CN102626629A - Preparation method of load-type metallic oxide ozone catalytic oxidation catalyst - Google Patents
Preparation method of load-type metallic oxide ozone catalytic oxidation catalyst Download PDFInfo
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Abstract
The invention relates to a preparation method of a catalyst, in particular to a preparation method of a load-type metallic oxide ozone catalytic oxidation catalyst, which is characterized by comprising the following steps of (1) selecting ceramic filter bulbs to serve as a carrier, washing through deionized water, soaking for 24h by using diluted hydrochloric acid, and washing through the deionized water to effluent neuter for stoving; (2) dipping for 24h in nickel nitrate solution with the concentration of 0.1-1.0mol/L and drying; (3) roasting for 5h in a muffle furnace at 500 DEG C to obtain roasting objects; and (4) washing through the deionized water and stoving to obtain the load-type metallic oxide ozone catalytic oxidation catalyst. The preparation method is simple, low in cost, capable of greatly improving oxidation rate and efficiency of ozone on organic pollutant, good in product stability and capable of repeatedly using, and having important significant on application and dissemination of catalytic ozonation techniques.
Description
Technical field
The present invention relates to a kind of catalytic ozone oxidation catalyst, be specifically related to a kind of load metal oxide catalytic ozonation Preparation of catalysts method, be meant that with the conventional ceramic filter bulb be carrier, is the preparation method of the loaded catalyst of active component with the nickel oxide.
Background technology
Along with developing rapidly of China's industrial or agricultural; The production of various chemical substances and use increasing; The waste water that contains the difficult degradation toxic organics in a large number is discharged into water body; The aggravation that causes natural water body to pollute, resident's health is arrived in serious threat, and has restricted economy, society and development of science and technology.
For the organic pollution that has high chemical stability, poisonous difficult for biological degradation in the water, adopt oxidation technology to handle usually.Ozone is a kind of extremely strong oxidant (oxidation-reduction potential 2.07V), and its oxidability is only second to fluorine, has that oxidability is strong, reaction speed soon, does not produce advantages such as secondary pollution, is the ideal green oxidant.At present, ozonation technology has been widely used in feedwater and the sewage disposal process separately, but also has a lot of problems:
(1) ozone is unstable in water, and mass-transfer efficiency is low, causes the practical efficiency of ozone not high, has increased processing cost;
(2) the ozone oxidation selectivity is high, and low to the reaction rate of some organic pollution, clearance is low, and salinity is low;
(3) in independent ozone oxidation process, some organic matter can be oxidized to small-molecule substances such as carboxylic acid, ketone, aldehydes, and the small-molecule substance of generation is prone to form some poisonous and hazardous accessory substances in subsequent technique.
These shortcomings and deficiencies to ozonation technology; The application of ozone technology has in recent years had very big improvement; Mainly can be summed up as two types: the first, ozone combine with other conventional unit for treating water (like ozone and flocculation coupling, ozone and biotechnology coupling, ozone and membrane technology coupling etc.); The second, the improvement of ozone treatment unit self mainly is meant ozone oxidation and other some chemical oxidation technology couplings, promotes dissolving and the decomposition of ozone in water, improves the treatment effeciency of oxidation technology, mainly contains H
2O
2∕ O
3, UV ∕ O
3, metal catalytic ozonation technology etc.
O3 catalytic oxidation is to utilize ozone generation under catalyst action that organic pollution in intermediate product (like OH) the oxidation Decomposition water of strong oxidability is more arranged; These intermediate product oxidabilities are extremely strong; The reaction non-selectivity; The high stability that fast oxidation Decomposition ozone can't oxidation, the organic matter of difficult degradation, this technology is the novel ozone oxidized method that development in recent years is got up, and belongs to second kind and improves one's methods.Different according to the catalyst form, O3 catalytic oxidation mainly is divided into two types: homogeneous catalysis ozone oxidation and heterogeneous catalysis ozone oxidation.
The homogeneous catalysis ozone oxidation has catalytic efficiency preferably, but mainly has two shortcomings.The first, catalyst is prone to loss in reaction, and recovery difficult is big, and recycling rate of waterused is low, and processing cost is high; The second, introduce metal ion in the processed water, not only increased the difficulty of subsequent treatment, increased processing cost, and the security of water outlet caused a hidden trouble, should not in drinking water treatment, use, limited should technology the scope of application.
The heterogeneous catalysis ozone oxidation is to use solid metallic, metal oxide or loads on metal or metal oxide on the carrier as the O3 catalytic oxidation technology of catalyst, and can be used for the metal oxide that catalysis ozone decomposes mainly is that some typical transition metal oxides are (like NiO, MnO
2, CuO, TiO
2, Fe
2O
3Deng).Compare with the homogeneous catalysis ozonation technology; The heterogeneous catalysis ozone oxidation not only can effectively improve the oxidation efficiency of ozone; Improve the clearance of organic pollution; And catalyst have convenient reclaims, can reuse, preparation technology is simple, production cost is low, advantage such as easy operating and maintenance in the use, is a kind of oxidation technology that the degradation of contaminant of application prospect is arranged very much.
Summary of the invention
The object of the present invention is to provide a kind of load metal oxide catalytic ozonation Preparation of catalysts method, the catalyst that this method is prepared is active high, and the preparation method is simple, and cost is low.
To achieve these goals, the technical scheme that the present invention taked is: a kind of load metal oxide catalytic ozonation Preparation of catalysts method is characterized in that it comprises the steps:
(1) chooses ceramic filtration ball that particle diameter is about 3.0mm as carrier,, washed ceramic filtration ball is soaked 24h with watery hydrochloric acid, dry after being washed till water outlet neutrality with deionized water again, obtain pretreated ceramic filtration ball with washed with de-ionized water 2～5 times;
(2) be 0.1～1.0mol/L nickel nitrate (Ni (NO with pretreated ceramic filtration ball in concentration
3)
26H
2O) flood in the solution, behind the dipping 24h that the macerate that obtains is dry, obtain the ceramic filtration ball behind the impregnation drying;
(3) with the 500 ℃ of following roasting 5h in Muffle furnace of the ceramic filtration ball behind the impregnation drying, obtain calcining matter;
(4) calcining matter spends oven dry after the deionised water 2～5 times, obtains load metal oxide catalytic ozonation catalyst.
Ceramic filtration ball used herein is that market is bought, and is the grey black spherical particle, and diameter is about 3.0mm, and bulk density is less than 1.3, and compression strength is greater than 50.
The used nickel salt of the present invention is a Nickelous nitrate hexahydrate, analyzes pure.
The outward appearance of the ceramic filtration ball load nickel oxide that the present invention makes is the dark brown spheroid.
The invention has the beneficial effects as follows:
(1) adopts above-mentioned catalyst degraded hardly degraded organic substance; Under same experimental conditions; Degradation rate is compared remarkable quickening with the independent oxidation of ozone; Compare not that load nickel oxide ceramic filtration ball catalytic degradation speed also improves a lot, promptly the catalyst prepared of this method has advantages of high catalytic activity.
(2) this catalyst is a carrier with the conventional ceramic filter bulb, draws materials extensively, and is cheap; This catalyst preparation process is simple, safety, no complex reaction process, and it is low to produce preparation cost.
(3) this catalyst stability is good, and in the cycle repeats test, catalytic effect still can keep preferably.
Description of drawings
Fig. 1 is an Experimental equipment of the present invention, among the figure: 1. drier; 2. ozone generator and flowmeter; 3. reactor; 4. catalyst layer; 5. distribution device; 6. sample tap; 7. device for absorbing tail gas.
Fig. 2 is the catalytic effect comparison diagram.
Fig. 3 is the comparison diagram before and after the ceramic filtration ball load.Can know by figure, successfully load on the ceramic filtration ball through NiO after the roasting.
The specific embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with instance, but content of the present invention not only is confined to following instance.
Embodiment 1:
A kind of load metal oxide catalytic ozonation Preparation of catalysts method, it comprises the steps:
(1) preliminary treatment of carrier: choose conventional ceramic filter bulb that particle diameter is about 3.0mm as carrier; With washed with de-ionized water 2～5 times; Washed ceramic filtration ball is soaked 24h with the watery hydrochloric acid of 0.1mol/L, dry after being washed till water outlet neutrality with deionized water again, obtain pretreated ceramic filtration ball;
(2) be 0.5mol/L nickel nitrate (Ni (NO with pretreated ceramic filtration ball in concentration
3)
26H
2O) flood in the solution, behind the dipping 24h that the macerate that obtains is dry, obtain the ceramic filtration ball behind the impregnation drying;
(3) (heating rate is 10 ℃/min) roasting 5h, obtains calcining matter in Muffle furnace under 500 ℃ with the ceramic filtration ball behind the impregnation drying;
(4) calcining matter spends oven dry after the deionised water 2～5 times, obtains load metal oxide catalytic ozonation catalyst.
Above-mentioned catalyst is used to contain the degraded of p-nitrophenol simulated wastewater, p-nitrophenol concentration 50mg/L, reaction temperature is 25 ℃, catalyst amounts 100g/L, experiment is to carry out under the condition of 3.3mg/min at ozone output.As a comparison, under same experimental conditions, use the ceramic filtration ball O3 catalytic oxidation and the independent oxidation p-nitrophenol of ozone of not load respectively.The result is as shown in Figure 2, and ▲ line is O3 catalytic oxidation of the present invention, ● line is the ceramic filtration ball O3 catalytic oxidation, and the ■ line is the independent oxidation of ozone.Can know that by Fig. 2 the present invention has significantly improved the degradation effect of ozone, explain that the catalyst that this method is prepared has advantages of high catalytic activity.
Embodiment 2:
A kind of load metal oxide catalytic ozonation Preparation of catalysts method, it comprises the steps:
(1) preliminary treatment of carrier: choose ceramic filtration ball that particle diameter is about 3.0mm as carrier; With washed with de-ionized water 2～5 times; Washed ceramic filtration ball is soaked 24h with the watery hydrochloric acid of 0.1mol/L, dry after being washed till water outlet neutrality with deionized water again, obtain pretreated ceramic filtration ball;
(2) be 0.1mol/L nickel nitrate (Ni (NO with pretreated ceramic filtration ball in concentration
3)
26H
2O) flood in the solution, behind the dipping 24h that the macerate that obtains is dry, obtain the ceramic filtration ball behind the impregnation drying;
(3) (heating rate is 10 ℃/min) roasting 5h, obtains calcining matter in Muffle furnace under 500 ℃ with the ceramic filtration ball behind the impregnation drying;
(4) calcining matter spends oven dry after the deionised water 2～5 times, obtains load metal oxide catalytic ozonation catalyst.
Above-mentioned catalyst is used to contain the degraded of p-nitrophenol simulated wastewater, p-nitrophenol concentration 50mg/L, reaction temperature is 25 ℃, catalyst amounts 100g/L, experiment is to carry out under the condition of 3.3mg/min at ozone output.The degradation rate of p-nitrophenol reaches 84% behind the catalytic degradation 70min.Explain that the catalyst that this method is prepared has advantages of high catalytic activity.
Embodiment 3:
A kind of load metal oxide catalytic ozonation Preparation of catalysts method, it comprises the steps:
(1) preliminary treatment of carrier: choose ceramic filtration ball that particle diameter is about 3.0mm as carrier; With washed with de-ionized water 2～5 times; Washed ceramic filtration ball is soaked 24h with the watery hydrochloric acid of 0.1mol/L, dry after being washed till water outlet neutrality with deionized water again, obtain pretreated ceramic filtration ball;
(2) be 0.3mol/L nickel nitrate (Ni (NO with pretreated ceramic filtration ball in concentration
3)
26H
2O) flood in the solution, behind the dipping 24h that the macerate that obtains is dry, obtain the ceramic filtration ball behind the impregnation drying;
(3) (heating rate is 10 ℃/min) roasting 5h, obtains calcining matter in Muffle furnace under 500 ℃ with the ceramic filtration ball behind the impregnation drying;
(4) calcining matter spends oven dry after the deionised water 2～5 times, obtains load metal oxide catalytic ozonation catalyst.
Above-mentioned catalyst is used to contain the degraded of p-nitrophenol simulated wastewater, p-nitrophenol concentration 50mg/L, reaction temperature is 25 ℃, catalyst amounts 100g/L, experiment is to carry out under the condition of 3.3mg/min at ozone output.The degradation rate of p-nitrophenol reaches 91% behind the catalytic degradation 70min.Explain that the catalyst that this method is prepared has advantages of high catalytic activity.
Embodiment 4:
A kind of load metal oxide catalytic ozonation Preparation of catalysts method, it comprises the steps:
(1) preliminary treatment of carrier: choose ceramic filtration ball that particle diameter is about 3.0mm as carrier; With washed with de-ionized water 2～5 times; Washed ceramic filtration ball is soaked 24h with the watery hydrochloric acid of 0.1mol/L, dry after being washed till water outlet neutrality with deionized water again, obtain pretreated ceramic filtration ball;
(2) be 0.7mol/L nickel nitrate (Ni (NO with pretreated ceramic filtration ball in concentration
3)
26H
2O) flood in the solution, behind the dipping 24h that the macerate that obtains is dry, obtain the ceramic filtration ball behind the impregnation drying;
(3) (heating rate is 10 ℃/min) roasting 5h, obtains calcining matter in Muffle furnace under 500 ℃ with the ceramic filtration ball behind the impregnation drying;
(4) calcining matter spends oven dry after the deionised water 2～5 times, obtains load metal oxide catalytic ozonation catalyst.
Above-mentioned catalyst is used to contain the degraded of p-nitrophenol simulated wastewater, p-nitrophenol concentration 50mg/L, reaction temperature is 25 ℃, catalyst amounts 100g/L, experiment is to carry out under the condition of 3.3mg/min at ozone output.The degradation rate of p-nitrophenol reaches 88% behind the catalytic degradation 70min.Explain that the catalyst that this method is prepared has advantages of high catalytic activity.
Embodiment 5:
A kind of load metal oxide catalytic ozonation Preparation of catalysts method, it comprises the steps:
(1) preliminary treatment of carrier: choose ceramic filtration ball that particle diameter is about 3.0mm as carrier; With washed with de-ionized water 2～5 times; Washed ceramic filtration ball is soaked 24h with the watery hydrochloric acid of 0.1mol/L, dry after being washed till water outlet neutrality with deionized water again, obtain pretreated ceramic filtration ball;
(2) be 1.0mol/L nickel nitrate (Ni (NO with pretreated ceramic filtration ball in concentration
3)
26H
2O) flood in the solution, behind the dipping 24h that the macerate that obtains is dry, obtain the ceramic filtration ball behind the impregnation drying;
(3) (heating rate is 10 ℃/min) roasting 5h, obtains calcining matter in Muffle furnace under 500 ℃ with the ceramic filtration ball behind the impregnation drying;
(4) calcining matter spends oven dry after the deionised water 2～5 times, obtains load metal oxide catalytic ozonation catalyst.
Above-mentioned catalyst is used to contain the degraded of p-nitrophenol simulated wastewater, p-nitrophenol concentration 50mg/L, reaction temperature is 25 ℃, catalyst amounts 100g/L, experiment is to carry out under the condition of 3.3mg/min at ozone output.The degradation rate of p-nitrophenol reaches 92% behind the catalytic degradation 70min.Explain that the catalyst that this method is prepared has advantages of high catalytic activity.
Embodiment 6
The recycle experiment: the catalyst that embodiment 1 is reclaimed spends deionised water 2～5 times, and at 120 ℃ of oven dry down, the catalyst after obtaining regenerating.Catalyst after the regeneration is used to contain the degraded of p-nitrophenol simulated wastewater, p-nitrophenol concentration 50mg/L, 25 ℃ of reaction temperatures, catalyst amounts 100g/L, experiment is to carry out the recycle experiment under the condition of 3.3mg/min at ozone output.Circulating, the degradation rate of p-nitrophenol still can reach 87% after three times.Explain after catalyst circulation that this method prepares is used three times and still have advantages of high catalytic activity.
Claims (2)
1. a load metal oxide catalytic ozonation Preparation of catalysts method is characterized in that it comprises the steps:
(1) chooses ceramic filtration ball as carrier,, washed ceramic filtration ball is soaked 24h with watery hydrochloric acid, dry after being washed till water outlet neutrality with deionized water again, obtain pretreated ceramic filtration ball with washed with de-ionized water 2～5 times;
(2) be to flood in 0.1～1.0mol/L nickel nitrate solution pretreated ceramic filtration ball in concentration, behind the dipping 24h that the macerate that obtains is dry, obtain the ceramic filtration ball behind the impregnation drying;
(3) with the 500 ℃ of following roasting 5h in Muffle furnace of the ceramic filtration ball behind the impregnation drying, obtain calcining matter;
(4) calcining matter spends oven dry after the deionised water 2～5 times, obtains load metal oxide catalytic ozonation catalyst.
2. a kind of load metal oxide catalytic ozonation Preparation of catalysts method according to claim 1, it is characterized in that: the diameter of the said ceramic filtration ball of step 1) is 3.0mm, and bulk density is less than 1.3, and compression strength is greater than 50.
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| CN103102593A (en) * | 2013-02-20 | 2013-05-15 | 四川大学 | Supported metal oxide catalytic synergistic inorganic flame retardant polypropylene composite material and preparation method thereof |
| CN103752354A (en) * | 2014-01-10 | 2014-04-30 | 天津市环境保护科学研究院 | Regeneration method and device used for deactivation catalyst layer of membrane ozone catalytic reactor |
| CN104014346A (en) * | 2014-05-16 | 2014-09-03 | 程帆 | Heterogeneous metal catalyst for ozonation enhancement as well as preparation method and application of catalyst |
| CN105080565A (en) * | 2015-06-03 | 2015-11-25 | 博天环境集团股份有限公司 | Method for preparing supported ozone oxidation catalyst |
| CN108435180A (en) * | 2018-02-05 | 2018-08-24 | 北京铭泽源环境工程有限公司 | A kind of support type ozone high grade oxidation catalyst and preparation method thereof |
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| CN108841558A (en) * | 2018-06-12 | 2018-11-20 | 枣阳市灵鹿酒业有限公司 | A kind of method of accelerated ageing yellow rice wine |
| CN110950419A (en) * | 2019-11-29 | 2020-04-03 | 萍乡煤科环保科技有限公司 | Ozone catalyst modification device |
| CN113332975A (en) * | 2021-04-15 | 2021-09-03 | 浙江大学 | Honeycomb ceramic etching supported catalyst and preparation method and application thereof |
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| CN114797839A (en) * | 2021-01-27 | 2022-07-29 | 陕西青朗万城环保科技有限公司 | Ozone decomposition catalyst and preparation method thereof |
| CN116987008A (en) * | 2023-08-14 | 2023-11-03 | 西陇科学股份有限公司 | Process for preparing gradient acetonitrile by using metal oxide supported catalyst |
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| CN104014346A (en) * | 2014-05-16 | 2014-09-03 | 程帆 | Heterogeneous metal catalyst for ozonation enhancement as well as preparation method and application of catalyst |
| CN105080565A (en) * | 2015-06-03 | 2015-11-25 | 博天环境集团股份有限公司 | Method for preparing supported ozone oxidation catalyst |
| CN108435180A (en) * | 2018-02-05 | 2018-08-24 | 北京铭泽源环境工程有限公司 | A kind of support type ozone high grade oxidation catalyst and preparation method thereof |
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| CN110950419A (en) * | 2019-11-29 | 2020-04-03 | 萍乡煤科环保科技有限公司 | Ozone catalyst modification device |
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Application publication date: 20120808 |