CN105289629B - UV stable agent method in a kind of lanthanum based perovskite type oxide catalyst ozone degradation water - Google Patents
UV stable agent method in a kind of lanthanum based perovskite type oxide catalyst ozone degradation water Download PDFInfo
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Abstract
Present invention offer is a kind of to prepare the preparation method of high-specific surface area lanthanum based perovskite type oxide and its application in catalytic ozonation using mantle plate, belongs to water technology and environment functional material field.Lanthanum based perovskite type oxide is prepared using Surfactant CTAB, metal nitrate as main material using the precipitation method, improves the degradation capability to UV stabilizer PBSA in high-level oxidation technology.The problem of present invention is handled to UV stabilizer poor removal effect for existing conventional sewage, it is proposed that a kind of perofskite type oxide prepared using soft template method is used as catalyst, and realize the application in high-level oxidation technology, the shortcomings that overcoming traditional ozone oxidation, not only realize the features such as technique is simple in catalyst preparation, cost is cheap and environmental pollution is small, and the ability that ozone decomposed produces living radical is improved, realize the efficient removal to organic pollution.
Description
Technical field
The present invention relates to ultraviolet steady in a kind of preparation method and its catalysis ozone degradation water of lanthanum based perovskite type oxide
Determine agent method.
Background technology
PBSA (2-phenylbenzimidazole-5-sulfonic acid, referred to as
PBSA it is one of most basic medicine and personal care articles (PPCPs)) as a kind of active suncream composition.As one kind
Water-soluble suncream composition, PBSA are a kind of micro quantity organic pollutants, and the influence to water environment has potential threat.Relevant research
Show, the aquatile such as fish can accumulate this pollutant into adipose tissue, and probably be transferred to the next generation.Except this
In addition, another harm of suncream, which is shown in neonate's human milk samples, is found containing ultraviolet absorber.PBSA is to go
Except organic matter and some nutriments are target and the sewage treatment plant of design-build is generally difficult to remove, or even imitated without removing
Fruit.Such compound may have certain environmental persistence and long-distance migration ability.In view of these pollutants to water quality
Influence, it is necessary to further ensure water quality safety by further treatment technique.
Heterogeneous catalytic ozonation technology is a kind of economic, efficient wastewater treatment technology of advanced oxidation, is to strengthen ozone oxygen
Change and go one of new technology of high stability organic pollution in water removal.It is characterized in producing strong oxidizing property, the hydroxyl of non-selectivity
Free radical (OH), the thorough mineralising of organic pollution is set to be converted into carbon dioxide and water.This high-level oxidation technology is
The processing of many water pollutants provides new method.Heterogeneous catalytic ozonation technology is aoxidized using catalyst such as metal
Thing, metal or metal oxide supported in carrier, activated carbon and hollow microporous material etc., to promote ozone decomposed to produce more
More OH carry out degradable organic pollutant, and heterogeneous catalytic ozonation technology overcomes some of traditional ozonation technology and asked
Topic, as yield of ozone is not high and utilization rate is relatively low, the oxidation activity of ozone has certain selectivity, so as to add ozone oxygen
Processing cost of change etc..Therefore, a kind of not only economical and practical but also safely and effectively catalytic ozonation technology is developed, prepares one
Kind cheap and better catalytic activity catalyst turn into solve existing issue there is an urgent need to.
Composite oxides have excellent oxidation/reduction characteristic, high mechanical properties, good heat endurance, thus existing
For being widely used as catalyst in chemical industry.Wherein, perovskite composite oxide is especially noticeable, and its formula is expressed as
ABO3.Its catalytic activity depends primarily on B bits element, and a small amount of other alkaline-earth metal or transition metal are adulterated in B positions, can be significantly
Change its catalytic performance.The effect of A positions ion main stabilization structure.Just because perofskite type oxide has flexible design
Property so that such material is quite favored in fields such as physics, chemistry.But the application prospect of these materials compares table because its is low
Area and limited.It is therefore possible to use soft template method prepares mesoporous perovskite-type oxide catalysts, to pass through soft template
Addition improve catalyst specific surface area, so as to improve catalytic activity, and be initially formed template compared with hard template method and add calcium titanium
The method of ore deposit is compared, and soft template method has the simple advantage of preparation process step.Therefore, it is a kind of catalysis for there are bright prospects
Agent.
The content of the invention
The present invention is directed to the polluted-water containing UV stabilizer PBSA, to solve existing conventional sewage poor processing effect
Problem, innovative proposing prepare perovskite-type oxide catalysts in heterogeneous catalytic ozonation technology with soft template method
Application, and for soft template method prepare perovskite-type oxide catalysts preparation and application conditions illustrate.This hair
The bright specific surface area for being intended to improve perovskite-type oxide catalysts by the introducing of soft template, and prepared using the precipitation method, profit
Formed with the self assembly ability of metal it is mesoporous, to improve the avtive spot of catalyst, so as to improve the catalytic capability of catalyst,
Realize the fast degradation to organic matter.
The present invention provides preparation and its catalytic degradation UV stabilizer effect research of a kind of lanthanum based perovskite type oxide,
It is characterized in that (one) forms loose structure using soft template and its ability of self assembly；Prepared by means of the simple precipitation method
Perovskite-type oxide catalysts；The specific surface area and pore volume of traditional perofskite type oxide are improved, and then strengthens ozone pair
The degradation capability of hardly degraded organic substance.It is characterized in that (two) can complete to prepare by following process：(1) 0~2g ten is weighed
Six alkyl trimethyl ammonium bromides (CTAB), are dissolved in 10~50ml deionized waters at room temperature；(2) 2 are added in above-mentioned solution
~8mmol lanthanum nitrates and 2~8mmol cobalt nitrates simultaneously stir, and solution are warming up into 60~80 DEG C, and further stir 30~60 points
Clock；(3) after solution temperature is reduced to room temperature, it is 12~13 that 4.0mo1/L NaOH to pH, which are added dropwise, and solution gradually becomes suspension
Liquid；(4) suspension is stirred 6~8 hours at 60~80 DEG C, be then stirred at room temperature 10~14 hours；(5) dry, will
The amorphous precursor for the sample that step (4) is obtained is put into baking oven, and crystallization is dried at 90~110 DEG C；(6) calcine,
The dried powder obtained through step (5) is calcined 3.8~4.2 hours at 700~800 DEG C；(7) cool down, be naturally cooling to room temperature.
The present invention provides preparation and its catalytic degradation UV stabilizer effect research of a kind of lanthanum based perovskite type oxide,
It is characterized in that (three) technique is realized by following steps：(1) O needed for technique3Concentration is 0.5~2.0mg/L；(2)
Lanthanum based perovskite type oxide catalyst throwing amount is 0.5~2.0g/L needed for technique；(3) pollutant concentration is in staying water
2.0~10.0mg/L；(4) time of contact is 10~60min；(5) reaction system pH scopes are 3.0~9.00.
Accompanying drawing content
Accompanying drawing is the LaCoO prepared using CTAB as template that embodiment one obtains3It is smelly in catalysis for catalyst
Removal efficiency figure in oxygen oxidation system to UV stabilizer PBSA, wherein ■ represent independent ozone oxidation PBSA removal effect
Can, ▲ represent CTAB/LaCoO3To PBSA adsorption capacity, ● represent CTAB/LaCoO3O3 catalytic oxidation removes PBSA effect
Energy.It can be seen that CTAB/LaCoO3Catalysis oxidation decontaminates removal effect of the more independent ozonation technology of technology to PBSA
Fruit significantly improves, and CTAB/LaCoO3There is certain adsorption capacity to pollutant PBSA, can equally realize to being polluted in water body
Thing PBSA reinforcing removes.
Embodiment
By the preparation method of this lanthanum based perovskite type oxide and its in catalytic degradation water UV stabilizer efficiency
The application of research illustrates, and technical solution of the present invention is not limited to following enumerated embodiment, in addition to each specific
Any combination between embodiment.
Embodiment one：The preparation method of present embodiment lanthanum based perovskite type oxide catalyst is：(1) weigh
0~2g cetyl trimethylammonium bromides (CTAB), are dissolved in 10~50ml deionized waters at room temperature；(2) in above-mentioned solution
Middle addition 2~8mmol lanthanum nitrates and 2~8mmol cobalt nitrates simultaneously stir, and solution are warming up into 60~80 DEG C, and further stir
30~60 minutes；(3) after solution temperature is reduced to room temperature, it is 12~13 that 4.0mo1/LNaOH to pH, which is added dropwise, and solution is gradual
It is changed into suspension；(4) suspension is stirred 6~8 hours at 60~80 DEG C, be then stirred at room temperature 10~14 hours；(5)
Dry, the amorphous precursor for the sample that step (4) is obtained is put into baking oven, and crystallization is dried at 90~110 DEG C；
(6) calcine, the dried powder obtained through step (5) is calcined 3.8~4.2 hours at 700~800 DEG C；(7) cool down, drop naturally
Warm to room temperature.
Technology is decontaminated in O3 catalytic oxidation system to realize according to following steps：(1) O needed for technique3Concentration be 0.5~
2.0mg/L；(2) lanthanum based perovskite type oxide catalyst throwing amount is 0.5~2.0g/L needed for technique；(3) in staying water
Pollutant concentration is 2.0~10.0mg/L；(4) time of contact is 10~60min；(5) reaction system pH scopes be 3.0~
9.00。
Removal of the lanthanum based perovskite type oxide catalyst being prepared in present embodiment to UV stabilizer PBSA
Rate reaches more than 80%, can strengthen absorption and oxidation to PBSA, realizes the reinforcing to UV stabilizer PBSA and removes, and
It is cheap and catalyst preparation process is simple, it is a kind of catalyst with extensive prospect.
In the lanthanum based perovskite type oxide catalyst degradation water that present embodiment obtains in the effect research of UV stabilizer,
It can realize that the reinforcing to difficult for biological degradation UV stabilizer pollutant PBSA present in water removes.It can be sent out from accompanying drawing
It is existing, using CTAB/LaCoO3As catalyst to PBSA clearance up to more than 80%, more independent ozone oxidation improves 35
Percentage point, and CTAB/LaCoO3Catalyst has certain adsorption capacity, can equally improve the reinforcing to PBSA and remove.
Claims (1)
- A kind of 1. UV stable agent method in lanthanum based perovskite type oxide catalyst ozone degradation water, it is characterised in that：Using soft Template and its ability of self assembly, form loose structure；Perovskite-type oxide catalysts are prepared by means of the simple precipitation method； The specific surface area and pore volume of traditional perofskite type oxide are improved, and then strengthens degraded energy of the ozone to hardly degraded organic substance Power；Described lanthanum based perovskite type oxide catalyst, it is characterised in that complete to prepare by following process：(1) 2g cetyl trimethylammonium bromides (CTAB) are weighed, are dissolved at room temperature in 10~50mL deionized waters；(2) 2~8mmol lanthanum nitrates and 2~8mmol cobalt nitrates are added in above-mentioned solution and is stirred, solution is warming up to 60~ 80 DEG C, and further stir 30~60 minutes；(3) after solution temperature is reduced to room temperature, it is 12~13 that 4.0mo1/L NaOH to pH, which are added dropwise, and solution gradually becomes outstanding Supernatant liquid；(4) suspension is stirred 6~8 hours at 60~80 DEG C, be then stirred at room temperature 10~14 hours；(5) dry, the amorphous precursor for the sample that step (4) is obtained is put into baking oven, is dried at 90~110 DEG C Crystallization；(6) calcine, the dried powder obtained through step (5) is calcined 3.8~4.2 hours at 700~800 DEG C；(7) cool down, be naturally cooling to room temperature；UV stabilizer is realized by following steps in described lanthanum based perovskite type oxide catalyst degradation water：(1) O needed for technique3Concentration is 0.5~2.0mg/L；(2) lanthanum based perovskite type oxide catalyst throwing amount is 0.5~2.0g/L needed for technique；(3) pollutant concentration is 2.0~10.0mg/L in staying water；(4) time of contact is 10~60min；(5) reaction system pH scopes are 3.0~9.00.
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| CN108002543B (en) * | 2017-11-30 | 2020-07-31 | 天津大学 | Application of acinetobacter to degradation of ultraviolet absorbent PBSA |
| CN109607743B (en) * | 2018-12-21 | 2021-11-26 | 北京林业大学 | Catalytic ozonation water treatment pollution removal technology based on enhanced electron transfer efficiency |
| CN110280251B (en) * | 2019-06-20 | 2022-08-19 | 北京北华中清环境工程技术有限公司 | Lanthanum ferrite ozone catalyst for advanced treatment and preparation method thereof |
| CN115445605B (en) * | 2022-09-20 | 2023-06-23 | 中国地质大学（武汉） | Application of aluminum-doped lanthanum-manganese perovskite catalyst |
| CN116196933A (en) * | 2023-01-09 | 2023-06-02 | 江西嘉陶无机材料有限公司 | Porous perovskite catalyst LaCo 0.7 Fe 0.3 O 3 Preparation method and application thereof |
| CN115970724A (en) * | 2023-02-13 | 2023-04-18 | 浙江理工大学 | Preparation method of ceramic membrane with catalytic ozonation function |
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