CN103962149A - Method for preparing multiphase ozonation solid catalyst for water treatment by using rare earth molecular sieve waste residues - Google Patents
Method for preparing multiphase ozonation solid catalyst for water treatment by using rare earth molecular sieve waste residues Download PDFInfo
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- CN103962149A CN103962149A CN201310415484.1A CN201310415484A CN103962149A CN 103962149 A CN103962149 A CN 103962149A CN 201310415484 A CN201310415484 A CN 201310415484A CN 103962149 A CN103962149 A CN 103962149A
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Abstract
The invention discloses a method for preparing a multiphase ozonation solid catalyst for water treatment by using rare earth molecular sieve waste residues. According to the method, metallic oxide and rare-earth oxide in the waste residues are sufficiently utilized as active agents for ozonation. The solid catalyst is suitable for various wastewater treatment, purposes of treating waste by waste and turning harm into good are achieved, the defects that the environment is polluted and the land is occupied by the waste residues are overcome, and remarkable economic benefits and environmental benefits are provided.
Description
1, technical field
The present invention relates to utilize rare earth containing zeolite waste residue to prepare the heterogeneous ozone oxidation solid catalyst of water treatment, belong to technical field of environmental science, be specifically related to the catalyst of solid slag utilization and wastewater treatment ozone oxidation.
2, background technology
Ozone has extremely strong oxidability, and oxidability is only second to fluorine, higher than chlorine and potassium permanganate, in water, can decompose voluntarily, there is no secondary pollution, is water treatment green oxidation medicament.Ozone not only has very strong disinfection ability, and micro-pollution hardly degraded organic substance in all right oxidation removal water, at present, is used widely in water treatment field.
The effect quality that adopts ozone technology, key is to improve the oxidability of ozone and the utilization rate of ozone.Traditional ozone oxidation ability and removal hardly degraded organic substance ability are lower, reported in literature take homogeneous phase as main at present, catalyst wiring solution-forming is added to the water catalyst and exists with ionic species, although this catalyst can improve the oxidability of ozone, but exist catalyst to be difficult to reclaim to reuse cause secondary pollution, increase the shortcomings such as difficulty of subsequent treatment.Ozone oxidation solid catalyst arises at the historic moment, and obtains in recent years the great attention of colleges and universities, scientific research department.Ozone oxidation solid catalyst is to take porous material as carrier, as active carbon, haydite, silica gel etc., by having, the metal nitrate of catalytic activity or one or more in sulfate are compound water-soluble by a certain percentage, by carrier impregnation a few hours in solution, then dry, roasting forms.But easily cause in process of production the security incidents such as inflammable and explosive, produce hypertoxic hyponitric acid gas, contaminated environment simultaneously.
Rare earth containing zeolite is the catalyst of petroleum cracking, produce in process of production many waste residues, these waste residues are by 50～60% silica gel, 15～20% silica-alumina gels form, contain multiple virulent metal oxide, rare-earth oxide, content is in 10～12% left and right, these metal oxides and rare-earth oxide are respectively lanthana, cerium oxide, praseodymium oxide, iron oxide, cobalt oxide, nickel oxide, cupric oxide, zinc oxide, manganese oxide, titanium oxide, cadmium oxide etc., contaminated environment, land occupation.These virulent metal oxides, the active constituent of ozone oxidation just, silica gel, silica-alumina gel has more much higher hole adsorptivity, if make a kind of solid catalyst, the ozone oxidation making it in waste water has better catalytic action, hardly degraded organic substance in waste water is had to better removal effect, this catalyst is activating agent because containing Multimetal oxide and rare-earth oxide, can be applicable to different wastewater treatments, therefore, utilize molecular sieve waste residue to prepare ozone oxidation catalyst, there is very great using value, both solved the contaminated environment of waste residue, again resource is recycled.
3, summary of the invention
The present invention seeks to utilize rare earth containing zeolite waste residue to prepare the heterogeneous ozone oxidation solid catalyst of water treatment, make metal oxide, rare-earth oxide in waste residue, by the permanent catalyst that becomes ozone oxidation in catalyst that is fixed on of sintering, improve the ability of ozone oxidation, improve the ability of hardly degraded organic substance in oxidize water, thereby reduce ozone oxidation operating cost.
The present invention is achieved through the following technical solutions the present invention, utilizes rare earth containing zeolite waste residue to prepare the heterogeneous ozone oxidation solid catalyst of water treatment, comprises the steps and process.
A. dehydrating of waste residue: waste residue contains 50～60% the crystallization water, dehydrates on far-infrared dryer.200～300 ℃ of baking temperatures.B. pulverize: by dehydrating rear waste residue, add 1～2% anthracite and pulverize in the lump, particle diameter is less than 0.1mm and is transferred in storage bin.C. granulation: at garden dish granulator granulation, produce the particle of particle diameter 0.5～0.8cm, spray into Ludox and make its proportioning of binding agent when granulation: waste residue powder: Ludox=100: 3～4.D. dry roasting: 200～300 ℃ of oven dry, then roasting forms the heterogeneous ozone oxidation solid catalyst of water treatment in 1100～1200 ℃ of stoves.
Activating agent of the present invention is to utilize metal oxide intrinsic in waste residue, rare-earth oxide, content is 10～12%, load on 50～60% silica gel, on 15～24% silica-alumina gels, drying dehydration, pulverizing, granulation, roasting form the heterogeneous ozone oxidation solid catalyst of water treatment.
The present invention has following beneficial effect with respect to prior art:
1. be twice laid, the treatment of wastes with processes of wastes against one another, has digested waste residue, has improved environmental pollution, has saved land resource.
2. utilize the silica gel of waste residue, the activating agent of silica-alumina gel porous adsorptivity and contained metal oxide ozone oxidation catalyst processed, has reduced Catalyst Production cost greatly.
3. catalyst is after roasting, and activating agent metal oxide is distributed on the loss that had both solved poisonous metal oxide in catalyst micropore securely, has improved again catalytic activity, reusable.
4. catalyst, because of metal oxide and rare-earth oxide containing multiple catalysts activity, is applicable to different wastewater treatments.
5. because can improving the ability of ozone oxidation containing rare-earth oxide and removing hardly degraded organic substance ability in water.
4, accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention
1-far-infrared dryer 2-pulverizer 3-granulating disc 4-roaster in figure
5, the specific embodiment
Embodiment 1, and a kind of rare earth containing zeolite waste residue that utilizes is prepared the heterogeneous ozone oxidation solid catalysis of water treatment agent method technique:
A. dehydrating of waste residue: 200～300 ℃ of baking temperatures.Waste residue contains 50% the crystallization water, at far-infrared dryer, dehydrates.B. pulverize: by dehydrating rear waste residue, add 1～2% anthracite and pulverize in the lump, powder particle diameter is less than 0.1mm, is transferred to storage bin standby.C. granulation: at garden dish granulator granulation, produce the particle of particle diameter 0.5～0.8cm, spray into Ludox and make binding agent in granulation process, its proportioning: powder: Ludox=100: 3～4.D. dry roasting: 200～300 ℃ of oven dry, 1100～1200 ℃ of roastings, form the heterogeneous ozone oxidation solid catalyst of water treatment.
Utilize ozone oxidation solid catalyst to process Coking Plant Wastewater, ozone dosage is: O3: COD=0.5: 1, COD drops to 90mg/L by original 120mg/L, adds after catalyst at same ozone dosage, and COD drops to 50mg/L, and treatment effeciency improves 33%.
Embodiment 2, utilize ozone oxidation solid catalyst to process Yingkou City's oil refinery waste water (catalyst is with embodiment 1), and ozone dosage is: O3: COD=1, COD drops to 340mg/L by original 540mg/L.Add after ozone catalytic agent, under same ozone dosage, COD drops to 140mg/L, and treatment effeciency improves 37%.
Embodiment 3, utilize ozone oxidation solid catalyst to process certain chemical plant wastewater (catalyst is with embodiment 1), and ozone dosage is: O3: COD=1, COD drops to 1350mg/L by original 1800mg/L.Add after ozone catalytic agent, COD drops to 800mg/L, and efficiency improves 31%.
Embodiment 4, utilize ozone oxidation solid catalyst to process certain printing and dyeing mill's waste water (catalyst is with embodiment 1), and ozone dosage is: O3: COD=0.8, COD drops to 280mg/L by original 480mg/L.Add after ozone catalytic agent catalysis, at same ozone, take out under dosage, COD drops to 90mg/L, and treatment effeciency improves 40%.
Claims (3)
1. utilize rare earth containing zeolite waste residue to prepare its feature of method of the heterogeneous ozone oxidation solid catalyst of water treatment, comprise following technology and step:
A. dehydrating of waste residue: waste residue is containing the crystallization water 50～60%, at far-infrared dryer drying and dehydrating, 200～300 ℃ of baking temperatures; B. pulverize: by dehydrating rear waste residue, add 1～2% anthracite and pulverize in the lump, be crushed to particle diameter and be less than 0.1mm, proceed to storage bin standby; C. granulation: produce the particle of particle diameter 0.5～0.8cm with garden dish comminutor, when granulation, spray into Ludox and make binding agent, its proportioning: powder: Ludox=100: 2～3; D. oven dry, roasting: 200～300 ℃ of oven dry, form the heterogeneous ozone oxidation solid catalyst of water treatment for 10 minutes through 1100～1200 ℃ of roastings.
2. according to claim 1, described waste residue is containing silica gel 50～60%, and silicon-aluminum containing gel 15～24%, contains 10～12% metal oxide, rare-earth oxide.(MnO、TiO
2、Fe
2O
3、Co
2O
3、NiO、CuO、CaO、BaO、ZrO
2、K
2O、Na
2O、MgO、La
2O
3、CeO
2、WO
3、Au
2o、Pr6O
11) 。
3. molecular sieve waste residue according to claim 1 is prepared the method for the heterogeneous ozone oxidation catalyst of water treatment, the particle of its particle diameter 0.5～0.8cm.
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Cited By (7)
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| CN106800332A (en) * | 2017-01-16 | 2017-06-06 | 东北大学 | A kind of method for treating water of utilization slag catalysis ozone |
| CN108483555A (en) * | 2018-05-28 | 2018-09-04 | 江苏金环环保设备有限公司 | Multiple-effect repair materials as well as preparation method and application thereof for black and odorous water reparation |
| CN111792751A (en) * | 2020-06-18 | 2020-10-20 | 神马实业股份有限公司 | Treatment method of caprolactam production wastewater |
| CN112209490A (en) * | 2020-07-24 | 2021-01-12 | 东莞理工学院 | Improving O content in modified domestic garbage incinerator slag3Method for treating urban black smelly water effect |
| CN112645429A (en) * | 2020-07-24 | 2021-04-13 | 东莞理工学院 | Method for improving effect of catalytic ozone treatment of organic wastewater by household garbage incinerator slag |
| CN112892549A (en) * | 2021-01-25 | 2021-06-04 | 天津大学 | Catalyst for treating sewage by electrocatalytic oxidation and preparation method thereof |
| CN113134355A (en) * | 2021-04-29 | 2021-07-20 | 国网山东省电力公司电力科学研究院 | Cobalt ion contaminated soil-based catalyst and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106800332A (en) * | 2017-01-16 | 2017-06-06 | 东北大学 | A kind of method for treating water of utilization slag catalysis ozone |
| CN108483555A (en) * | 2018-05-28 | 2018-09-04 | 江苏金环环保设备有限公司 | Multiple-effect repair materials as well as preparation method and application thereof for black and odorous water reparation |
| CN111792751A (en) * | 2020-06-18 | 2020-10-20 | 神马实业股份有限公司 | Treatment method of caprolactam production wastewater |
| CN112209490A (en) * | 2020-07-24 | 2021-01-12 | 东莞理工学院 | Improving O content in modified domestic garbage incinerator slag3Method for treating urban black smelly water effect |
| CN112645429A (en) * | 2020-07-24 | 2021-04-13 | 东莞理工学院 | Method for improving effect of catalytic ozone treatment of organic wastewater by household garbage incinerator slag |
| CN112209490B (en) * | 2020-07-24 | 2022-03-01 | 东莞理工学院 | Improving O content in modified domestic garbage incinerator slag3Method for treating urban black smelly water effect |
| CN112892549A (en) * | 2021-01-25 | 2021-06-04 | 天津大学 | Catalyst for treating sewage by electrocatalytic oxidation and preparation method thereof |
| CN112892549B (en) * | 2021-01-25 | 2022-03-01 | 天津大学 | Catalyst for treating sewage by electrocatalytic oxidation and preparation method thereof |
| CN113134355A (en) * | 2021-04-29 | 2021-07-20 | 国网山东省电力公司电力科学研究院 | Cobalt ion contaminated soil-based catalyst and preparation method and application thereof |
| CN113134355B (en) * | 2021-04-29 | 2022-12-20 | 国网山东省电力公司电力科学研究院 | Cobalt ion contaminated soil-based catalyst and preparation method and application thereof |
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Effective date of registration: 20160315 Address after: 337000 No. 188 East Avenue, Pingxiang Economic Development Zone, Jiangxi, Anyuan Patentee after: Zhang Zhenhui Patentee after: Yi Zhijian Patentee after: Wang Xiang Address before: 337000 No. 188 East Avenue, Pingxiang Economic Development Zone, Jiangxi, Anyuan Patentee before: Zhang Zhenhui |
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