic analysis, and ozone tail gas is used 2% liquor kalii iodide absorption.
This tests described reactor is flat class flask formula closed reactor, and its dischargeable capacity is 1.2L.
Fig. 1 is the clearance of parachloronitrobenzene and the graph of relation in reaction time, when the △ in Fig. 1 represents to test the polynary poly-hydroxyl float stone of two employings and is ozone catalytic agent, the clearance of ozone oxidation parachloronitrobenzene and the graph of relation in reaction time, when zero in Fig. 1 represents that the contrast test I of test two adopts float stone to be ozone catalytic agent, the clearance of ozone oxidation parachloronitrobenzene and the graph of relation in reaction time, the clearance of parachloronitrobenzene and the graph of relation in reaction time when the in Fig. 1 represents to test two the independent ozone oxidation of contrast test II; As seen from Figure 1, in ozone oxidation system, in water, pCNB concentration all reduces with the increase in reaction time, and wherein, in test dimerization hydroxyl float stone and ozone coupling removal water, pCNB is most effective.Reaction is during 20min, and poly-hydroxyl float stone is removed pCNB efficiency in water and reached 93%, than independent ozone oxidation and float stone O3 catalytic oxidation clearance, has improved respectively 31 percentage points.Above result of the test shows, gathers pCNB in hydroxyl float stone and ozone coupling degraded removal water and has obvious cooperative effect.
Fig. 2 is the EPR spectrogram of DMPO-OH in O3 catalytic oxidation process, when the A in Fig. 2 represents to test the polynary poly-hydroxyl float stone of two employings and is ozone catalytic agent, the EPR spectrogram of DMPO-OH in O3 catalytic oxidation process, when the B in Fig. 2 represents to test two contrast test I and adopts float stone to be ozone catalytic agent, the EPR spectrogram of DMPO-OH in O3 catalytic oxidation process, when the C in Fig. 2 represents to test two the independent ozone oxidation of contrast test II, the EPR spectrogram of DMPO-OH in O3 catalytic oxidation process; In Fig. 2, can find out, the characteristic quadruple division of the spectrogram peak of DMPO-OH addition compound product forms, and ratio of peak is 1:2:2:1.During independent ozone oxidation, there is the hydroxyl radical free radical (OH) of denier to generate, add after float stone and poly-hydroxyl float stone, the curve peak intensity of 1:2:2:1 is obviously strengthened, illustrate that these two kinds of catalyst have improved the growing amount of OH in ozone decomposed process significantly, by above experimental data, catalystic converter system is introduced float stone and poly-hydroxyl pumice Catalyst, and generate OH, wherein poly-hydroxyl float stone catalytic activity is the strongest.
Claims (6)
1. a preparation method for polynary poly-hydroxyl float stone ozone catalytic agent, is characterized in that the preparation method of polynary poly-hydroxyl float stone ozone catalytic agent carries out according to the following steps:
one,ultrasonic cleaning: under the condition that is 40KHz with distilled water in frequency by float stone, ultrasonic cleaning is 2 times ~ 4 times, and single scavenging period is 5min ~ 10min; Two, acid solution soaks: it is that the acid solution environment of 0.5mol/L ~ 1.0mol/L soaks 3h ~ 6h that the float stone after step 1 ultrasonic cleaning is put into concentration, obtains mixed liquor A; Three, filter, washing and dry: the mixed liquor A that step 2 is obtained is filtered, and by distilled water flushing 5 times ~ 7 times for the solid obtaining after filtering, in temperature, is then dry 12h ~ 24h under the condition of 60 ℃ ~ 120 ℃, obtains solid B; Four, aluminum salt solution dipping: the solid B that step 3 is obtained immerses in the aluminum salt solution that concentration is 0.5mol/L ~ 5.0mol/L, and dip time is 24h ~ 48h, obtains suspension C; Five, filtration, washing and roasting: the suspension C that step 4 is obtained filters, by distilled water flushing 5 times ~ 7 times for the solid obtaining after filtering, be then roasting 4h ~ 6h under the condition of 450 ℃ ~ 650 ℃ in temperature, obtains solid D; Six, metal salt solution dipping: the solid D that step 5 is obtained immerses in the metal salt solution that concentration is 0.5mol/L ~ 5.0mol/L, and dip time is 48h ~ 72h, obtains suspension E; Seven, activation processing: it is 9 ~ 12 that suspension E step 6 being obtained with alkaline solution regulates pH value, then staticly settles 30min ~ 60min, is finally activation processing 24h ~ 48h under 40 ℃ ~ 80 ℃ conditions in temperature, obtains mixed liquor F; Eight, filter, wash and be dried: after the mixed liquor F that step 7 is obtained filters, obtaining solid formation, then the pH that solid formation is washed with distilled water to cleaning solution is invariable, in temperature, be finally dry 24h ~ 48h under 40 ℃ ~ 80 ℃ conditions, obtain the agent of polynary poly-hydroxyl float stone ozone catalytic; Wherein acid solution described in step 2 is salpeter solution, hydrochloric acid solution or sulfuric acid solution; Aluminum salt solution described in step 4 is aluminum nitrate solution, aluminum sulfate solution or liquor alumini chloridi; Metal salt solution described in step 6 is two or more the mixture in iron nitrate solution, ferrum sulfuricum oxydatum solutum, ferric chloride solution, zinc nitrate solution, solution of zinc sulfate, liquor zinci chloridi, cobalt nitrate solution, cobalt sulfate solution and cobalt chloride solution.
2. the preparation method of a kind of polynary poly-hydroxyl float stone ozone catalytic according to claim 1 agent, the particle diameter that it is characterized in that float stone described in step 1 is 0.1mm ~ 10cm.
3. the preparation method of a kind of polynary poly-hydroxyl float stone ozone catalytic according to claim 1 agent, is characterized in that alkaline solution described in step 7 is sodium hydroxide solution, potassium hydroxide solution or ammonia spirit.
4. according to the preparation method of a kind of polynary poly-hydroxyl float stone ozone catalytic agent described in claim 1,2 or 3, the acid solution environment that it is characterized in that described in step 2, the float stone after step 1 ultrasonic cleaning being put into concentration and be 0.6mol/L ~ 0.9mol/L soaks 4h ~ 5h, obtains mixed liquor A.
5. the preparation method of a kind of polynary poly-hydroxyl float stone ozone catalytic according to claim 4 agent, it is characterized in that the solid B described in step 4, step 3 being obtained immerses in the aluminum salt solution that concentration is 1.0mol/L ~ 4.0mol/L, dip time is 30h ~ 46h, obtains suspension C.
6. the preparation method of a kind of polynary poly-hydroxyl float stone ozone catalytic according to claim 4 agent, it is characterized in that the solid D described in step 6, step 5 being obtained immerses in the metal salt solution that concentration is 1.0mol/L ~ 4.0mol/L, dip time is 50h ~ 70h, obtains suspension E.
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