CN102335600A - Preparation method of expandable graphite catalyst and method for treating ozonized water of catalysis - Google Patents
Preparation method of expandable graphite catalyst and method for treating ozonized water of catalysis Download PDFInfo
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- CN102335600A CN102335600A CN2011101940769A CN201110194076A CN102335600A CN 102335600 A CN102335600 A CN 102335600A CN 2011101940769 A CN2011101940769 A CN 2011101940769A CN 201110194076 A CN201110194076 A CN 201110194076A CN 102335600 A CN102335600 A CN 102335600A
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Abstract
The invention relates to a preparation method of an expandable graphite catalyst and a method for treating ozonized water of catalysis, which relate to the methods for preparing a catalyst and treating water. The invention solves the problems that the selectivity and the degrading unthoroughness for difficult degraded organic pollutant by a single ozonization process are existed, a chloridized disinfection by-product with stronger toxicity is generated in a subsequent chlorine disinfection process after the individual ozonizated by-product micromolecule organic acid is generated, the breeding of microbe like bacteria in a pipe network after entering into the pipe network. The preparation method comprises the following steps: preparing the expandable graphite, stirring and washing the expandable graphite in a nitric acid solution, performing vacuum pump filtration, washing by deionized water, dehydrating, and pickling twice and placing into an oven for drying to obtain the expandable graphite catalyst. The preparative expandable graphite is combined with the organic pollutant degraded by ozone by the removal rate of 75%, the products are carbon dioxide and water, the invention has the advantages that no secondary pollution problem is generated, the performance of the catalyst is stable and the pollutants removal effect is reserved after using for three times.
Description
Technical field
The present invention relates to a kind of Preparation of catalysts method and method for treating water.
Background technology
Along with develop rapidly economic and industry, water resource receive organic contamination such as three industrial wastes, municipal refuse, agricultural chemicals and heavy metal pollution more and more serious.According to statistics; Water pollutant has reached kind more than 2,000 at present; Microorganisms such as organic chemistry material (like chloroform, agricultural chemicals etc.), heavy metal (like lead, mercury, arsenic etc.) and bacterium, pathogenic bacteria are major pollution sources, and wherein organic pollution is the main type of Drinking Water in China resource pollution.In the face of complicated at present water quality condition; Conventional water treatment process " coagulation-deposition-filtration-sterilization " can play very big effect to turbidity removal and sterilization; But be difficult to effectively remove for the micro-content organism that dissolves in the water; Can't satisfy resident living to requirements in water quality; Therefore, strengthen conventional treatment process or on the conventional water treatment process basis, increase new treatment process (preliminary treatment, advanced oxidation, biological activated carbon, membrane filtration, ion-exchange etc.) for ensureing that drinking water quality safety seems particularly important.Practice and research show; Ozone oxidation is to remove a kind of important method of organic pollution in the water technology; But exist problems such as the selectivity of degradation of pollutant and no thoroughnesses; Separately accessory substance-little molecule aldehyde of producing of ozone oxidation, ketone, carboxylic acid etc. have brought very big potential hazard to cholorination, get into the problem of growing that pipe network also can cause microorganisms such as bacterium in the pipe network.
Summary of the invention
The present invention will solve the selectivity and degraded no thoroughness of independent ozonisation technology to persistent organic pollutants; The cholorination accessory substance that toxigenicity is stronger after separately the small molecular by product organic acid of ozonisation generates gets into the technical problem of growing that pipe network also will cause microorganisms such as bacterium in the pipe network; And the method for expanded graphite Preparation of catalysts method and catalytic ozonation water treatment thereof is provided.The present invention is representational difficult degradation small molecular organic acid with oxalic acid; With ozone is main oxidant, utilizes expanded graphite catalytic ozonation system that the oxalic acid permineralization is decomposed, and produces carbon dioxide and water; Do not produce secondary pollution, realize that efficient, the safety of drinking water purifies.
Expanded graphite Preparation of catalysts method makes is undertaken by following step: step 1, perchloric acid and SPA mixed under 5～20 ℃ of conditions, add potassium permanganate and natural flake graphite then successively, the mass ratio of natural flake graphite and potassium permanganate is 1: 0.05～0.2; The mass ratio of natural flake graphite and perchloric acid is 1: 1～6, and the mass ratio of natural flake graphite and SPA is 1: 0.2～1, again heated at constant temperature 10～180min in 10～80 ℃ water-bath; Vacuum filtration is washed till neutrality with deionized water, dehydration; Under 50～80 ℃ of conditions, dry; Put into Muffle furnace, expand down, promptly obtain expanded graphite at 200～1100 ℃; Step 2, be that 0.6% salpeter solution, mass concentration are that 0.5% sulfuric acid solution, mass concentration are that 0.6% hydrochloric acid solution or mass concentration are agitator treating 12～72 hours in 0.5% the phosphoric acid solution in mass concentration with expanded graphite; Vacuum filtration is washed till neutrality with deionized water again, dehydration; Pickling secondary then; Place baking oven again, oven dry obtains the expanded graphite catalyst in 100 ℃.
The method of expanded graphite catalyst ozonization water treatment is with the preliminary treatment of water process, carries out catalytic ozonation again and handles, after post processing gets final product water outlet; It is characterized in that said; The expanded graphite catalyst exists with the fluid bed form in the ozone contact reaction device; It is that Xiang Shuizhong adds catalyst and feeds ozone and under 2～35 ℃ of conditions, reacts that catalytic ozonation is handled, and the reaction time 2.5～40min of catalytic ozonation, ozone dosage are 0.5～40mg/min; Catalyst is the expanded graphite catalyst of method for preparing, and catalyst throwing amount is 0.05～10g/L.
Through peroxidating, intercalation, expanded and obtain the expanded graphite catalyst, the new sheet surfaces that produces is active high, is easy to produce the living radical of strong oxidizing property with natural flake graphite in the present invention; During simultaneously mostly the hole of expanded graphite is, macroporous structure, be convenient to the diffusion in hole inside such as ozone and polluter, resistance to mass tranfer is less; Degradation efficiency is high, and in addition, expanded graphite is high temperature resistant, acid and alkali-resistance, flexibility; Stability is very high, and life cycle is long.Method for treating water of the present invention is accomplished through a cover ozone contact stirred reactor; Concrete operation is that the ozone that ozone generator produces is distributed in the whole reactor through the gas distribution system bottom the ozone contact reaction device uniformly; Under the effect of agitator, water fully contacts with catalyst with ozone, utilizes catalyst to come the polluter in the catalytic ozonation degradation water; Improve independent ozonisation ability, reacted tail gas is provided with device for absorbing tail gas.Expanded graphite catalytic ozonation system among the present invention can be applied to water factory separately or unite other technologies carry out simultaneously.In addition, the consersion unit in the expanded graphite catalytic ozonation system of the present invention is identical with existing water factory water treatment facilities, need not to change or transform water factory, and the preliminary treatment of water and post processing mode are identical with existing water factory technology.Utilize the expanded graphite associating ozone degradation organic pollution for preparing among the present invention, clearance can reach 75%, and product is carbon dioxide and water, the non-secondary pollution problem, and the stable performance of catalyst is used three times continuously, and the depollution effect is constant basically.
The specific embodiment
Technical scheme of the present invention is not limited to the following cited specific embodiment, also comprises the combination in any between each specific embodiment.
The specific embodiment one: this embodiment expanded graphite Preparation of catalysts method makes is undertaken by following step:
Step 1, perchloric acid and SPA are mixed under 5～20 ℃ of conditions, add potassium permanganate and natural flake graphite then successively, the mass ratio of natural flake graphite and potassium permanganate is 1: 0.05～0.2; The mass ratio of natural flake graphite and perchloric acid is 1: 1～6, and the mass ratio of natural flake graphite and SPA is 1: 0.2～1, again heated at constant temperature 10～180min in 10～80 ℃ water-bath; Vacuum filtration is washed till neutrality with deionized water, dehydration; Under 50～80 ℃ of conditions, dry; Put into Muffle furnace, expand down, promptly obtain expanded graphite at 200～1100 ℃;
Step 2, be that 0.6% salpeter solution, mass concentration are that 0.5% sulfuric acid solution, mass concentration are that 0.6% hydrochloric acid solution or mass concentration are agitator treating 12～72 hours in 0.5% the phosphoric acid solution in mass concentration with expanded graphite; Vacuum filtration is washed till neutrality with deionized water again, dehydration; Pickling secondary then; Place baking oven again, oven dry obtains the expanded graphite catalyst in 100 ℃.
The specific embodiment two: what this embodiment and the specific embodiment one were different is: the mass ratio of the said graphite of step 1 and perchloric acid, phosphoric acid and potassium permanganate is 1: 2: 0.4: 0.1.Other is identical with the specific embodiment one.
The specific embodiment three: what this embodiment was different with the specific embodiment one or two is: the said bath temperature of step 1 is 30 ℃, and be 90min heat time heating time.Other step is identical with the specific embodiment one or two with parameter.
The specific embodiment four: what this embodiment was different with one of specific embodiment one to three is: the said bake out temperature of step 1 is 70 ℃, and drying time is 90min.Other step is identical with one of specific embodiment one to three with parameter.
The specific embodiment five: what this embodiment was different with one of specific embodiment one to four is: step 1 expands down at 500 ℃.Other step is identical with one of specific embodiment one to four with parameter.
The specific embodiment six: what this embodiment was different with one of specific embodiment one to five is: the used acid of white picking is rare nitric acid of pH value=1 in the step 2, the 24h consuming time of pickling for the first time, the 12h consuming time of pickling for the second time.Other step is identical with one of specific embodiment one to five with parameter.
The specific embodiment seven: the method for expanded graphite catalyst ozonization water treatment is with the preliminary treatment of water process in this embodiment, carries out catalytic ozonation again and handles, after post processing gets final product water outlet; It is that Xiang Shuizhong adds catalyst and feeds ozone and under 2～35 ℃ of conditions, reacts that said catalytic ozonation is handled; Reaction time 2.5～the 40min of catalytic ozonation; The ozone dosage is 0.5～40mg/min; Catalyst is the expanded graphite catalyst of the specific embodiment one preparation, and catalyst throwing amount is 0.05～10g/L.
The specific embodiment eight: what this embodiment and the specific embodiment seven were different is; The ozone dosage is 1～30mg/min.Other step is identical with the specific embodiment seven with parameter.
The specific embodiment nine: what this embodiment and the specific embodiment seven were different is: the ozone dosage is 5～20mg/min.Other step is identical with the specific embodiment seven with parameter.
The specific embodiment ten: what this embodiment and the specific embodiment seven were different is: the ozone dosage is 10mg/min.Other step is identical with the specific embodiment seven with parameter.
The specific embodiment 11: what this embodiment was different with one of specific embodiment seven to ten is: catalyst throwing amount is 0.5～5g/L.Other step is identical with one of specific embodiment seven to ten with parameter.
The specific embodiment 11: what this embodiment was different with one of specific embodiment seven to ten is: catalyst throwing amount is 2g/L.Other step is identical with one of specific embodiment seven to ten with parameter.
The specific embodiment 12: what this embodiment and the specific embodiment seven to 11 were different is: said preliminary treatment is with water deposition again behind coagulation.Other step is identical with the specific embodiment seven to 11 with parameter.
The specific embodiment 13: this embodiment expanded graphite Preparation of catalysts method makes is undertaken by following step: step 1, perchloric acid (mass concentration is 72%) and SPA (mass concentration is 85%) mixed under 30 ℃ of conditions, add potassium permanganate and 50 order natural flake graphites then successively, natural flake graphite: perchloric acid: phosphoric acid: potassium permanganate=1: 2: 0.4: 0.1 (mass ratio); Heated at constant temperature 90min in 70 ℃ water-bath again; (purpose is vacuum filtration: depickling), be washed till neutrality with deionized water, dehydration; Under 70 ℃ of conditions, dry 90min; Put into Muffle furnace, expand down, promptly obtain expanded graphite at 500 ℃; Step 2, be agitator treating 24 hours in 0.6% the salpeter solution with expanded graphite in mass concentration, vacuum filtration is washed till neutrality with deionized water again; Dehydration, (the used acid of white picking is rare nitric acid of pH value=1 to the pickling secondary, the 24h consuming time of pickling for the first time then; The 12h consuming time of pickling for the second time); Place baking oven again, oven dry obtains the expanded graphite catalyst in 100 ℃.
The expanded graphite catalyst exists with the fluid bed form in the ozone contact reaction device, after water carries out coagulation-deposition-filtration treatment, gets into the catalytic ozonation reaction tank, carries out post processing after the oxidation reaction and gets final product water outlet.In the catalytic ozonation reaction tank; Gas distribution system through ozone contact reaction device bottom behind the ozone generator generation ozone gets into reaction system; Catalyst adds from reactor head, stirs through agitator whole system is mixed, and the ozone dosage is for being about 21.6mg/min; Catalyst throwing amount 0.3g/L, reaction time 20min.
Before this embodiment is handled water entering catalytic ozonation reactor; The initial concentration of oxalic acid is 1.0mmol/L, and solution pH=3 this moment is behind expanded graphite catalytic ozonation degraded 20min; The concentration of water mesoxalic acid is 0.25mmol/L; Clearance is up to 75%, (ozone oxidation oxalic acid separately, clearance is less than 2% during 20min; Expanded graphite adsorbs oxalic acid separately, and clearance is less than 3% during 20min).After the test result of TOC shows the oxidized degraded of oxalic acid, do not have other organic products to generate, all generated carbon dioxide and water, non-secondary pollution.
Claims (10)
1. expanded graphite Preparation of catalysts method, it is characterized in that expanded graphite Preparation of catalysts method makes is undertaken by following step:
Step 1, perchloric acid and SPA are mixed under 5～20 ℃ of conditions, add potassium permanganate and natural flake graphite then successively, the mass ratio of natural flake graphite and potassium permanganate is 1: 0.05～0.2; The mass ratio of natural flake graphite and perchloric acid is 1: 1～6, and the mass ratio of natural flake graphite and SPA is 1: 0.2～1, again heated at constant temperature 10～180min in 10～80 ℃ water-bath; Vacuum filtration is washed till neutrality with deionized water, dehydration; Under 50～80 ℃ of conditions, dry; Put into Muffle furnace, expand down, promptly obtain expanded graphite at 200～1100 ℃;
Step 2, be that 0.6% salpeter solution, mass concentration are that 0.5% sulfuric acid solution, mass concentration are that 0.6% hydrochloric acid solution or mass concentration are agitator treating 12～72 hours in 0.5% the phosphoric acid solution in mass concentration with expanded graphite; Vacuum filtration is washed till neutrality with deionized water again, dehydration; Pickling secondary then; Place baking oven again, oven dry obtains the expanded graphite catalyst in 100 ℃.
2. expanded graphite Preparation of catalysts method according to claim 1, the mass ratio that it is characterized in that the said graphite of step 1 and perchloric acid, phosphoric acid and potassium permanganate is 1: 2: 0.4: 0.1.
3. expanded graphite Preparation of catalysts method according to claim 1 and 2 is characterized in that the said bath temperature of step 1 is 30 ℃, and be 90min heat time heating time.
4. expanded graphite Preparation of catalysts method according to claim 3 is characterized in that the said bake out temperature of step 1 is 70 ℃, and drying time is 90min.
5. expanded graphite Preparation of catalysts method according to claim 4 is characterized in that step 1 expands down at 500 ℃.
6. expanded graphite Preparation of catalysts method according to claim 5 is characterized in that the used acid of white picking is rare nitric acid of pH value=1 in the step 2, the 24h consuming time of pickling for the first time, the 12h consuming time of pickling for the second time.
7. the method for expanded graphite catalyst ozonization water treatment, this method be with water through preliminary treatment, carry out catalytic ozonation again and handle, after post processing gets final product water outlet; It is characterized in that it is that Xiang Shuizhong adds catalyst and feeds ozone and under 2～35 ℃ of conditions, reacts that said catalytic ozonation is handled; Reaction time 2.5～the 40min of catalytic ozonation; The ozone dosage is 0.5～40mg/min; Catalyst is the expanded graphite catalyst of claim 1 preparation, and catalyst throwing amount is 0.05～10g/L.
8. according to the method for the said expanded graphite catalyst of claim 7 ozonization water treatment, it is characterized in that the ozone dosage is 1～30mg/min.
9. according to the method for claim 7 or 8 said expanded graphite catalyst ozonization water treatment, it is characterized in that catalyst throwing amount is 0.5～5g/L.
10. according to the method for the said expanded graphite catalyst of claim 9 ozonization water treatment, it is characterized in that said preliminary treatment is that water is precipitated again behind coagulation.
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Cited By (4)
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| CN107744806A (en) * | 2017-10-16 | 2018-03-02 | 燕山大学 | A kind of preparation method of catalyst using expanded graphite as carrier catalysis ozone decomposition |
| CN111068513A (en) * | 2019-12-27 | 2020-04-28 | 东华大学 | Method for treating coating waste gas by manganese-loaded expanded graphite adsorption coupling catalysis ozone oxidation |
| CN112662381A (en) * | 2020-12-26 | 2021-04-16 | 国网甘肃省电力公司经济技术研究院 | Preparation method and application of framework material for adsorbing heat storage material |
| CN116354340A (en) * | 2023-03-14 | 2023-06-30 | 昆明理工大学 | Low-cost large-scale preparation method of high-quality graphene |
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| US20040000735A1 (en) * | 2002-06-28 | 2004-01-01 | Graftech Inc. | Partially expanded, free flowing, acid treated graphite flake |
| CN1462724A (en) * | 2003-04-30 | 2003-12-24 | 中国科学院山西煤炭化学研究所 | Method for preparing expanded graphite without sulphur |
| CN1613757A (en) * | 2004-11-16 | 2005-05-11 | 南京理工大学 | Preparation of expandable graphite at low-temperature |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107744806A (en) * | 2017-10-16 | 2018-03-02 | 燕山大学 | A kind of preparation method of catalyst using expanded graphite as carrier catalysis ozone decomposition |
| CN107744806B (en) * | 2017-10-16 | 2020-01-07 | 燕山大学 | Preparation method of catalyst for catalytically decomposing ozone by taking expanded graphite as carrier |
| CN111068513A (en) * | 2019-12-27 | 2020-04-28 | 东华大学 | Method for treating coating waste gas by manganese-loaded expanded graphite adsorption coupling catalysis ozone oxidation |
| CN112662381A (en) * | 2020-12-26 | 2021-04-16 | 国网甘肃省电力公司经济技术研究院 | Preparation method and application of framework material for adsorbing heat storage material |
| CN116354340A (en) * | 2023-03-14 | 2023-06-30 | 昆明理工大学 | Low-cost large-scale preparation method of high-quality graphene |
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Application publication date: 20120201 |