WO2021120467A1 - Nitrogen-modified perovskite composite molecular sieve photocatalyst, and preparation method and application thereof - Google Patents

Nitrogen-modified perovskite composite molecular sieve photocatalyst, and preparation method and application thereof Download PDF

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WO2021120467A1
WO2021120467A1 PCT/CN2020/084904 CN2020084904W WO2021120467A1 WO 2021120467 A1 WO2021120467 A1 WO 2021120467A1 CN 2020084904 W CN2020084904 W CN 2020084904W WO 2021120467 A1 WO2021120467 A1 WO 2021120467A1
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photocatalyst
nitrogen
molecular sieve
composite molecular
perovskite composite
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French (fr)
Chinese (zh)
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吴敏
刘颖
厉明升
王传传
李志豪
赵颖丹
张仲琨
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东南大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/005—Spinels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Definitions

  • the invention relates to a photocatalyst and a preparation method and application thereof, in particular to a photocatalyst of a nitrogen-modified perovskite composite molecular sieve and a preparation method and application thereof.
  • Aromatic compounds are a class of compounds with a benzene ring structure. They have a stable structure, are difficult to decompose, and are highly toxic. Aromatic compounds come from the lignin and secondary metabolic processes of higher plants on the one hand, and on the other hand come from various chemical products synthesized in industry, such as pesticides, herbicides, dyes, explosives and so on. Aromatic compounds such as benzene, benzonitriles, and phenols are being produced in the amount of one million tons per year. These compounds are widely used in fuels and industrial solvents, and they, together with polycyclic aromatic compounds and chlorinated biphenyls, are used in the production of medicines. , Pesticides, plastic polymers, explosives and other daily necessities.
  • the existing treatment methods for aromatic wastewater mainly include physical treatment, chemical treatment, biological treatment and other methods such as low-temperature plasma technology, nano-photocatalytic technology, etc.
  • biodegradation method has a mature treatment process and low cost, it is only suitable for the treatment of low-concentration aromatic compounds; chemical oxidation and advanced oxidation technology methods refer to adding a certain amount of oxidants (oxygen, hydrogen peroxide, Ozone, etc.), under certain conditions, a strong oxidant is produced, which makes the aromatic compounds be oxidized and degraded, and finally completely mineralized into carbon dioxide and water.
  • oxidants oxygen, hydrogen peroxide, Ozone, etc.
  • the adsorption method is a more effective method for the treatment of aromatic compounds, mainly using porous materials to adsorb pollutants in the wastewater.
  • the pollutants in the adsorbent will enter the inside of the adsorbent through the pore structure of the adsorbent, and then the adsorbent can be treated to a certain extent, so that the adsorbent can be recycled.
  • cold plasma treatment of wastewater is a new wastewater treatment technology that combines high-energy electron radiation, ozone oxidation, and ultraviolet photolysis.
  • nano-photocatalytic technology has mild reaction conditions, can use ultraviolet light and sunlight and other conditions, directly and indirectly pollutants into CO2, water and other harmless substances, and consumes little energy and does not produce Secondary pollution.
  • Commonly used photocatalysts such as TiO2 have wide band gap, can not make full use of visible light, low quantum efficiency and other shortcomings, while perovskite catalyst has narrow band gap and small band gap, it is a better photocatalyst, but calcium Titanium ore has the problem of high electron-hole recombination rate, and does not respond well to a wide range of visible light.
  • the first object of the present invention is to provide an efficient, convenient, energy-saving and environmentally friendly nitrogen-modified perovskite composite molecular sieve photocatalyst.
  • the second object of the present invention is to provide a method for preparing the photocatalyst.
  • the third objective is to provide the application of the photocatalyst.
  • the photocatalyst of the nitrogen-modified perovskite composite molecular sieve of the present invention is N-LaFeO 3 @MCM-41.
  • the preparation method of the photocatalyst of the present invention includes the following steps:
  • step (1) a soft template agent is added to the A solution.
  • the soft template is cetyltrimethylammonium bromide (CTAB), which controls the size of the material and increases the specific surface area of the material.
  • CTAB cetyltrimethylammonium bromide
  • the complexing agent is any one of tartaric acid, malic acid, aspartic acid or lactic acid.
  • the aromatic compound is one of benzonitrile, p-methoxybenzonitrile, terephthalonitrile or bisphenol A.
  • the application of the photocatalyst of the present invention includes the following steps: adding a photocatalyst, a hole trapping agent, and aromatic compound organic wastewater to a photocatalytic reactor to perform a photocatalytic reaction, wherein the hole trapping agent and the aromatic
  • the volume ratio of the compound is 1:8-16, and the dosage of the photocatalyst per liter of the mixture of the hole trapping agent and the aromatic compound is 0.2-0.6g.
  • dark adsorption is performed before the photocatalytic reaction.
  • the hole trapping agent is one of methanol or ammonium oxalate.
  • the photocatalytic reaction provides visible light through a xenon lamp.
  • the photocatalyst of the present invention uses nitrogen-modified perovskite to reduce the forbidden band width of the catalyst and increase the visible light absorption area, thereby improving the efficiency of degrading aromatic compound organic wastewater; using molecular sieve MCM-41 as a carrier, Significantly increase the contact area between the catalyst and organic wastewater, and promote rapid catalytic degradation;
  • the preparation method of the photocatalyst of the present invention is easy to operate and has low cost; the method has simple equipment, flexible process, high purity of the material and easy control of the particle size; the method can use chemical reactions in the solution to make the raw materials at the molecular level Uniform mixing, so as to obtain a product with high uniformity, the uniformity of which can reach the size of molecules or atoms;
  • the photocatalyst of the present invention does not use various oxidants during the application process, and there is no need to worry about the problem of oxidant recovery, which greatly saves costs; does not produce sludge and secondary pollution; reacts under low temperature and normal pressure, and makes full use of visible light, saving energy.
  • Figure 1 shows the photocatalytic degradation mechanism of the present invention.
  • N-LaFeO 3 @MCM-41-1 catalyst methanol and bisphenol A wastewater to the photocatalytic reactor for photocatalytic reaction.
  • the volume ratio of methanol and bisphenol A wastewater is 1:8, per liter of methanol and bisphenol
  • the dosage of the photocatalyst in the mixture of wastewater A is 0.2g; first carry out the dark adsorption reaction for 30 minutes, after reaching the adsorption equilibrium, then provide visible light through the xenon lamp, and carry out the catalytic reaction at room temperature. At the same interval, take the supernatant and pass After 0.45 ⁇ m filter membrane, it was determined that the removal rate of bisphenol A reached more than 90% and the COD removal rate in the reaction system was 90%.
  • N-LaFeO 3 @MCM-41-2 catalyst methanol and benzonitrile wastewater to the photocatalytic reactor for photocatalytic reaction.
  • the volume ratio of methanol and benzonitrile wastewater is 1:16, which is equivalent to that per liter of methanol and benzonitrile wastewater.
  • the dosage of the photocatalyst in the mixture is 0.6g; first carry out the dark adsorption reaction for 30 minutes, after reaching the adsorption equilibrium, then provide visible light through the xenon lamp, and carry out the catalytic reaction at room temperature. At the same interval, take the supernatant and filter through 0.45 ⁇ m. After the membrane, it was determined that the removal rate of benzonitrile reached more than 90% and the COD removal rate in the reaction system was 92%.
  • N-LaFeO 3 @MCM-41-3 catalyst methanol and p-methoxybenzonitrile wastewater into the photocatalytic reactor for photocatalytic reaction.
  • the volume ratio of methanol and p-methoxybenzonitrile wastewater is 1:12.
  • the dosage of photocatalyst per liter of the mixture of methanol and p-methoxybenzonitrile wastewater is 0.4g; first carry out 30min dark adsorption reaction, after reaching adsorption equilibrium, then provide visible light through xenon lamp to carry out catalytic reaction, the same interval time period After taking the supernatant and passing through a 0.45 ⁇ m filter membrane, it was determined that the removal rate of p-methoxybenzonitrile reached more than 90% and the COD removal rate in the reaction system was 91%.
  • N-LaFeO 3 @MCM-41-4 catalyst methanol and bisphenol A wastewater to the photocatalytic reactor for photocatalytic reaction.
  • the volume ratio of methanol and bisphenol A wastewater is 1:8, per liter of methanol and bisphenol
  • the dosage of the photocatalyst in the mixture of A wastewater is 0.2g; first carry out the dark adsorption reaction for 30 minutes, after reaching the adsorption equilibrium, then provide visible light through the xenon lamp, and carry out the catalytic reaction at room temperature. At the same interval, take the supernatant and pass After 0.45 ⁇ m filter membrane, it was determined that the removal rate of bisphenol A reached more than 90% and the COD removal rate in the reaction system was 91%.
  • N-LaFeO 3 @MCM-41-5 catalyst methanol and bisphenol A wastewater to the photocatalytic reactor for photocatalytic reaction.
  • the volume ratio of methanol and bisphenol A wastewater is 1:8, per liter of methanol and bisphenol
  • the dosage of the photocatalyst in the mixture of A wastewater is 0.2g; first carry out the dark adsorption reaction for 30 minutes, after reaching the adsorption equilibrium, then provide visible light through the xenon lamp, and carry out the catalytic reaction at room temperature. At the same interval, take the supernatant and pass After 0.45 ⁇ m filter membrane, it was determined that the removal rate of bisphenol A reached more than 90% and the COD removal rate in the reaction system was 94%.
  • N-LaFeO 3 @MCM-41-6 catalyst oxalic acid and terephthalonitrile waste water to the photocatalytic reactor for photocatalytic reaction.
  • the volume ratio of oxalic acid and terephthalonitrile waste water is 1:8, per liter of oxalic acid and
  • the dosage of the photocatalyst in the mixture of terephthalonitrile wastewater is 0.2g; first carry out the dark adsorption reaction for 30 minutes, and after reaching the adsorption equilibrium, then provide visible light through the xenon lamp to carry out the catalytic reaction. After passing through a 0.45 ⁇ m filter membrane, it was determined that the removal rate of terephthalonitrile reached more than 90% and the COD removal rate in the reaction system was 93%.
  • N-LaFeO 3 @MCM-41-7 catalyst methanol and bisphenol A wastewater to the photocatalytic reactor for photocatalytic reaction.
  • the volume ratio of methanol and bisphenol A wastewater is 1:8, per liter of methanol and bisphenol
  • the dosage of the photocatalyst in the mixture of wastewater A is 0.2g; first carry out the dark adsorption reaction for 30 minutes, after reaching the adsorption equilibrium, then provide visible light through the xenon lamp, and carry out the catalytic reaction at room temperature. At the same interval, take the supernatant and pass After 0.45 ⁇ m filter membrane, it was determined that the removal rate of bisphenol A did not reach 80% and the COD removal rate in the reaction system was 70%.
  • N-LaFeO 3 @MCM-41-8 catalyst methanol and bisphenol A wastewater to the photocatalytic reactor for photocatalytic reaction.
  • the volume ratio of methanol and bisphenol A wastewater is 1:8, per liter of methanol and bisphenol
  • the dosage of the photocatalyst in the mixture of A wastewater is 0.2g; first carry out the dark adsorption reaction for 30 minutes, after reaching the adsorption equilibrium, then provide visible light through the xenon lamp, and carry out the catalytic reaction at room temperature. At the same interval, take the supernatant and pass After 0.45 ⁇ m filter membrane, it was determined that the removal rate of bisphenol A did not reach 80% and the COD removal rate in the reaction system was 78%.
  • any one of tartaric acid, malic acid, aspartic acid and lactic acid was used as a complexing agent, urea was used as a mineralizer, and MCM-41 was used as a carrier.
  • Nitrogen was successfully prepared by a sol-gel method.
  • the carrier of Comparative Example 2 is ⁇ -Al 2 O 3 , and the prepared catalyst N-LaFeO 3 @ ⁇ -Al 2 O 3 is not efficient in degrading aromatic compounds because the specific surface area of ⁇ -Al 2 O 3 is not as good as that of MCM- 41 is large, the contact area during degradation is not sufficient, so the removal rate is not ideal.
  • Comparative Example 3 uses citric acid as the complexing agent synthesis catalyst for a longer reaction time, and the entire experimental period is significantly longer than the complexing agent used in this patent.
  • the catalyst obtained by this method has an unsatisfactory effect on the degradation of aromatic compounds, and neither the concentration of waste water nor the removal rate of COD reaches 90%.

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Abstract

A nitrogen-modified perovskite composite molecular sieve photocatalyst, and a preparation method and application thereof. The photocatalyst is N-LaFeO 3@MCM-41. The preparation method for the photocatalyst comprises: weighing lanthanum nitrate, ferric nitrate, urea, and MCM-41 according to a molar ratio of 1:1:1-3:3-7, adding water for dissolution, and stirring to form a solution A; adding water into a complexing agent for dissolution and stirring to form a solution B, wherein the molar ratio of the complexing agent to lanthanum nitrate is 1-4:1; and slowly adding the solution B into the solution A to be polymerized into sol, drying and calcining to obtain the photocatalyst, and applying the photocatalyst to treatment of aromatic compound organic wastewater. The photocatalyst can efficiently degrade aromatic compound organic wastewater, the preparation method is convenient to operate and low in costs, and the photocatalyst is applied to treatment of aromatic compound organic wastewater without secondary pollution, and is energy-saving and environment-friendly.

Description

一种氮改性钙钛矿复合分子筛的光催化剂及其制备方法与应用方法Photocatalyst of nitrogen-modified perovskite composite molecular sieve and preparation method and application method thereof 技术领域Technical field
本发明涉及一种光催化剂及其制备方法与应用，尤其涉及一种氮改性钙钛矿复合分子筛的光催化剂及其制备方法与应用。The invention relates to a photocatalyst and a preparation method and application thereof, in particular to a photocatalyst of a nitrogen-modified perovskite composite molecular sieve and a preparation method and application thereof.
背景技术Background technique
芳香族化合物是一类具有苯环结构的化合物，它们结构稳定，不易分解，且毒性很强。芳香族化合物一方面来自高等植物的木质素和次生代谢过程，另一方面来自工业上合成的各种化学产品，如杀虫剂、除草剂、染料、炸药等。苯、苯腈类和酚类等芳香族化合物正以每年百万吨的数量被制造出来，这些化合物广泛的用于燃料和工业溶剂，而且它们和多环芳香化合物、氯代联苯是生产医药、农药、塑料聚合物、炸药和其它日用品的最初原料。它们可通过多种途径进入环境，人工合成的产品在环境当中较难为微生物降解，在利用时不可避免地泄漏到环境中，造成对水体、土壤和大气的严重污染，可对人体造成严重的损害，产生癌变、突变和畸变效应。由此可见，芳香族化合物废水的治理是一个十分值得重视的问题。Aromatic compounds are a class of compounds with a benzene ring structure. They have a stable structure, are difficult to decompose, and are highly toxic. Aromatic compounds come from the lignin and secondary metabolic processes of higher plants on the one hand, and on the other hand come from various chemical products synthesized in industry, such as pesticides, herbicides, dyes, explosives and so on. Aromatic compounds such as benzene, benzonitriles, and phenols are being produced in the amount of one million tons per year. These compounds are widely used in fuels and industrial solvents, and they, together with polycyclic aromatic compounds and chlorinated biphenyls, are used in the production of medicines. , Pesticides, plastic polymers, explosives and other daily necessities. They can enter the environment through a variety of ways. Artificially synthesized products are more difficult to be degraded by microorganisms in the environment, and will inevitably leak into the environment during use, causing serious pollution to water, soil and atmosphere, and serious damage to the human body. , Produce cancerous, mutation and aberration effects. It can be seen that the treatment of aromatic wastewater is a very important issue.
现有芳香族化合物废水的处理方法主要有物理处理法、化学处理法、生物处理法及其他方法如低温等离子技术、纳米光催化技术等。生物降解法虽然具有成熟的处理工艺，成本低，但是仅仅适用于低浓度的芳香族化合物的处理；化学氧化及高级氧化技术法是指在废水中加入一定量的氧化剂(氧气、过氧化氢、臭氧等)，在一定的条件下， 产生强氧化剂，使得芳香族化合物被氧化降解，最终完全矿化成为二氧化碳和水的方法。该方法虽然处理效果好，但是由于氧化剂回收比较困难，操作费用昂贵，从而影响了其使用；吸附法是处理芳香族化合物比较有效的方法，主要是利用多孔材料来吸附废水中的污染物，废水中的污染物会通过吸附剂的孔道结构进入吸附剂的内部，然后再可以将吸附剂进行一定的处理，使得吸附剂可以循环使用。但设备投资量大，吸附剂重复利用性低和再生问题有待解决；冷等离子体处理废水技术是一种兼具高能电子辐射、臭氧氧化和紫外光解等种作用于一体的全新的废水处理技术，但是该法耗能较大；纳米光催化技术具有反应条件温和、可利用紫外光和太阳光等条件，将污染物直接间接为CO2、水及其他无害物质，耗能小且不会产生二次污染。常用的TiO2等光催化剂存在禁带宽度宽，不能充分利用可见光，量子效率低等缺点，而钙钛矿催化剂禁带宽度较窄，带隙较小，是一种较好的光催化剂，但是钙钛矿存在电子-空穴的复合率较高的问题，对大范围的可见光响应不好。The existing treatment methods for aromatic wastewater mainly include physical treatment, chemical treatment, biological treatment and other methods such as low-temperature plasma technology, nano-photocatalytic technology, etc. Although the biodegradation method has a mature treatment process and low cost, it is only suitable for the treatment of low-concentration aromatic compounds; chemical oxidation and advanced oxidation technology methods refer to adding a certain amount of oxidants (oxygen, hydrogen peroxide, Ozone, etc.), under certain conditions, a strong oxidant is produced, which makes the aromatic compounds be oxidized and degraded, and finally completely mineralized into carbon dioxide and water. Although this method has a good treatment effect, it is difficult to recycle the oxidant and the operation cost is expensive, which affects its use. The adsorption method is a more effective method for the treatment of aromatic compounds, mainly using porous materials to adsorb pollutants in the wastewater. The pollutants in the adsorbent will enter the inside of the adsorbent through the pore structure of the adsorbent, and then the adsorbent can be treated to a certain extent, so that the adsorbent can be recycled. However, the amount of equipment investment is large, the reusability of adsorbents is low, and the regeneration problem needs to be solved; cold plasma treatment of wastewater is a new wastewater treatment technology that combines high-energy electron radiation, ozone oxidation, and ultraviolet photolysis. , But this method consumes a lot of energy; nano-photocatalytic technology has mild reaction conditions, can use ultraviolet light and sunlight and other conditions, directly and indirectly pollutants into CO2, water and other harmless substances, and consumes little energy and does not produce Secondary pollution. Commonly used photocatalysts such as TiO2 have wide band gap, can not make full use of visible light, low quantum efficiency and other shortcomings, while perovskite catalyst has narrow band gap and small band gap, it is a better photocatalyst, but calcium Titanium ore has the problem of high electron-hole recombination rate, and does not respond well to a wide range of visible light.
发明内容Summary of the invention
发明目的：本发明的第一目的在于提供一种高效、便捷、节能环保的氮改性钙钛矿复合分子筛的光催化剂，本发明的第二目的在于提供所述光催化剂的制备方法，本发明的第三目的在于提供所述光催化剂的应用。Object of the invention: The first object of the present invention is to provide an efficient, convenient, energy-saving and environmentally friendly nitrogen-modified perovskite composite molecular sieve photocatalyst. The second object of the present invention is to provide a method for preparing the photocatalyst. The third objective is to provide the application of the photocatalyst.
技术方案：本发明的氮改性钙钛矿复合分子筛的光催化剂为 N-LaFeO 3@MCM-41。 Technical scheme: The photocatalyst of the nitrogen-modified perovskite composite molecular sieve of the present invention is N-LaFeO 3 @MCM-41.
本发明的光催化剂的制备方法，包括如下步骤：The preparation method of the photocatalyst of the present invention includes the following steps:
(1)按摩尔比1：1：1-3：3-7称取硝酸镧、硝酸铁、尿素和MCM-41，加水溶解，搅拌形成A液；(1) Weigh lanthanum nitrate, ferric nitrate, urea and MCM-41 at a massage ratio of 1:1:1-3:3-7, add water to dissolve, and stir to form liquid A;
(2)将络合剂加水溶解，搅拌形成B液，其中，所述络合剂与硝酸镧的摩尔比为1-4：1；(2) Dissolve the complexing agent in water and stir to form liquid B, wherein the molar ratio of the complexing agent to lanthanum nitrate is 1-4:1;
(3)将所述B液缓慢加入A液中聚合成溶胶，干燥、煅烧得到光催化剂。(3) The solution B is slowly added to the solution A to polymerize to form a sol, and then dried and calcined to obtain a photocatalyst.
进一步地，步骤(1)中，所述A液中添加软模板剂。Further, in step (1), a soft template agent is added to the A solution.
优选的，所述软模板剂为十六烷基三甲基溴化铵(CTAB)，控制材料的尺寸和提高材料比表面积。Preferably, the soft template is cetyltrimethylammonium bromide (CTAB), which controls the size of the material and increases the specific surface area of the material.
进一步地，步骤(2)中，所述络合剂为酒石酸、苹果酸、天冬氨酸或乳酸中的任意一种。Further, in step (2), the complexing agent is any one of tartaric acid, malic acid, aspartic acid or lactic acid.
本发明的光催化剂在芳香族化合物有机废水中的应用。The application of the photocatalyst of the present invention in aromatic compound organic wastewater.
进一步地，所述的芳香族化合物为苯腈、对甲氧基苯腈、对苯二腈或双酚A中的一种。Further, the aromatic compound is one of benzonitrile, p-methoxybenzonitrile, terephthalonitrile or bisphenol A.
进一步地，本发明的光催化剂的应用包括如下步骤：在光催化反应器中加入光催化剂、空穴捕获剂和芳香族化合物有机废水进行光催化反应，其中，所述空穴捕获剂和芳香族化合物的体积比为1:8-16，每升空穴捕获剂和芳香族化合物的混合物中光催化剂的投加量为0.2～0.6g。Further, the application of the photocatalyst of the present invention includes the following steps: adding a photocatalyst, a hole trapping agent, and aromatic compound organic wastewater to a photocatalytic reactor to perform a photocatalytic reaction, wherein the hole trapping agent and the aromatic The volume ratio of the compound is 1:8-16, and the dosage of the photocatalyst per liter of the mixture of the hole trapping agent and the aromatic compound is 0.2-0.6g.
进一步地，在所述光催化反应之前先进行暗吸附。Further, dark adsorption is performed before the photocatalytic reaction.
进一步地，所述空穴捕获剂为甲醇或草酸铵中的一种。Further, the hole trapping agent is one of methanol or ammonium oxalate.
进一步地，所述光催化反应通过氙灯提供可见光。Further, the photocatalytic reaction provides visible light through a xenon lamp.
有益效果：与现有技术相比，本发明具有如下显著优点：Beneficial effects: Compared with the prior art, the present invention has the following significant advantages:
(1)本发明的光催化剂利用氮改性的钙钛矿降低了催化剂的禁带宽度，提高可见光的可吸收区域，从而提高降解芳香族化合物有机废水的效率；利用分子筛MCM-41作为载体，显著提高了催化剂与有机废水的接触面积，促进快速催化降解；(1) The photocatalyst of the present invention uses nitrogen-modified perovskite to reduce the forbidden band width of the catalyst and increase the visible light absorption area, thereby improving the efficiency of degrading aromatic compound organic wastewater; using molecular sieve MCM-41 as a carrier, Significantly increase the contact area between the catalyst and organic wastewater, and promote rapid catalytic degradation;
(2)本发明光催化剂的制备方法操作方便且成本低；该法设备简单，工艺灵活，材料的纯度高且粒级容易控制；该法可以利用溶液中的化学反应，使原料在分子水平上均匀的混合，从而得到均匀性很高的产物，其均匀度可达分子或原子尺寸；(2) The preparation method of the photocatalyst of the present invention is easy to operate and has low cost; the method has simple equipment, flexible process, high purity of the material and easy control of the particle size; the method can use chemical reactions in the solution to make the raw materials at the molecular level Uniform mixing, so as to obtain a product with high uniformity, the uniformity of which can reach the size of molecules or atoms;
(3)本发明光催化剂在应用过程中不使用各种氧化剂，不需要担心氧化剂回收问题，大大地节约成本；不产生污泥及二次污染；低温常压下反应，且充分利用可见光，节约能源。(3) The photocatalyst of the present invention does not use various oxidants during the application process, and there is no need to worry about the problem of oxidant recovery, which greatly saves costs; does not produce sludge and secondary pollution; reacts under low temperature and normal pressure, and makes full use of visible light, saving energy.
附图说明Description of the drawings
图1为本发明的光催化降解机理。Figure 1 shows the photocatalytic degradation mechanism of the present invention.
具体实施方式Detailed ways
下面结合附图对本发明的技术方案作进一步说明。The technical scheme of the present invention will be further described below in conjunction with the drawings.
实施例1Example 1
按照摩尔比为1:1:1:3称量2.1646g硝酸镧、2.02g硝酸铁、 0.3g尿素和0.9012g MCM-41于三口烧瓶中，加入50mL蒸馏水溶解，搅拌均匀形成A液；根据酒石酸：硝酸镧的摩尔比为1:1加入0.7505g酒石酸，加入15mL蒸馏水，溶解搅拌均匀形成B液。将B液在搅拌下缓慢加入到A液中，在80℃水浴下反应聚合成溶胶，过夜干燥得到干凝胶，以2℃/min的速率在700℃下煅烧4h，得到催化剂N-LaFeO 3@MCM-41-1。 Weigh 2.1646g lanthanum nitrate, 2.02g ferric nitrate, 0.3g urea and 0.9012g MCM-41 in a three-necked flask according to the molar ratio of 1:1:1:3, add 50mL distilled water to dissolve, stir evenly to form liquid A; according to tartaric acid : The molar ratio of lanthanum nitrate is 1:1, add 0.7505g tartaric acid, add 15mL distilled water, dissolve and stir evenly to form liquid B. Slowly add solution B to solution A under stirring, react and polymerize into a sol at 80°C in a water bath, dry overnight to obtain a dry gel, and calcinate at a rate of 2°C/min at 700°C for 4 hours to obtain a catalyst N-LaFeO 3 @MCM-41-1.
在光催化反应器中加入N-LaFeO 3@MCM-41-1催化剂、甲醇和双酚A废水进行光催化反应，甲醇和双酚A废水的体积比为1:8，每升甲醇和双酚A废水的混合物中光催化剂的投加量为0.2g；首先进行30min暗吸附反应，达到吸附平衡后，然后通过氙灯提供可见光，常温下进行催化反应，相同间隔时间段，取上清液并过0.45μm滤膜后测定双酚A的去除率达到90％以上和反应体系中的COD去除率为90％。 Add N-LaFeO 3 @MCM-41-1 catalyst, methanol and bisphenol A wastewater to the photocatalytic reactor for photocatalytic reaction. The volume ratio of methanol and bisphenol A wastewater is 1:8, per liter of methanol and bisphenol The dosage of the photocatalyst in the mixture of wastewater A is 0.2g; first carry out the dark adsorption reaction for 30 minutes, after reaching the adsorption equilibrium, then provide visible light through the xenon lamp, and carry out the catalytic reaction at room temperature. At the same interval, take the supernatant and pass After 0.45μm filter membrane, it was determined that the removal rate of bisphenol A reached more than 90% and the COD removal rate in the reaction system was 90%.
实施例2Example 2
按照摩尔比为1:1:3:7称量2.1646g硝酸镧、2.02g硝酸铁、0.9g尿素和2.1028g MCM-41于三口烧瓶中，加入50mL蒸馏水溶解，搅拌均匀形成A液；根据苹果酸：硝酸镧的摩尔比为2:1加入1.3409g苹果酸，加入30mL蒸馏水，溶解搅拌均匀形成B液。将B液在搅拌下缓慢加入到A液，在80℃水浴下反应聚合成溶胶，过夜干燥得到干凝胶，以2℃/min的速率在700℃下煅烧4h，得到催化剂N-LaFeO 3@MCM-41-2。 Weigh 2.1646g lanthanum nitrate, 2.02g ferric nitrate, 0.9g urea and 2.1028g MCM-41 in a three-necked flask according to the molar ratio of 1:1:3:7, add 50mL distilled water to dissolve, stir evenly to form liquid A; The molar ratio of acid: lanthanum nitrate is 2:1. Add 1.3409g of malic acid, add 30mL of distilled water, dissolve and stir to form liquid B. Slowly add solution B to solution A under stirring, react and polymerize to form a sol in a water bath at 80°C, dry overnight to obtain a dry gel, and calcinate at a rate of 2°C/min at 700°C for 4 hours to obtain a catalyst N-LaFeO 3 @ MCM-41-2.
在光催化反应器中加入N-LaFeO 3@MCM-41-2催化剂、甲醇和苯 腈废水进行光催化反应，甲醇和苯腈废水的体积比为1:16，每升甲醇和苯腈废水的混合物中光催化剂的投加量为0.6g；首先进行30min暗吸附反应，达到吸附平衡后，然后通过氙灯提供可见光，常温下进行催化反应，相同间隔时间段，取上清液并过0.45μm滤膜后测定苯腈的去除率达到90％以上和反应体系中的COD去除率为92％。 Add N-LaFeO 3 @MCM-41-2 catalyst, methanol and benzonitrile wastewater to the photocatalytic reactor for photocatalytic reaction. The volume ratio of methanol and benzonitrile wastewater is 1:16, which is equivalent to that per liter of methanol and benzonitrile wastewater. The dosage of the photocatalyst in the mixture is 0.6g; first carry out the dark adsorption reaction for 30 minutes, after reaching the adsorption equilibrium, then provide visible light through the xenon lamp, and carry out the catalytic reaction at room temperature. At the same interval, take the supernatant and filter through 0.45μm. After the membrane, it was determined that the removal rate of benzonitrile reached more than 90% and the COD removal rate in the reaction system was 92%.
实施例3Example 3
按照摩尔比为1:1:2:5称量2.1646g硝酸镧、2.02g硝酸铁、0.6g尿素和1.502g MCM-41于三口烧瓶中，加入50mL蒸馏水溶解搅拌均匀形成A液；根据乳酸：硝酸镧的摩尔比例为3:1的量加入1.3512g乳酸作为络合剂，加入45mL蒸馏水，溶解搅拌均匀形成B液。将B液在搅拌下缓慢加入到A液中，在80℃水浴下反应聚合成溶胶，过夜干燥得到干凝胶，以2℃/min的速率在700℃下煅烧4h，得到催化剂N-LaFeO 3@MCM-41-3。 Weigh 2.1646g lanthanum nitrate, 2.02g ferric nitrate, 0.6g urea and 1.502g MCM-41 according to the molar ratio of 1:1:2:5 into a three-necked flask, add 50mL distilled water to dissolve and stir to form liquid A; according to lactic acid: The molar ratio of lanthanum nitrate is 3:1, 1.3512 g of lactic acid is added as a complexing agent, and 45 mL of distilled water is added to dissolve and stir to form liquid B. Slowly add solution B to solution A under stirring, react and polymerize into a sol at 80°C in a water bath, dry overnight to obtain a dry gel, and calcinate at a rate of 2°C/min at 700°C for 4 hours to obtain a catalyst N-LaFeO 3 @MCM-41-3.
在光催化反应器中加入N-LaFeO 3@MCM-41-3催化剂、甲醇和对甲氧基苯腈废水进行光催化反应，甲醇和对甲氧基苯腈废水的体积比为1:12，每升甲醇和对甲氧基苯腈废水的混合物中光催化剂的投加量为0.4g；首先进行30min暗吸附反应，达到吸附平衡后，然后通过氙灯提供可见光，进行催化反应，相同间隔时间段，取上清液并过0.45μm滤膜后测定对甲氧基苯腈的去除率达到90％以上和反应体系中的COD去除率为91％。 Add N-LaFeO 3 @MCM-41-3 catalyst, methanol and p-methoxybenzonitrile wastewater into the photocatalytic reactor for photocatalytic reaction. The volume ratio of methanol and p-methoxybenzonitrile wastewater is 1:12. The dosage of photocatalyst per liter of the mixture of methanol and p-methoxybenzonitrile wastewater is 0.4g; first carry out 30min dark adsorption reaction, after reaching adsorption equilibrium, then provide visible light through xenon lamp to carry out catalytic reaction, the same interval time period After taking the supernatant and passing through a 0.45 μm filter membrane, it was determined that the removal rate of p-methoxybenzonitrile reached more than 90% and the COD removal rate in the reaction system was 91%.
实施例4Example 4
按照摩尔比为1:1:1:4称量2.1646g硝酸镧、2.02g硝酸铁、 0.3g尿素和1.2016g MCM-41于三口烧瓶中，加入50mL蒸馏水溶解，搅拌均匀形成A液；根据天冬氨酸：硝酸镧的摩尔比例为4:1的量加入2.662g天冬氨酸作为络合剂，加入60mL蒸馏水，溶解搅拌均匀形成B液。将B液在搅拌下缓慢加入到A液中，在80℃水浴下反应聚合成溶胶，过夜干燥得到干凝胶，以2℃/min的速率在700℃下煅烧4h，得到催化剂N-LaFeO 3@MCM-41-4。 Weigh 2.1646g lanthanum nitrate, 2.02g ferric nitrate, 0.3g urea and 1.2016g MCM-41 in a three-necked flask according to the molar ratio of 1:1:1:4, add 50mL of distilled water to dissolve, and stir to form liquid A; The molar ratio of aspartic acid: lanthanum nitrate is 4:1, 2.662 g of aspartic acid is added as a complexing agent, and 60 mL of distilled water is added to dissolve and stir to form liquid B. Slowly add solution B to solution A under stirring, react and polymerize into a sol at 80°C in a water bath, dry overnight to obtain a dry gel, and calcinate at a rate of 2°C/min at 700°C for 4 hours to obtain a catalyst N-LaFeO 3 @MCM-41-4.
在光催化反应器中加入N-LaFeO 3@MCM-41-4催化剂、甲醇和双酚A废水进行光催化反应，甲醇和双酚A废水的体积比为1:8，每升甲醇和双酚A废水的混合物中光催化剂的投加量为0.2g；首先进行30min暗吸附反应，达到吸附平衡后，然后通过氙灯提供可见光，常温下进行催化反应，相同间隔时间段，取上清液并过0.45μm滤膜后测定双酚A的去除率达到90％以上和反应体系中的COD去除率为91％。 Add N-LaFeO 3 @MCM-41-4 catalyst, methanol and bisphenol A wastewater to the photocatalytic reactor for photocatalytic reaction. The volume ratio of methanol and bisphenol A wastewater is 1:8, per liter of methanol and bisphenol The dosage of the photocatalyst in the mixture of A wastewater is 0.2g; first carry out the dark adsorption reaction for 30 minutes, after reaching the adsorption equilibrium, then provide visible light through the xenon lamp, and carry out the catalytic reaction at room temperature. At the same interval, take the supernatant and pass After 0.45μm filter membrane, it was determined that the removal rate of bisphenol A reached more than 90% and the COD removal rate in the reaction system was 91%.
实施例5Example 5
按照摩尔比为1:1:2:5称量2.1646g硝酸镧、2.02g硝酸铁、0.6g尿素和1.502g MCM-41于三口烧瓶中，加入50mL蒸馏水溶解，搅拌均匀形成A液；根据酒石酸：硝酸镧的摩尔比例为2:1的量加入1.5009g酒石酸作为络合剂，加入30mL蒸馏水，溶解搅拌均匀形成B液。将B液在搅拌下缓慢加入到A液中，在80℃水浴下反应聚合成溶胶，过夜干燥得到干凝胶，以2℃/min的速率在700℃下煅烧4h，得到催化剂N-LaFeO 3@MCM-41-5。 Weigh 2.1646g lanthanum nitrate, 2.02g ferric nitrate, 0.6g urea and 1.502g MCM-41 in a three-necked flask according to the molar ratio of 1:1:2:5, add 50mL of distilled water to dissolve, stir evenly to form liquid A; according to tartaric acid : The molar ratio of lanthanum nitrate is 2:1, 1.5009 g of tartaric acid is added as a complexing agent, 30 mL of distilled water is added, and the mixture is dissolved and stirred to form liquid B. Slowly add solution B to solution A under stirring, react and polymerize into a sol at 80°C in a water bath, dry overnight to obtain a dry gel, and calcinate at a rate of 2°C/min at 700°C for 4 hours to obtain a catalyst N-LaFeO 3 @MCM-41-5.
在光催化反应器中加入N-LaFeO 3@MCM-41-5催化剂、甲醇和双 酚A废水进行光催化反应，甲醇和双酚A废水的体积比为1:8，每升甲醇和双酚A废水的混合物中光催化剂的投加量为0.2g；首先进行30min暗吸附反应，达到吸附平衡后，然后通过氙灯提供可见光，常温下进行催化反应，相同间隔时间段，取上清液并过0.45μm滤膜后测定双酚A的去除率达到90％以上和反应体系中的COD去除率为94％。 Add N-LaFeO 3 @MCM-41-5 catalyst, methanol and bisphenol A wastewater to the photocatalytic reactor for photocatalytic reaction. The volume ratio of methanol and bisphenol A wastewater is 1:8, per liter of methanol and bisphenol The dosage of the photocatalyst in the mixture of A wastewater is 0.2g; first carry out the dark adsorption reaction for 30 minutes, after reaching the adsorption equilibrium, then provide visible light through the xenon lamp, and carry out the catalytic reaction at room temperature. At the same interval, take the supernatant and pass After 0.45μm filter membrane, it was determined that the removal rate of bisphenol A reached more than 90% and the COD removal rate in the reaction system was 94%.
实施例6Example 6
按照摩尔比为1:1:3:6称量2.1646g硝酸镧、2.02g硝酸铁、0.9g尿素和1.8024g MCM-41于三口烧瓶中，加入50mL蒸馏水溶解，再按照硝酸盐：CTAB的摩尔比为1:1加入1.8223g CTAB作为模板剂提高催化剂的比表面积，搅拌均匀形成A液；根据乳酸：硝酸镧的摩尔比例为3:1加入1.3512g乳酸作为络合剂，加入45mL蒸馏水，溶解搅拌均匀形成B液。将B液在搅拌下缓慢加入到A液中，在80℃水浴下反应聚合成溶胶，过夜干燥得到干凝胶，以2℃/min的速率在700℃下煅烧4h，得到催化剂N-LaFeO 3@MCM-41-6。 Weigh 2.1646g lanthanum nitrate, 2.02g ferric nitrate, 0.9g urea and 1.8024g MCM-41 according to the molar ratio of 1:1:3:6 in a three-necked flask, add 50mL distilled water to dissolve, and then according to the nitrate: the mole of CTAB When the ratio is 1:1, add 1.8223g CTAB as a template to increase the specific surface area of the catalyst, and stir to form liquid A; according to the molar ratio of lactic acid: lanthanum nitrate of 3:1, add 1.3512g lactic acid as a complexing agent, add 45mL distilled water, and dissolve Stir evenly to form liquid B. Slowly add solution B to solution A under stirring, react and polymerize into a sol at 80°C in a water bath, dry overnight to obtain a dry gel, and calcinate at a rate of 2°C/min at 700°C for 4 hours to obtain a catalyst N-LaFeO 3 @MCM-41-6.
在光催化反应器中加入N-LaFeO 3@MCM-41-6催化剂、草酸和对苯二腈废水进行光催化反应，草酸和对苯二腈废水的体积比为1:8，每升草酸和对苯二腈废水的混合物中光催化剂的投加量为0.2g；首先进行30min暗吸附反应，达到吸附平衡后，然后通过氙灯提供可见光，进行催化反应，相同间隔时间段，取上清液并过0.45μm滤膜后测定对苯二腈的去除率达到90％以上和反应体系中的COD去除率为93％。 Add N-LaFeO 3 @MCM-41-6 catalyst, oxalic acid and terephthalonitrile waste water to the photocatalytic reactor for photocatalytic reaction. The volume ratio of oxalic acid and terephthalonitrile waste water is 1:8, per liter of oxalic acid and The dosage of the photocatalyst in the mixture of terephthalonitrile wastewater is 0.2g; first carry out the dark adsorption reaction for 30 minutes, and after reaching the adsorption equilibrium, then provide visible light through the xenon lamp to carry out the catalytic reaction. After passing through a 0.45 μm filter membrane, it was determined that the removal rate of terephthalonitrile reached more than 90% and the COD removal rate in the reaction system was 93%.
对比例1Comparative example 1
按照摩尔比为1:1:3称量2.1646g硝酸镧、2.02g硝酸铁和0.9012g MCM-41于三口烧瓶中，加入50mL蒸馏水溶解，搅拌均匀形成A液；根据酒石酸：硝酸镧的摩尔比为1:1加入0.7505g酒石酸，加入15mL蒸馏水，溶解搅拌均匀形成B液。将B液在搅拌下缓慢加入到A液中，在80℃水浴下反应聚合成溶胶，过夜干燥得到干凝胶，以2℃/min的速率在700℃下煅烧4h，得到催化剂N-LaFeO 3@MCM-41-7。 Weigh 2.1646g lanthanum nitrate, 2.02g ferric nitrate and 0.9012g MCM-41 in a three-necked flask according to the molar ratio of 1:1:3, add 50mL of distilled water to dissolve, and stir to form liquid A; according to the molar ratio of tartaric acid: lanthanum nitrate Add 0.7505g tartaric acid to 1:1, add 15mL distilled water, dissolve and stir evenly to form liquid B. Slowly add solution B to solution A under stirring, react and polymerize into a sol at 80°C in a water bath, dry overnight to obtain a dry gel, and calcinate at a rate of 2°C/min at 700°C for 4 hours to obtain a catalyst N-LaFeO 3 @MCM-41-7.
在光催化反应器中加入N-LaFeO 3@MCM-41-7催化剂、甲醇和双酚A废水进行光催化反应，甲醇和双酚A废水的体积比为1:8，每升甲醇和双酚A废水的混合物中光催化剂的投加量为0.2g；首先进行30min暗吸附反应，达到吸附平衡后，然后通过氙灯提供可见光，常温下进行催化反应，相同间隔时间段，取上清液并过0.45μm滤膜后测定双酚A的去除率未达到80％和反应体系中的COD去除率为70％。 Add N-LaFeO 3 @MCM-41-7 catalyst, methanol and bisphenol A wastewater to the photocatalytic reactor for photocatalytic reaction. The volume ratio of methanol and bisphenol A wastewater is 1:8, per liter of methanol and bisphenol The dosage of the photocatalyst in the mixture of wastewater A is 0.2g; first carry out the dark adsorption reaction for 30 minutes, after reaching the adsorption equilibrium, then provide visible light through the xenon lamp, and carry out the catalytic reaction at room temperature. At the same interval, take the supernatant and pass After 0.45μm filter membrane, it was determined that the removal rate of bisphenol A did not reach 80% and the COD removal rate in the reaction system was 70%.
对比例2Comparative example 2
按照摩尔比为1:1:1:3称量2.1646g硝酸镧、2.02g硝酸铁、0.3g尿素和1.5294gγ-Al 2O 3于三口烧瓶中，加入50mL蒸馏水溶解，搅拌均匀形成A液；根据酒石酸：硝酸镧的摩尔比为1:1加入0.7505g酒石酸，加入15mL蒸馏水，溶解搅拌均匀形成B液。将B液在搅拌下缓慢加入到A液中，在80℃水浴下反应聚合成溶胶，过夜干燥得到干凝胶，以2℃/min的速率在700℃下煅烧4h，得到催化剂N-LaFeO 3@γ-Al 2O 3。 Weigh 2.1646g of lanthanum nitrate, 2.02g of ferric nitrate, 0.3g of urea and 1.5294g of γ-Al 2 O 3 in a three-necked flask according to the molar ratio of 1:1:1:3, add 50mL of distilled water to dissolve, and stir to form liquid A; According to the molar ratio of tartaric acid: lanthanum nitrate of 1:1, add 0.7505 g of tartaric acid, add 15 mL of distilled water, and dissolve and stir to form liquid B. Slowly add solution B to solution A under stirring, react and polymerize into a sol at 80°C in a water bath, dry overnight to obtain a dry gel, and calcinate at a rate of 2°C/min at 700°C for 4 hours to obtain a catalyst N-LaFeO 3 @γ-Al 2 O 3 .
在光催化反应器中加入N-LaFeO 3@MCM-41-8催化剂、甲醇和双酚A废水进行光催化反应，甲醇和双酚A废水的体积比为1:8，每升甲醇和双酚A废水的混合物中光催化剂的投加量为0.2g；首先进行30min暗吸附反应，达到吸附平衡后，然后通过氙灯提供可见光，常温下进行催化反应，相同间隔时间段，取上清液并过0.45μm滤膜后测定双酚A的去除率未达到80％和反应体系中的COD去除率为78％。 Add N-LaFeO 3 @MCM-41-8 catalyst, methanol and bisphenol A wastewater to the photocatalytic reactor for photocatalytic reaction. The volume ratio of methanol and bisphenol A wastewater is 1:8, per liter of methanol and bisphenol The dosage of the photocatalyst in the mixture of A wastewater is 0.2g; first carry out the dark adsorption reaction for 30 minutes, after reaching the adsorption equilibrium, then provide visible light through the xenon lamp, and carry out the catalytic reaction at room temperature. At the same interval, take the supernatant and pass After 0.45μm filter membrane, it was determined that the removal rate of bisphenol A did not reach 80% and the COD removal rate in the reaction system was 78%.
对比例3Comparative example 3
按照摩尔比为1:1:1:3称量2.1646g硝酸镧、2.02g硝酸铁、0.3g尿素和0.9012g MCM-41于三口烧瓶中，加入50mL蒸馏水溶解，搅拌均匀形成A液；根据柠檬酸：硝酸镧的摩尔比为1:1加入0.9607g柠檬酸，加入15mL蒸馏水，溶解搅拌均匀形成B液。将B液在搅拌下缓慢加入到A液中，在80℃水浴下反应聚合成溶胶，过夜干燥得到干凝胶，以2℃/min的速率在700℃下煅烧4h，得到催化剂N-LaFeO 3@MCM-41-9。 Weigh 2.1646g lanthanum nitrate, 2.02g ferric nitrate, 0.3g urea and 0.9012g MCM-41 in a three-necked flask according to the molar ratio of 1:1:1:3, add 50mL of distilled water to dissolve, and stir to form liquid A; The molar ratio of acid:lanthanum nitrate is 1:1. Add 0.9607g of citric acid, add 15mL of distilled water, dissolve and stir evenly to form liquid B. Slowly add solution B to solution A under stirring, react and polymerize into a sol at 80°C in a water bath, dry overnight to obtain a dry gel, and calcinate at a rate of 2°C/min at 700°C for 4 hours to obtain a catalyst N-LaFeO 3 @MCM-41-9.
在光催化反应器中加入N-LaFeO 3@MCM-41-9催化剂、甲醇和双酚A废水进行光催化反应，甲醇和双酚A废水的体积比为1:8，每升甲醇和双酚A废水的混合物中光催化剂的投加量为0.2g；进行30min暗吸附反应，达到吸附平衡后，然后通过氙灯提供可见光，常温下进行催化反应，相同间隔时间段，取上清液并过0.45μm滤膜后测定双酚A，结果表明双酚A的去除率只达到80％，且反应体系中的COD去除率为72％。 Add N-LaFeO 3 @MCM-41-9 catalyst, methanol and bisphenol A wastewater to the photocatalytic reactor for photocatalytic reaction. The volume ratio of methanol and bisphenol A wastewater is 1:8, per liter of methanol and bisphenol The dosage of photocatalyst in the mixture of A wastewater is 0.2g; after 30min dark adsorption reaction, after reaching adsorption equilibrium, visible light is provided by xenon lamp, and catalytic reaction is carried out at room temperature. At the same interval, take the supernatant and pass 0.45 The measurement of bisphenol A after the μm filter membrane showed that the removal rate of bisphenol A only reached 80%, and the COD removal rate in the reaction system was 72%.
实施例1-6采用酒石酸、苹果酸、天冬氨酸和乳酸中的任意一种 为络合剂，尿素为矿化剂，以MCM-41作为载体，通过溶胶-凝胶法成功制备了氮掺杂改性复合型催化剂N-LaFeO3@MCM-41，在可见光下，加入一定量的空穴捕获剂，催化降解芳香族化合物苯腈、对甲氧基苯腈、对苯二腈和双酚A中的任意一种有机废水，且化合物和COD的降解效率均达到90％以上。In Examples 1-6, any one of tartaric acid, malic acid, aspartic acid and lactic acid was used as a complexing agent, urea was used as a mineralizer, and MCM-41 was used as a carrier. Nitrogen was successfully prepared by a sol-gel method. Doped and modified composite catalyst N-LaFeO3@MCM-41, under visible light, adding a certain amount of hole trapping agent to catalyze the degradation of aromatic compounds benzonitrile, p-methoxybenzonitrile, terephthalonitrile and bisphenol Any one of organic wastewater in A, and the degradation efficiency of compound and COD both reach more than 90%.
对比例1对LaFeO 3@MCM-41催化剂没有进行氮改性，此催化剂降解芳香族化合物废水的效果并不理想，与氮改性的催化剂相比，废水的有机物浓度和COD的去除率均未达到理想效果。 In Comparative Example 1, LaFeO 3 @MCM-41 catalyst was not modified by nitrogen. The effect of this catalyst on the degradation of aromatic wastewater was not ideal. Compared with the catalyst modified by nitrogen, the organic matter concentration and COD removal rate of the wastewater were not satisfactory. To achieve the desired effect.
对比例2的载体为γ-Al 2O 3，制备的催化剂N-LaFeO 3@γ-Al 2O 3降解芳香族化合物的效率并不高，因为γ-Al 2O 3的比表面积不如MCM-41大，降解时的接触面积不够充分，因此去除率不理想。 The carrier of Comparative Example 2 is γ-Al 2 O 3 , and the prepared catalyst N-LaFeO 3 @γ-Al 2 O 3 is not efficient in degrading aromatic compounds because the specific surface area of γ-Al 2 O 3 is not as good as that of MCM- 41 is large, the contact area during degradation is not sufficient, so the removal rate is not ideal.
对比例3采用柠檬酸作为络合剂合成催化剂的反应时间较长，整个实验周期明显比本专利所用的络合剂久。该法得到的催化剂降解芳香族化合物的效果不理想，废水的浓度和COD去除率均未达到90％。Comparative Example 3 uses citric acid as the complexing agent synthesis catalyst for a longer reaction time, and the entire experimental period is significantly longer than the complexing agent used in this patent. The catalyst obtained by this method has an unsatisfactory effect on the degradation of aromatic compounds, and neither the concentration of waste water nor the removal rate of COD reaches 90%.

Claims (10)

  1. 一种氮改性钙钛矿复合分子筛的光催化剂，其特征在于：所述光催化剂为N-LaFeO 3@MCM-41。 A photocatalyst of a nitrogen-modified perovskite composite molecular sieve, characterized in that: the photocatalyst is N-LaFeO 3 @MCM-41.
  2. 一种权利要求1所述氮改性钙钛矿复合分子筛的光催化剂的制备方法，其特征在于，包括如下步骤：A method for preparing the photocatalyst of the nitrogen-modified perovskite composite molecular sieve according to claim 1, characterized in that it comprises the following steps:
    (1)按摩尔比1：1：1-3：3-7称取硝酸镧、硝酸铁、尿素和MCM-41，加水溶解，搅拌形成A液；(1) Weigh lanthanum nitrate, ferric nitrate, urea and MCM-41 at a massage ratio of 1:1:1-3:3-7, add water to dissolve, and stir to form liquid A;
    (2)将络合剂加水溶解，搅拌形成B液，其中，所述络合剂与硝酸镧的摩尔比为1-4：1；(2) Dissolve the complexing agent in water and stir to form liquid B, wherein the molar ratio of the complexing agent to lanthanum nitrate is 1-4:1;
    (3)将所述B液缓慢加入A液中聚合成溶胶，干燥、煅烧得到光催化剂。(3) The solution B is slowly added to the solution A to polymerize to form a sol, and then dried and calcined to obtain a photocatalyst.
  3. 根据权利要求2所述氮改性钙钛矿复合分子筛的光催化剂的制备方法，其特征在于：步骤(1)中，所述A液中添加软模板剂。The method for preparing a photocatalyst of a nitrogen-modified perovskite composite molecular sieve according to claim 2, characterized in that: in step (1), a soft template agent is added to the A liquid.
  4. 根据权利要求2所述氮改性钙钛矿复合分子筛的光催化剂的制备方法，其特征在于：步骤(2)中，所述络合剂为酒石酸、苹果酸、天冬氨酸或乳酸中的任意一种。The method for preparing the photocatalyst of the nitrogen-modified perovskite composite molecular sieve according to claim 2, characterized in that: in step (2), the complexing agent is selected from tartaric acid, malic acid, aspartic acid or lactic acid Any kind.
  5. 一种权利要求1所述氮改性钙钛矿复合分子筛的光催化剂在治理芳香族化合物有机废水中的应用。An application of the photocatalyst of the nitrogen-modified perovskite composite molecular sieve of claim 1 in the treatment of aromatic compound organic wastewater.
  6. 根据权利要求5所述氮改性钙钛矿复合分子筛的光催化剂的应用，其特征在于：所述的芳香族化合物为苯腈、对甲氧基苯腈、对苯二腈或双酚A中的一种。The application of the photocatalyst of the nitrogen-modified perovskite composite molecular sieve according to claim 5, wherein the aromatic compound is benzonitrile, p-methoxybenzonitrile, terephthalonitrile or bisphenol A. Kind of.
  7. 根据权利要求5所述氮改性钙钛矿复合分子筛的光催化剂的应用， 其特征在于，包括如下步骤：在光催化反应器中加入光催化剂、空穴捕获剂和芳香族化合物有机废水进行光催化反应，其中，所述空穴捕获剂和芳香族化合物的体积比为1:8-16，每升空穴捕获剂和芳香族化合物的混合物中光催化剂的投加量为0.2～0.6g。The application of the photocatalyst of the nitrogen-modified perovskite composite molecular sieve according to claim 5, characterized in that it comprises the following steps: adding a photocatalyst, a hole trapping agent and an aromatic compound organic wastewater to a photocatalytic reactor for photocatalysis. Catalytic reaction, wherein the volume ratio of the hole trapping agent and the aromatic compound is 1:8-16, and the dosage of the photocatalyst per liter of the mixture of the hole trapping agent and the aromatic compound is 0.2-0.6g.
  8. 根据权利要求7所述氮改性钙钛矿复合分子筛的光催化剂的应用，其特征在于：在所述光催化反应之前先进行暗吸附。The application of the photocatalyst of the nitrogen-modified perovskite composite molecular sieve according to claim 7, characterized in that: dark adsorption is performed before the photocatalytic reaction.
  9. 根据权利要求7所述氮改性钙钛矿复合分子筛的光催化剂的应用，其特征在于：所述空穴捕获剂为甲醇或草酸铵中的一种。The application of the photocatalyst of the nitrogen-modified perovskite composite molecular sieve according to claim 7, wherein the hole trapping agent is one of methanol or ammonium oxalate.
  10. 根据权利要求7所述氮改性钙钛矿复合分子筛的光催化剂的应用，其特征在于：所述光催化反应通过氙灯提供可见光。The application of the photocatalyst of the nitrogen-modified perovskite composite molecular sieve according to claim 7, wherein the photocatalytic reaction provides visible light through a xenon lamp.
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