CN103143360A - 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 present 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 the urban water supply water quality safety.In water treatment field, the metal catalytic ozonation technology has become the current research focus because of the characteristics such as its efficient oxidation performance, catalyst be easily separated.In recent years, be accompanied by the development of nanometer technology, the researcher utilizes nano-metal-oxide to be applied to the ozone catalytic system as catalyst and removes organic pollutants, has obtained good catalytic effect.The 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) in water, micro-hardly degraded organic substance shows stronger catalytic activity to removing with nano transition metal oxides, mechanism research finds that the adsorbed hydroxyl content is its highly active key factor, but catalyst is difficult to reclaim, easily cause secondary pollution in reaction system, limits its large-scale promotion application in actual water treatment.
Float stone is the nature of glass of a kind of porous, lightweight acid volcano effusive rock, 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 characteristics such as pollution-free, "dead", be widely used in building, field of printing and dyeing, also represent broad prospect of application at catalytic field.The researcher finds that float stone can adsorb ozone in water and promote its decomposition, strengthens organic matter ability in ozone oxidation water.Therefore, seek 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, remove effectively that in water, micro quantity organic pollutant has important theory significance and actual application value.
Summary of the invention
The present invention will solve existing nano transition metal hydroxylate catalyst to have the difficult recovery of catalyst in organic process in O3 catalytic oxidation water, 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, carry out according to the following steps:
One, ultrasonic cleaning: be ultrasonic cleaning 2 times～4 times under the condition of 40KHz in frequency with distilled water with float stone, the 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 the step 1 ultrasonic cleaning is put into concentration, obtains mixed liquor A; Three, filter, washing and dry: the mixed liquor A that step 2 obtains is filtered, and with distilled water flushing 5 times～7 times, is then dry 12h～24h under the condition of 60 ℃～120 ℃ in temperature with the solid that obtains after filtering, obtains solid B; Four, aluminum salt solution dipping: the solid B immersion concentration that step 3 is obtained is in the aluminum salt solution of 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, and with distilled water flushing 5 times～7 times, is then roasting 4h～6h under the condition of 450 ℃～650 ℃ in temperature with the solid that obtains after filtering, obtains solid D; Six, metal salt solution dipping: the solid D immersion concentration that step 5 is obtained is in the metal salt solution of 0.5mol/L～5.0mol/L, and dip time is 48h～72h, obtains suspension E; Seven, activation process: being 9～12 with alkaline solution with the suspension E adjusting pH value that step 6 obtains, then staticly settling 30min～60min, is activation process 24h～48h under 40 ℃～80 ℃ conditions in temperature at last, obtains mixed liquor F; Eight, filter, washing and dry: after the mixed liquor F that step 7 is obtained filters solid formation, then the pH that solid formation is washed with distilled water to cleaning solution is invariable, be dry 24h～48h under 40 ℃～80 ℃ conditions in temperature at last, namely get 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 the hole of draining simultaneously.
Advantage of the present invention: one, the polynary poly-hydroxyl float stone ozone catalytic agent of the present invention's preparation has advantages of that as the catalyst that catalysis ozone decomposes the generation hydroxyl radical free radical catalytic elimination organic pollution is active by force, self stability is high, be easy to recycle and do not produce secondary pollution; Two, complete, the even compact of the polynary poly-hydroxyl float stone ozone catalytic agent particle crystalline form of the present invention preparation and particle diameter are evenly distributed, and have specific area large, and settling property is good, and active component is combined with carrier closely, and very easy and moisture is from, the advantage that is evenly distributed; Three, the polynary poly-hydroxyl float stone ozone catalytic agent of the present invention's preparation 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 is simple, easily synthetic, with low cost, can be applied in engineering of water treatment on a large scale.
Description of drawings
Fig. 1 is the clearance of parachloronitrobenzene and the graph of relation in reaction time, △ in Fig. 1 represents to test two when adopting polynary poly-hydroxyl float stones to be the ozone catalytic agent, the clearance of ozone oxidation parachloronitrobenzene and the graph of relation in reaction time, when the contrast test I of the expression of zero in Fig. 1 test two adopts float stone to be the ozone catalytic agent, the clearance of parachloronitrobenzene and the graph of relation in reaction time when the clearance of ozone oxidation parachloronitrobenzene and the graph of relation in reaction time, the in Fig. 1 represent to test two the independent ozone oxidation of contrast test II;
Fig. 2 is the EPR spectrogram of DMPO-OH in the O3 catalytic oxidation process, A in Fig. 2 represents to test two when adopting polynary poly-hydroxyl float stones to be the ozone catalytic agent, the EPR spectrogram of DMPO-OH in the O3 catalytic oxidation process, B in Fig. 2 represents to test two contrast test I when adopting float stone to be the ozone catalytic agent, the EPR spectrogram of DMPO-OH in the 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 the 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, carry out according to the following steps:
One, ultrasonic cleaning: be ultrasonic cleaning 2 times～4 times under the condition of 40KHz in frequency with distilled water with float stone, the 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 the step 1 ultrasonic cleaning is put into concentration, obtains mixed liquor A; Three, filter, washing and dry: the mixed liquor A that step 2 obtains is filtered, and with distilled water flushing 5 times～7 times, is then dry 12h～24h under the condition of 60 ℃～120 ℃ in temperature with the solid that obtains after filtering, obtains solid B; Four, aluminum salt solution dipping: the solid B immersion concentration that step 3 is obtained is in the aluminum salt solution of 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, and with distilled water flushing 5 times～7 times, is then roasting 4h～6h under the condition of 450 ℃～650 ℃ in temperature with the solid that obtains after filtering, obtains solid D; Six, metal salt solution dipping: the solid D immersion concentration that step 5 is obtained is in the metal salt solution of 0.5mol/L～5.0mol/L, and dip time is 48h～72h, obtains suspension E; Seven, activation process: being 9～12 with alkaline solution with the suspension E adjusting pH value that step 6 obtains, then staticly settling 30min～60min, is activation process 24h～48h under 40 ℃～80 ℃ conditions in temperature at last, obtains mixed liquor F; Eight, filter, washing and dry: after the mixed liquor F that step 7 is obtained filters solid formation, then the pH that solid formation is washed with distilled water to cleaning solution is invariable, be dry 24h～48h under 40 ℃～80 ℃ conditions in temperature at last, namely get the agent of polynary poly-hydroxyl float stone ozone catalytic.
The effect of the ultrasonic cleaning described in the present embodiment step 1 is in order to clean the float stone surfaces externally and internally gas in the hole of draining simultaneously.
The polynary poly-hydroxyl float stone ozone catalytic agent of present embodiment preparation is decomposed as catalysis ozone the catalyst that generates hydroxyl radical free radical and is had advantages of that the catalytic elimination organic pollution is active by force, self stability is high, be easy to recycle and do not produce secondary pollution.
The polynary poly-hydroxyl float stone ozone catalytic agent particle crystalline form of present embodiment preparation 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, and very easy and moisture is from, the advantage that is evenly distributed.
The polynary poly-hydroxyl float stone ozone catalytic agent of present embodiment preparation 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 is simple, easily synthetic, with low cost, can be applied in engineering of water treatment on a large scale.
The specific embodiment two: what present embodiment was different from the specific embodiment one is: 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: what present embodiment was different from the specific embodiment one or two is: acid solution described in step 2 is salpeter solution, hydrochloric acid solution or sulfuric acid solution.Other is identical with the specific embodiment one or two.
The specific embodiment four: what present embodiment was different from one of specific embodiment one to three is: 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: what present embodiment was different from one of specific embodiment one to four is: 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 the described metal salt solution of present embodiment is mixed solution, be mixed by any ratio between each component.
The specific embodiment six: what present embodiment was different from one of specific embodiment one to five is: 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: what present embodiment was different from one of specific embodiment one to six is: the acid solution environment of described in step 2, the float stone after the 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: what present embodiment was different from one of specific embodiment one to seven is: it is in the aluminum salt solution of 1.0mol/L～4.0mol/L that the solid B that described in step 4, step 3 is obtained immerses concentration, dip time is 30h～46h, obtains suspension C.Other is identical with one of specific embodiment one to seven.
The specific embodiment nine: what present embodiment was different from one of specific embodiment one to eight is: it is in the metal salt solution of 1.0mol/L～4.0mol/L that the solid D that described in step 6, step 5 is obtained immerses concentration, 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, carry out according to the following steps:
One, ultrasonic cleaning: be ultrasonic cleaning 2 times under the condition of 40KHz in frequency with distilled water with float stone (particle diameter 0.6mm), the 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 the step 1 ultrasonic cleaning is put into concentration, obtains mixed liquor A; Three, filter, washing and dry: the mixed liquor A that step 2 obtains is filtered, and with distilled water flushing 5 times, is then dry 12h under the condition of 80 ℃ in temperature with the solid that obtains after filtering, obtains solid B; Four, aluminum nitrate solution dipping: the solid B immersion concentration that step 3 is obtained is in the aluminum nitrate solution of 3.0mol/L, and dip time 48h gets suspension C; Five, filtration, washing and roasting: the suspension C that step 4 is obtained filters, and with distilled water flushing 6 times, is then roasting 5h under the condition of 550 ℃ in temperature with the solid that obtains after filtering, obtains solid D; Six, iron and cobalt nitrate solution dipping: the solid D immersion concentration that step 5 is obtained is that in the iron and cobalt nitrate solution of 3.0mol/L, dip time is 72h, obtains suspension E; Seven, activation process: being 12 with sodium hydroxide solution with the suspension E adjusting pH value that step 6 obtains, then staticly settling 60min, is activation process 48h under 60 ℃ of conditions in temperature at last, obtains mixed liquor F; Eight, filter, washing and dry: after the mixed liquor F that step 7 is obtained filters solid formation, then the pH that solid formation is washed with distilled water to cleaning solution is invariable, be dry 24h under 60 ℃ of conditions in temperature at last, namely get the agent of polynary poly-hydroxyl float stone ozone catalytic.
Test two: utilize when testing a polynary poly-hydroxyl float stone for preparing for the ozone catalytic agent removal usefulness of ozone oxidation parachloronitrobenzene:
The reactor that will contain 1L distilled water (pH of preset distilled water is 6.86) is placed in bain-marie, and controlling the reaction solution temperature constant by thermostat is 23 ℃, passes into O in reactor
3/ O
2Mist, stop aeration when the concentration of ozone is 0.6mg/L in the aqueous solution, then add the pCNB(parachloronitrobenzene at once in reactor) 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, take a sample from sample tap at 0min, 1min, 5min, 10min and 20min, institute's water sampling need be used the Na of 100 μ L immediately
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 uses 2% liquor kalii iodide absorption.
The described reactor of this test is flat class flask formula closed reactor, and its dischargeable capacity is 1.2L.
The contrast test I of test two: when adopting float stone to be the ozone catalytic agent, the removal usefulness of ozone oxidation parachloronitrobenzene:
The reactor that will contain 1L distilled water (pH of preset distilled water is 6.86) is placed in bain-marie, and controlling the reaction solution temperature constant by thermostat is 23 ℃, passes into O in reactor
3/ O
2Mist, stop aeration when the concentration of ozone is 0.6mg/L in the aqueous solution, then add the pCNB(parachloronitrobenzene at once in reactor) 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, take a sample from sample tap at 0min, 1min, 5min, 10min and 20min, institute's water sampling need be used the Na of 100 μ L immediately
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, and liquid-phase chromatographic analysis, ozone tail gas use 2% liquor kalii iodide absorption.
The described reactor of this test 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 will contain 1L distilled water (pH of preset distilled water is 6.86) is placed in bain-marie, and controlling the reaction solution temperature constant by thermostat is 23 ℃, passes into O in reactor
3/ O
2Mist, stop aeration when the concentration of ozone is 0.6mg/L in the aqueous solution, then add the pCNB(parachloronitrobenzene at once in reactor), 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, takes a sample from sample tap at 0min, 1min, 5min, 10min and 20min, and institute's water sampling need be used the Na of 100 μ L immediately
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, and liquid-phase chromatographic analysis, ozone tail gas use 2% liquor kalii iodide absorption.
The described reactor of this test 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, △ in Fig. 1 represents to test two when adopting polynary poly-hydroxyl float stones to be the ozone catalytic agent, the clearance of ozone oxidation parachloronitrobenzene and the graph of relation in reaction time, when the contrast test I of the expression of zero in Fig. 1 test two adopts float stone to be the ozone catalytic agent, the clearance of parachloronitrobenzene and the graph of relation in reaction time when the clearance of ozone oxidation parachloronitrobenzene and the graph of relation in reaction time, the in Fig. 1 represent to test two the independent ozone oxidation of contrast test II; As seen from Figure 1, in the 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 removes that in water, pCNB efficient reaches 93%, improved respectively 31 percentage points than independent ozone oxidation and float stone O3 catalytic oxidation clearance.Above result of the test shows, in poly-hydroxyl float stone and ozone coupling degraded removal water, pCNB has obvious cooperative effect.
Fig. 2 is the EPR spectrogram of DMPO-OH in the O3 catalytic oxidation process, A in Fig. 2 represents to test two when adopting polynary poly-hydroxyl float stones to be the ozone catalytic agent, the EPR spectrogram of DMPO-OH in the O3 catalytic oxidation process, B in Fig. 2 represents to test two contrast test I when adopting float stone to be the ozone catalytic agent, the EPR spectrogram of DMPO-OH in the 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 the O3 catalytic oxidation process; By finding out in Fig. 2, the characteristic quadruple of the spectrogram of DMPO-OH addition compound product divides the peak and 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, after adding 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 the 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 (9)
1. the preparation method of 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: be ultrasonic cleaning 2 times～4 times under the condition of 40KHz in frequency with distilled water with float stone, the 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 the step 1 ultrasonic cleaning is put into concentration, obtains mixed liquor A; Three, filter, washing and dry: the mixed liquor A that step 2 obtains is filtered, and with distilled water flushing 5 times～7 times, is then dry 12h～24h under the condition of 60 ℃～120 ℃ in temperature with the solid that obtains after filtering, obtains solid B; Four, aluminum salt solution dipping: the solid B immersion concentration that step 3 is obtained is in the aluminum salt solution of 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, and with distilled water flushing 5 times～7 times, is then roasting 4h～6h under the condition of 450 ℃～650 ℃ in temperature with the solid that obtains after filtering, obtains solid D; Six, metal salt solution dipping: the solid D immersion concentration that step 5 is obtained is in the metal salt solution of 0.5mol/L～5.0mol/L, and dip time is 48h～72h, obtains suspension E; Seven, activation process: being 9～12 with alkaline solution with the suspension E adjusting pH value that step 6 obtains, then staticly settling 30min～60min, is activation process 24h～48h under 40 ℃～80 ℃ conditions in temperature at last, obtains mixed liquor F; Eight, filter, washing and dry: after the mixed liquor F that step 7 is obtained filters solid formation, then the pH that solid formation is washed with distilled water to cleaning solution is invariable, be dry 24h～48h under 40 ℃～80 ℃ conditions in temperature at last, namely get the agent of polynary poly-hydroxyl float stone ozone catalytic.
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 acid solution described in step 2 is salpeter solution, hydrochloric acid solution or sulfuric acid solution.
4. the preparation method of a kind of polynary poly-hydroxyl float stone ozone catalytic according to claim 1 agent, is characterized in that aluminum salt solution described in step 4 is aluminum nitrate solution, aluminum sulfate solution, liquor alumini chloridi or aluminium carbonate solution.
5. the preparation method of a kind of polynary poly-hydroxyl float stone ozone catalytic according to claim 1 agent is characterized in that 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.
6. 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.
7. the preparation method of 2,3,4,5 or 6 described a kind of polynary poly-hydroxyl float stone ozone catalytic agent according to claim 1,, the acid solution environment that it is characterized in that described in step 2, the float stone after the step 1 ultrasonic cleaning being put into concentration and be 0.6mol/L～0.9mol/L soaks 4h～5h, obtains mixed liquor A.
8. the preparation method of a kind of polynary poly-hydroxyl float stone ozone catalytic according to claim 7 agent, it is characterized in that it is in the aluminum salt solution of 1.0mol/L～4.0mol/L that the solid B that described in step 4, step 3 is obtained immerses concentration, dip time is 30h～46h, obtains suspension C.
9. the preparation method of a kind of polynary poly-hydroxyl float stone ozone catalytic according to claim 7 agent, it is characterized in that it is in the metal salt solution of 1.0mol/L～4.0mol/L that the solid D that described in step 6, step 5 is obtained immerses concentration, dip time is 50h～70h, obtains suspension E.
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| CN109174137B (en) * | 2018-11-12 | 2020-05-22 | 南京大学 | Modified ceramsite ozone catalyst, preparation method and application |
| CN111889065A (en) * | 2019-05-06 | 2020-11-06 | 中国石油化工股份有限公司 | Modified macroporous material and preparation method thereof |
| CN111889107A (en) * | 2019-05-06 | 2020-11-06 | 中国石油化工股份有限公司 | Hydrogenation protection catalyst and preparation method thereof |
| CN111889107B (en) * | 2019-05-06 | 2022-07-08 | 中国石油化工股份有限公司 | Hydrogenation protection catalyst and preparation method thereof |
| CN111889065B (en) * | 2019-05-06 | 2023-04-18 | 中国石油化工股份有限公司 | Modified macroporous material and preparation method thereof |
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