WO2021196522A1 - 一种石化废水深度处理用负载型双组分金属氧化物催化剂及其制备方法 - Google Patents

一种石化废水深度处理用负载型双组分金属氧化物催化剂及其制备方法 Download PDF

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WO2021196522A1
WO2021196522A1 PCT/CN2020/113673 CN2020113673W WO2021196522A1 WO 2021196522 A1 WO2021196522 A1 WO 2021196522A1 CN 2020113673 W CN2020113673 W CN 2020113673W WO 2021196522 A1 WO2021196522 A1 WO 2021196522A1
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supported
metal oxide
catalytic oxidation
component metal
preparing
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French (fr)
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吴昌永
周岳溪
付丽亚
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中国环境科学研究院
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Priority to US17/265,989 priority patent/US11666892B2/en
Publication of WO2021196522A1 publication Critical patent/WO2021196522A1/zh

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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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
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    • 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
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0213—Preparation of the impregnating solution
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • 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
    • 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
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)

Definitions

  • the invention belongs to the technical field of ozone catalyst preparation, especially for the secondary biological effluent water quality of petrochemical wastewater, and relates to a supported two-component ozone catalytic oxidation with ⁇ -A12O3 pellets as a carrier and active components of copper oxide and manganese oxide Catalyst preparation method.
  • the petrochemical industry is the country’s pillar industry and one of the heavy pollution industries.
  • the wastewater discharged during its production process contains a large amount of toxic and refractory organic matter. Ecological safety and drinking water cause great harm to human health.
  • the total amount of industrial wastewater discharged every year in my country exceeds 2.1 ⁇ 1010 tons, most of which are discharged after being treated by centralized integrated sewage treatment plants.
  • the advanced treatment of the integrated sewage treatment plant is the last barrier to ensure that the petrochemical integrated wastewater treatment meets the discharge standards.
  • my country's requirements for the petrochemical industry drainage standards are becoming more and more stringent.
  • the new standard in addition to increasing the COD limit for direct drainage of petrochemical sewage treatment plants to 60 or 50mg/L, the new standard also adds the concentration discharge limit of 60 characteristic organic pollutants. Based on this, the effluent of many domestic petrochemical integrated sewage treatment plants can no longer meet the requirements of the new standards, and there is an urgent need for advanced treatment technology to improve the effluent quality of sewage plants.
  • Ozone has strong oxidizing properties and can oxidize almost all organic pollutants in water.
  • ozone oxidizes organic pollutants through molecular reactions and free radical reactions.
  • Molecular reaction that is, ozone molecules directly oxidize organic matter. This kind of reaction is selective. In most cases, it mainly attacks the parts with high electron cloud density in chemical molecules to cause electrophilic reactions.
  • Heterogeneous catalytic ozonation produces more oxidizing hydroxyl radicals by catalyzing ozonolysis, which can degrade organic pollutants that are difficult to be oxidized by ozone alone in water and thoroughly mineralize them.
  • the core of this technology is the preparation of ozone catalytic oxidation catalyst.
  • Catalysts in heterogeneous ozone catalytic oxidation generally use supported metals or metal oxides, activated carbon, etc. These catalysts usually have a large specific surface area.
  • alumina is selected as a carrier, and a metal or metal oxide is supported on it to prepare a heterogeneous catalytic ozone oxidation catalyst. Because alumina has the following characteristics: (1) good strength and hardness; (2) moderate quality, which can form a semi-suspended state under the action of water flow; (3) has a large specific surface area, porosity, and strong adsorption capacity ; (4) Low price. Therefore, ⁇ -A12O3 pellets were screened out as the carrier of metal active components.
  • ozone interacts with Lewis acid sites to generate ⁇ OH, and forms active sites in the presence of metals such as CuOx and MnOx. MnOx can enhance ⁇ OH formation and surface ⁇ OH activity.
  • the technical problem to be solved by the present invention is to address the more stringent emission standards faced by comprehensive petrochemical wastewater containing large amounts of low-concentration toxic and refractory organics, and the general low efficiency of ozone-catalyzed oxidation advanced treatment catalysts, and to develop a suitable water quality Ozone catalytic oxidant improves the removal rate of difficult-to-degrade organics in water, reduces the dosage of ozone, and saves operating costs.
  • a preparation method of a supported two-component metal oxide ozone catalytic oxidation catalyst includes the following steps:
  • Carrier activation buy commercially available activated alumina balls as the carrier, the particle size of the carrier is 2-5mm, wash with deionized water to neutral, then activate with 0.1mol/L hydrochloric acid solution for 2h, and rinse with deionized water again To neutral, dry for 12h at 105°C for later use;
  • Carrier impregnation immerse the activated alumina carrier in the impregnation solution for 24 hours at a temperature of 40°C, dry it for 24 hours after impregnation, and then dry it at 105°C for 12 hours.
  • Each 100g alumina carrier requires 100 mL of impregnation solution;
  • Catalyst roasting the impregnated and dried catalyst is roasted in a muffle furnace at 350-400°C for 2 hours to obtain a roasted product;
  • Catalyst cleaning the roasted product is washed with deionized water and dried to obtain a supported bimetal oxide ozone catalytic oxidation catalyst.
  • the copper-manganese-supported ozone catalytic oxidation catalyst prepared by the invention is a light blue sphere.
  • the ⁇ -Al 2 O 3 carrier used in the present invention is a white spherical particle, which is commercially available, and its preferred further feature is that it has a diameter of 2-5 mm.
  • the Mn(NO 3 ) 2 of the present invention can be a 50% Mn(NO 3 ) 2 solution (industrial grade), and Cu(NO 3 ) 2 can be Cu(NO 3 ) 3 ⁇ 3H 2 O (industrial grade) ,
  • concentration of EDTA-2Na (industrial grade) in the dipping solution is 0.1 mol/L.
  • a mixed solution is prepared by preparing a copper nitrate solution with a concentration of 0.10-0.16 mol/L and a manganese nitrate solution with a concentration of 0.02-0.04 mol/L, and mixing the copper nitrate solution and the manganese nitrate solution 1:1.
  • the concentration of EDTA in the immersion solution obtained in the above step (b) is 0.1 mol/L.
  • the molar ratio of copper ions and manganese ions in the impregnation solution obtained in the above step (b) is 4:1.
  • the calcination temperature in step (d) is preferably 350-400°C, and the calcination time is preferably 2h.
  • the catalyst uses industrially produced ⁇ -Al 2 O 3 particles as the carrier, which can provide the catalyst with thermal stability, compressive strength, larger specific surface and pore size, good adsorption, and surface hydroxyl groups may promote Ozone decomposition produces hydroxyl radicals, which provide sufficient active sites for active components.
  • the raw materials are wide, the preparation process of the catalyst is simple and safe, there is no complicated reaction process, the production cost is low, and it is suitable for large-scale industrial production.
  • the catalyst has good mechanical properties and stability, can be used repeatedly, and has a service life of more than 4 years.
  • the technical principle of the present invention is as follows:
  • the organic matter in the secondary effluent of petrochemical wastewater mainly exists in hydrophilic organic matter and hydrophobic acidic organic matter.
  • the hydrophobic acidic organic matter can be directly oxidized by ozone, a small part of it is mineralized and removed, and most of it is converted into hydrophilic organic matter.
  • the hydrophilic organic matter must be removed by a catalytic oxidation process.
  • the secondary effluent of petrochemical wastewater contains anions with a concentration of more than 1000mg/L, which is likely to cause the quenching waste of hydroxyl radicals.
  • the invention can make the hydrophilic organic matter adsorb and enrich on the surface of the catalyst, and then redox reaction occurs at the active site of the surface.
  • the secondary effluent of petrochemical wastewater contains a relatively high concentration of anion quencher on the surface of the prepared catalyst, and there is almost no change in the concentration of the prepared catalyst, and there is no enrichment effect. Repeatedly, local quenching protection at the metal active site, strengthening the oxidation process.
  • the ozone catalytic oxidation unit has an effective protective effect, can reduce the dosage of ozone, effectively degrade the hydrophilic organic matter in the wastewater that is difficult to be oxidized by ozone alone, and oxidize organic pollutants more thoroughly, with a higher removal rate, and can reduce Operating costs.
  • the TOC removal rate is generally increased by more than 50% compared with the efficiency of common commercially available catalysts.
  • Figure 1 The influence of the molar ratio of different active components on the TOC removal rate of the secondary effluent of petrochemical catalyzed oxidation by ozone.
  • FIG. 2 Comparison of the TOC removal effect of the catalyst prepared by the present invention and the generally commercially available ozone catalytic oxidizer used for the treatment of the secondary effluent of the petrochemical industry.
  • Step (1) Buy commercially available activated alumina balls as the carrier, the particle size of the carrier is 3mm, wash with deionized water to neutral, then activate with 0.1mol/L hydrochloric acid solution for 2h, and rinse with deionized water again to neutral , Dry for 12h at 105°C for later use.
  • Step (2) preparing an impregnating solution with a combination of Mn 2+ and Cu 2+ ions, a combination of Cu 2+ and Fe 3+ ions, and a combination of Zn 2+ and Cu 2+ ions as the catalyst active components, respectively.
  • the sum of the molar amounts of the two ions in each combination of Mn 2+ and Cu 2+ , Cu 2+ and Fe 3+ , Zn 2+ and Cu 2+ is 0.2 mol.
  • the ratio of the molar amount of the corresponding complex ion is 1: 0, 0.9: 0.1, 0.8: 0.2, 0.7: 0.3, 0.6: 0.4, 0.5: 0.5, 0.4: 0.6, 0.3: 0.7, 0.2: 0.8, 0.1: 0.9, 0:1
  • the salt weighed in the above ratio is added to the corresponding container, and Na 2 EDTA is further added, and diluted with water to 1 L to obtain an immersion liquid.
  • the amount of Na 2 EDTA added was 33.6 g.
  • Step (3) Slowly add 1 kg of the ⁇ -Al 2 O 3 carrier that has undergone the activation treatment of step (1) of the present invention into the ionic impregnation solutions prepared above, immerse for 24 hours, and then take out the impregnated particles and dry for 24 hours , Dried at 105°C for 12h, placed in a muffle furnace at 350-400°C for 2h to prepare two-component supported catalysts with different components.
  • the above groups of catalysts were used in the ozone catalytic degradation test of petrochemical wastewater.
  • the above-mentioned ozone catalytic degradation test evaluation was carried out in a glass reactor.
  • the ozone dosage was controlled by an ozone concentration detector and a flow meter.
  • the ozone dosage was 0.5mg/min and the catalyst dosage was 100g/L, taken from the petrochemical park.
  • the effluent from the secondary sedimentation tank of the sewage treatment plant is used as the treatment object. After 60 minutes of reaction, samples are taken to determine the TOC value.
  • the effect of the molar ratio between the active components of the catalyst and the components on the removal rate and removal of the TOC of the secondary effluent of the petrochemical industry is shown in Figure 1. .
  • ozone catalytic oxidants for petrochemical secondary effluent treatment are selected.
  • the above-mentioned catalysts were purchased from four provinces across the country and named: Shandong 1#, Shandong 2#, Jiangsu 1#, Jiangxi 1#, and Guangdong 1#.
  • Catalytic degradation test of ozone to evaluate catalyst performance carried out in a glass reactor, and controlled the dosage of ozone by an ozone concentration detector and a flow meter.
  • the catalyst filling amount was 25g/L; the effluent from the secondary sedimentation tank of the comprehensive sewage plant in the petrochemical park was used as the Processing object.
  • the result is shown in Figure 2.
  • the results based on Fig. 2 show that the catalyst of the present invention is significantly higher than the generally commercially available catalysts for secondary effluent treatment of petrochemicals.
  • the wastewater used in this application is taken from the effluent of the second settling tank of a sewage treatment plant in a petrochemical industrial park in China, that is, the secondary effluent of petrochemical wastewater.
  • the plant has a processing scale of 2600m 3 /h.
  • the industrial influent of the integrated sewage treatment plant is a subsidiary of a petrochemical company More than 70 sets of production plants including oil refineries, pesticide plants, acrylonitrile plants, calcium carbide plants, fertilizer plants, and synthetic resin plants have discharged industrial wastewater after preliminary treatment, with a water volume of about 2100m 3 /h.
  • the secondary biological treatment process of the sewage plant is hydrolysis acidification-AO.
  • the characteristic organics such as refractory organics in the biochemical effluent of petrochemical wastewater are complex, and their properties are shown in Table 2.
  • Table 2 shows that the organic matter in wastewater mainly includes benzene, alkanes, heterocyclics, alcohols, esters, ketones, acids, nitriles, organic amines and other organic substances.
  • benzene, hydrocarbons, and heterocyclic substances are difficult to degrade by microorganisms, and contain 10-50 kinds of characteristic organic substances, and the average concentration is also at a relatively high level of 100-600 ⁇ g/L.
  • These organic substances in the biochemical effluent of petrochemical wastewater have a stable chemical structure and are difficult to biodegrade organic pollutants.
  • Table 1 Conventional water quality indicators for the secondary effluent part of a petrochemical wastewater plant

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Abstract

一种用于石化废水深度处理的负载型双组分金属氧化物臭氧催化氧化催化剂制备方法。将市售活性氧化铝球通过载体活化、浸渍液制备、载体浸渍、催化剂焙烧、催化剂清洗步骤得到负载型金属氧化物臭氧催化氧化催化剂。该方法简单，成本低，易制备，制得的催化剂对石化废水二级出水有专性较高的去除效率；产品稳定性好，可重复使用，对石化污水处理厂催化臭氧氧化技术的应用与节能降耗具有十分重要的意义。

Description

一种石化废水深度处理用负载型双组分金属氧化物催化剂及其制备方法 技术领域
本发明属于臭氧催化剂制备技术领域，特别是针对石化废水二级生物出水水质，涉及一种以γ-A12O3小球为载体，以氧化铜和氧化锰活性组分的负载型双组分臭氧催化氧化催化剂的制备方法。
背景技术
石油化工行业是国家的支柱产业，同时也是重污染行业之一，其生产过程中排放的废水中含有大量的有毒难降解有机物，如不能有效处理将会对受纳水体造成严重的污染，对水生态安全和饮用水人体健康造成极大的伤害。目前，我国每年排放的工业废水的总量超过2.1×1010吨，其中多数是经过集中式的综合污水处理厂处理后排放。对于大型的石化工业园区来讲，综合污水处理厂深度处理是保证石化综合废水处理达标排放的最后一道屏障。随着水体保护要求的提高，我国对石化行业排水标准的要求越来越严格，2015年4月16日原环境保护部颁布了《石油化学工业污染物排放标准》(GB31571-2015)(以下称新标准)，新标准除了将石化污水处理厂直排水的COD限值提高至60或50mg/L外，还加入了60种特征有机污染物的浓度排放限值。基于此，国内许多已有石化综合污水处理厂出水已无法满足新标准的要求，亟需深度处理工艺来提高污水厂出水水质。
石化综合废水深度处理技术较多，臭氧具有强氧化性，几乎能够氧化水体中所有的有机污染物，当臭氧溶解到水中时，臭氧通过分子反应和自由基反应两种方式氧化有机污染物。分子反应，即臭氧分子直接氧化有机物，该种反应方式具有选择性，在大部分情况下，主要攻击化学分子中电子云密度 高的部位，发生亲电反应。自由基反应，即臭氧通过形成羟基自由基(OH，E0＝2.80V)间接氧化有机物，该类反应一般较快且无选择性，基本对所有有机物都反应。并且在水中能短时间自行分解，不产生二次污染，但是其成本高，在水中溶解度低，对有机物氧化不彻底等缺点限制了其在水处理领域的应用。目前石化废水二级出水深度处理臭氧氧化对催化剂具有极强的依赖性，必须用臭氧催化剂氧化剂以提高臭氧催化氧化效率。现阶段，新建石化工业园区污水处理厂则缺乏科学合理的处理工艺，且催化剂的选择具有盲目性，臭氧消耗能力也比较大。非均相催化臭氧氧化通过催化臭氧分解产生氧化性更强的羟基基自由基，可以降解水中难以单独臭氧氧化的有机污染物并将其彻底矿化。此技术的核心是臭氧催化氧化催化剂的制备。
异相臭氧催化氧化中的催化剂一般采用负载型的金属或金属氧化物、活性炭等，这些催化剂通常具有较大比表面积。通常是选取氧化铝为载体，在其上负载金属或是金属氧化物来制备非均相催化臭氧氧化催化剂。因氧化铝具有以下特点：(1)较好的强度和硬度；(2)质量适中，能够在水流的作用下形成半悬浮状态；(3)具有较大地比表面积，孔隙率，吸附性能力强；(4)价格低廉。因此，筛选出γ-A12O3小球为金属活性组分的载体。在氧化铝表面，臭氧和Lewis酸位点相互作用产生·OH，并且在和CuOx和MnOx等金属存在下形成活性位点，MnOx能加强·OH的形成和表面·OH的活性。
发明内容
本发明要解决的技术问题是针对量大含低浓度有毒难降解有机物的石化综合废水面临的更加严格的排放标准，臭氧催化氧化深度处理催化剂效率普遍不高的问题，开发一种适合其水质的臭氧催化氧化剂，提高水中难降解 有机物的去除率，降低臭氧的投加量，节省运行成本。
本发明的技术方案如下：
一种负载型双组分金属氧化物臭氧催化氧化催化剂的制备方法，包括如下步骤：
(a)载体活化：购买市售活性氧化铝球作为载体，载体颗粒大小为2-5mm，用去离子水清洗至中性，再用0.1mol/L盐酸溶液活化2h，再次用去离子水冲洗至中性，105℃下干燥12h后备用；
(b)浸渍液制备：配置浓度为0.10-0.16mol/L的硝酸铜溶液和0.02-0.04mol/L的硝酸锰溶液混合液，向上述混合液中加入一定量的EDTA-2Na搅拌2h，使得EDTA-2Na浓度为0.1mol/L；
(c)载体浸渍：将活化好的氧化铝载体于浸渍液中浸渍24h，浸渍温度为40℃，浸渍后晾干24h，再于105℃烘干12h，每100g氧化铝载体需100mL浸渍液；
(d)催化剂焙烧：将浸渍干燥后的催化剂在马弗炉中于350-400℃下焙烧2h，得到焙烧物；
(e)催化剂清洗：将焙烧物用去离子水洗涤、烘干，得到负载型双金属氧化物臭氧催化氧化催化剂。
本发明制得的铜锰负载臭氧催化氧化催化剂为浅蓝色球体。
本发明所用γ-A1 2O 3载体为白色球形颗粒，市售，其优选的进一步特征是，直径2-5mm。
本发明所述的Mn(NO 3) 2可以为50％的Mn(NO 3) 2溶液(工业级)，Cu(NO 3) 2可以为Cu(NO 3) 3·3H 2O(工业级)，浸渍液中EDTA-2Na(工业级)浓度为0.1mol/L。 生产时控制指标：浸渍液没有不溶解残渣，铜离子浓度不低于0.16mol/L，锰离子浓度不低于0.04mol/L，EDTA-2Na浓度误差不超过±10％。
上述步骤(b)中通过配制浓度为0.10-0.16mol/L的硝酸铜溶液和0.02-0.04mol/L的硝酸锰溶液，将硝酸铜溶液和硝酸锰溶液1：1混合制备混合液。
上述步骤(b)中得到的浸渍液中EDTA浓度为0.1mol/L。
上述步骤(b)中得到的浸渍液中铜离子和锰离子的摩尔比为4：1。
上述制备过程中，对于步骤(d)所述的焙烧温度优选为350-400℃，焙烧时间优选2h。
本发明的有益效果是：
(1)采用铜锰双组分负载催化剂臭氧催化氧化降解石化废水中的有机物，在相同条件下，有机物降解速率比单独使用臭氧或者使用未负载的γ-A1 2O 3颗粒显著加快，比使用铜或锰单组分负载催化剂有较大提高，该催化剂尤其对石化废水二级出水难降解有机物(尤其是亲水性组分)具有较高催化活性。
(2)该催化剂以工业化生产的γ-A1 2O 3颗粒为载体，能够提供催化剂的热稳定性、抗压强度、较大的比表面和孔径，吸附性好，表面羟基基团可能会促进臭氧分解产生羟基自由基，为活性组分提供充分的活性点位。原料广泛，该催化剂制备工艺简单安全，无复杂反应过程，生产成本低，适合大规模的工业化生产。
(3)该催化剂具有较好的机械性能和稳定性，可重复使用，使用寿命可超过4年。
本发明的技术原理如下：石化废水二级出水中有机物主要以亲水性有机 物和疏水酸性有机物存在，疏水酸性有机物可被臭氧直接氧化，小部分矿化去除，大部分转化为亲水性有机物，而亲水性有机物必须通过催化氧化过程去除。石化废水二级出水中含有浓度超过1000mg/L的阴离子，容易造成羟基自由基的淬灭浪费。本发明可使得亲水性有机物在催化剂表面吸附富集，然后在表面活性位点发生氧化还原反应，反应完成之后氧化位点暴露，有机物在催化剂表面活性位点进一步吸附和氧化去除。石化废水二级出水中含有较高浓度的阴离子淬灭剂在该制备的催化剂表面浓度几乎没有变化，不存在富集作用。周而复始，在金属活性位点局部猝灭保护，强化氧化过程。臭氧催化氧化单元起到有效的保护作用，可降低臭氧的投加量，有效降解废水中难以被臭氧单独氧化的亲水性有机物，对有机污染物氧化更加彻底，去除率更高，同时可降低运行成本。
有益效果：采用本发明制备的催化剂，在处理石化废水二级出水时，同样条件下，TOC去除率比市售常见催化剂效率普遍提高50％以上。
下面结合附图对本发明的负载型双组分金属氧化物臭氧催化氧化剂的处理方法作进一步说明。
附图说明
图1：不同活性组分的摩尔比对臭氧催化氧化石化二级出水的TOC去除率的影响。
图2：本发明制得催化剂与一般市售用于石化二级出水处理的臭氧催化氧化剂对石化二级出水TOC去除效果对比。
具体实施方式
本发明选择不同金属活性组分按照不同的摩尔比制备催化剂，具体方法 如下：
步骤(1)：购买市售活性氧化铝球作为载体，载体颗粒大小为3mm，用去离子水清洗至中性，再用0.1mol/L盐酸溶液活化2h，再次用去离子水冲洗至中性，105℃下干燥12h后备用。
步骤(2)：以Mn 2+、Cu 2+离子组合，Cu 2+、Fe 3+离子组合，Zn 2+、Cu 2+离子组合分别作为催化剂活性组分制备浸渍液。在上述各组离子组合中，Mn 2+和Cu 2+，Cu 2+和Fe 3+，Zn 2+和Cu 2+每组组合中两种离子的摩尔量和为0.2mol。按照相应复合离子的摩尔量之比为1：0，0.9：0.1，0.8：0.2，0.7：0.3，0.6：0.4，0.5：0.5，0.4：0.6，0.3：0.7，0.2：0.8，0.1：0.9，0：1称取相应重量的Mn(NO 3) 2，Cu(NO 3) 2，Fe(NO 3) 3，Zn(NO 3) 2。将上述比例称取的盐分别加入相应的容器中，进一步加入Na 2EDTA，并加水稀释至1L，得到浸渍液。上述Na 2EDTA的加入量为33.6g。
步骤(3)：在上述制备得到的各组离子浸渍液中缓慢加入1kg经过本发明步骤(1)活化处理的γ-A1 2O 3载体，浸渍24h，然后取出浸渍后的颗粒物，晾干24h，在105℃烘干12h，置于马弗炉中350-400℃焙烧2h，制得不同组分的双组分负载型催化剂。
将上述各组催化剂用于石化废水的臭氧催化降解试验。上述臭氧催化降解试验评在玻璃反应器中进行，通过臭氧浓度检测仪和流量计控制臭氧投加量，其中臭氧投量为0.5mg/min，催化剂投量为100g/L，取自石化园区综合污水厂二沉池出水作为处理对象，反应60min后取样测定TOC值，催化剂活性组分和组分之间的摩尔比对于催化剂对石化二级出水TOC去除率和去除量的影响如图1所示。
从图1可以看出，不同多金属活性组分在不同的摩尔比条件下对催化臭氧氧化对废水TOC去除率的影响不同，Cu:Mn摩尔比在4:1时，臭氧催化氧化对废水TOC去除率最高，达到35％。因此，本研究最终确定催化剂的活性组分为Cu：Mn摩尔比为4:1。
进一步地，选取不同市售的用于石化二级出水处理的臭氧催化氧化剂。上述催化剂分别于全国四个省份采购得到，命名为：山东1#、山东2#、江苏1#、江西1#、广东1#。臭氧催化降解试验评价催化剂性能：在玻璃反应器中进行，通过臭氧浓度检测仪和流量计控制臭氧投加量，催化剂填充量为25g/L；以取自石化园区综合污水厂二沉池出水作为处理对象。结果如图2所示。基于图2的结果显示，本发明的催化剂显著高于一般市售用于石化二级出水处理的催化剂。
本申请所使用的废水取自中国某石化工业园区污水处理厂二沉池的出水，即石化废水二级出水，该厂处理规模2600m 3/h，该综合污水处理厂工业进水为石化公司下属的炼油厂、农药厂、丙烯腈厂、电石厂、化肥厂、合成树脂厂等70余套生产装置初步处理后排放的工业污水，水量约2100m 3/h。该污水厂二级生物处理工艺为水解酸化-AO。二级生化出水复杂，且各水质指标波动范围较大，相对标准偏差为0.4～25.1％(n＝60)，其性质如表1所示。由表可知，石化废水二级出水呈弱碱性，COD平均含量在80mg/L左右，而BOD 5含量为10mg/L，B/C值小于0.3，可生化性极低；并且氯离子和硫酸根含量较高，这两种离子是臭氧氧化系统自由基的淬灭剂，极大程度上限制了臭氧催化氧化效果的提高。
石化废水生化出水中的难降解有机物等特征有机物复杂，其性质如表2 所示。有表可知，废水中的有机物主要包括苯类、烷烃类、杂环类、醇类、酯类、酮类、酸类、腈类、有机胺类等有机物。其中，苯类、烃类、杂环类三类物质微生物难降解，含10～50种特征有机物，平均浓度也处于较高水平为100～600μg/L。石化废水生化出水中这些有机物化学结构稳定，属于难生物降解的有机污染物。
表1某石化污水厂二级出水部分常规水质指标
Figure PCTCN2020113673-appb-000001
表2石化废水生化出水特征有机物种类及其含量分析结果
Figure PCTCN2020113673-appb-000002
Figure PCTCN2020113673-appb-000003
以上所述的实施例仅仅是对本发明的优选实施方式进行描述，并非对本发明的范围进行限定，在不脱离本发明设计精神的前提下，本领域普通技术人员对本发明的技术方案作出的各种变形和改进，均应落入本发明权利要求书确定的保护范围内。

Claims (10)

  1. 一种负载型双组分金属氧化物臭氧催化氧化催化剂的制备方法，包括如下步骤：
    (a)载体活化：将活性氧化铝球用去离子水清洗至中性，再用盐酸溶液活化，再次用去离子水冲洗至中性，干燥后得到活化的氧化铝载体粒子，所述活性氧化铝球的粒径为2-5mm；
    (b)浸渍液制备：配置浓度为硝酸铜和硝酸锰的混合溶液，向上述混合溶液中加入EDTA-2Na，搅拌均匀后得到浸渍液；
    (c)载体浸渍：将活化好的氧化铝载体于浸渍液中浸渍，浸渍后晾干，之后进一步加热烘干；
    (d)催化剂焙烧：将浸渍干燥后的催化剂进行焙烧，得到焙烧物；
    (e)催化剂清洗：将焙烧物用去离子水洗涤、烘干，得到负载型双金属氧化物臭氧催化氧化催化剂。
  2. 如权利要求1所述的负载型双组分金属氧化物臭氧催化氧化催化剂的制备方法，其中所述步骤(a)中盐酸溶液的浓度为0.1mol/L，活化时间为2h。
  3. 如权利要求1所述的负载型双组分金属氧化物臭氧催化氧化催化剂的制备方法，其中所述步骤(a)中氧化铝粒子的粒径为2-5mm。
  4. 如权利要求1所述的负载型双组分金属氧化物臭氧催化氧化催化剂的制备方法，其中所述步骤(b)中通过配制浓度为0.10-0.16mol/L的硝酸铜溶液和0.02-0.04mol/L的硝酸锰溶液，将硝酸铜溶液和硝酸锰溶液1：1混合制备混合液。
  5. 如权利要求1所述的负载型双组分金属氧化物臭氧催化氧化催化剂的制备方法，其中所述步骤(b)中得到的浸渍液中EDTA浓度为0.1mol/L。
  6. 如权利要求1所述的负载型双组分金属氧化物臭氧催化氧化催化剂的制备方法，其中所述步骤(b)中得到的浸渍液中铜离子和锰离子的摩尔比为4：1。
  7. 如权利要求1所述的负载型双组分金属氧化物臭氧催化氧化催化剂的制备 方法，其中所述步骤(c)为将活化好的氧化铝载体于浸渍液中浸渍24h，浸渍温度为40℃。
  8. 如权利要求1所述的负载型双组分金属氧化物臭氧催化氧化催化剂的制备方法，其中所述步骤(c)中每100g氧化铝载体需100mL浸渍液。
  9. 如权利要求1所述的负载型双组分金属氧化物臭氧催化氧化催化剂的制备方法，其中所述步骤(d)中将浸渍干燥后的催化剂在马弗炉中于350-400℃下焙烧2h，得到焙烧物。
  10. 一种如权利要求1-9任一项所述的负载型双组分金属氧化物臭氧催化氧化催化剂的制备方法制备得到的催化剂。
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Publication number Priority date Publication date Assignee Title
CN115555008A (zh) * 2022-10-28 2023-01-03 徐涵 一种低阻抗、高孔隙率的多相高级氧化催化滤料及应用

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111282577A (zh) * 2020-03-30 2020-06-16 中国环境科学研究院 一种石化废水深度处理用负载型双组分金属氧化物催化剂及其制备方法
CN111977776B (zh) * 2020-08-28 2023-01-24 吉林大学 一种基于催化臭氧化的酸性含难降解水溶性高分子废水预处理方法
CN113117684A (zh) * 2021-04-19 2021-07-16 河北德龙环境工程股份有限公司 一种用于废水深度处理的三元氧化物臭氧催化剂的制备方法
CN114291883B (zh) * 2021-12-16 2023-05-02 湖南化工研究院有限公司 一种1-(4-氯苯基)-3-吡唑醇生产废水的预处理方法
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CN114632524A (zh) * 2022-05-18 2022-06-17 中国环境科学研究院 一种用于石化废水处理的铜-锰/三氧化二铝催化剂及其制备方法
CN115155584A (zh) * 2022-06-22 2022-10-11 广东中膜科技有限公司 一种氧化铝载高分散铁臭氧催化剂的制备方法及应用
CN115739101B (zh) * 2022-09-07 2024-05-28 南京大学 一种双金属负载型臭氧催化剂的可控制备方法及其水处理应用
CN116081891B (zh) * 2023-02-16 2023-11-17 浙江省机电设计研究院有限公司 高效环保型氯虫苯甲酰胺原药及中间体生产废水处理工艺
CN116987009A (zh) * 2023-08-14 2023-11-03 西陇科学股份有限公司 一种梯度级乙腈及其制备方法
CN117960251A (zh) * 2024-04-01 2024-05-03 陕西科技大学 一种催化滤芯、制备方法及其应用

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070298167A1 (en) * 2006-06-26 2007-12-27 Applied Materials, Inc. Ozone abatement in a re-circulating cooling system
CN102941084A (zh) * 2012-11-22 2013-02-27 大连理工大学 一种负载型双组分金属氧化物臭氧催化氧化催化剂的制备方法
CN104525206A (zh) * 2014-12-04 2015-04-22 格丰科技材料有限公司 一种去除废水中cod的多孔臭氧催化剂及其制备方法
CN105344360A (zh) * 2015-12-09 2016-02-24 哈尔滨工业大学 一种掺杂型纳米MnO2-CuO/Al2O3催化剂的制备方法和应用
CN108380214A (zh) * 2018-04-02 2018-08-10 南京万德斯环保科技股份有限公司 一种改性海泡石的制备及应用于废水处理的方法
CN108745361A (zh) * 2018-05-28 2018-11-06 上海安居乐环保科技股份有限公司 一种VOCs常温催化氧化材料及其制备方法和应用
CN109939695A (zh) * 2019-04-03 2019-06-28 宁夏大学 一种负载型o3催化剂的制备及其在煤化工高盐废水cod去除中的应用
CN111282577A (zh) * 2020-03-30 2020-06-16 中国环境科学研究院 一种石化废水深度处理用负载型双组分金属氧化物催化剂及其制备方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101584988B (zh) * 2009-03-30 2011-08-31 浙江工业大学 一种双组分复合型金属催化剂及其应用
CN105013504A (zh) * 2015-07-20 2015-11-04 华南理工大学 负载型二元复合金属氧化物臭氧催化氧化催化剂及其制备
CN105268452A (zh) * 2015-11-12 2016-01-27 西安石油大学 介孔负载型铜锰复合氧化物催化剂、制备及催化方法
CN106693974A (zh) * 2016-11-11 2017-05-24 大连理工大学 一种催化臭氧氧化去除水中氨氮的负载型金属氧化物催化剂的制备方法及应用
CN108236965A (zh) * 2016-12-27 2018-07-03 中国石油天然气股份有限公司 一种改性的加氢脱硫催化剂及其制备方法
CN107899568A (zh) * 2017-11-17 2018-04-13 大连理工大学 一种负载复合金属氧化物催化剂的制备方法及其在废气处理领域的应用
CN110270329A (zh) * 2019-06-18 2019-09-24 北京首创股份有限公司 用于处理水中难降解有机物的臭氧催化剂及其制备方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070298167A1 (en) * 2006-06-26 2007-12-27 Applied Materials, Inc. Ozone abatement in a re-circulating cooling system
CN102941084A (zh) * 2012-11-22 2013-02-27 大连理工大学 一种负载型双组分金属氧化物臭氧催化氧化催化剂的制备方法
CN104525206A (zh) * 2014-12-04 2015-04-22 格丰科技材料有限公司 一种去除废水中cod的多孔臭氧催化剂及其制备方法
CN105344360A (zh) * 2015-12-09 2016-02-24 哈尔滨工业大学 一种掺杂型纳米MnO2-CuO/Al2O3催化剂的制备方法和应用
CN108380214A (zh) * 2018-04-02 2018-08-10 南京万德斯环保科技股份有限公司 一种改性海泡石的制备及应用于废水处理的方法
CN108745361A (zh) * 2018-05-28 2018-11-06 上海安居乐环保科技股份有限公司 一种VOCs常温催化氧化材料及其制备方法和应用
CN109939695A (zh) * 2019-04-03 2019-06-28 宁夏大学 一种负载型o3催化剂的制备及其在煤化工高盐废水cod去除中的应用
CN111282577A (zh) * 2020-03-30 2020-06-16 中国环境科学研究院 一种石化废水深度处理用负载型双组分金属氧化物催化剂及其制备方法

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
DENG FENGXIA, QIU SHAN, CHEN CONG, DING XIAO, MA FANG: "Heterogeneous Catalytic Ozonation of Refinery Wastewater over Alumina-Supported Mn and Cu Oxides Catalyst", OZONE: SCIENCE AND ENGINEERING., LEWIS PUBLISHERS, CHELSEA, MI., US, vol. 37, no. 6, 2 November 2015 (2015-11-02), US, pages 546 - 555, XP055855612, ISSN: 0191-9512, DOI: 10.1080/01919512.2015.1065173 *
LI XIN, BIAN JIANG,ZHU XUE-DUO,QIANG LIANG-SHENG: "Preparation,Structural Characterization and Catalyst Activity of CuO-MnO2/Al2O3 Catalysts", CHEMICAL JOURNAL OF CHINESE UNIVERSITIES, JILIN DAXUE, BEIJING, CN, vol. 28, no. 6, 30 June 2007 (2007-06-30), CN, pages 1155 - 1159, XP055855605, ISSN: 0251-0790 *
WANG HONGPEI; LU YIYUAN; HAN YUXIANG; LU CHUNLIANG; WAN HAIQIN; XU ZHAOYI; ZHENG SHOURONG: "Enhanced catalytic toluene oxidation by interaction between copper oxide and manganese oxide in Cu-O-Mn/γ-Al2O3catalysts", APPLIED SURFACE SCIENCE, ELSEVIER, AMSTERDAM, NL, vol. 420, 19 May 2017 (2017-05-19), AMSTERDAM, NL, pages 260 - 266, XP085146238, ISSN: 0169-4332, DOI: 10.1016/j.apsusc.2017.05.133 *
XU AIJUN, ERYAN LIANG, JIE WANG, YIN ZHANG, YONGXIANG ZHAO: "Preparation of Ni / ZrO 2 catalysts for liquid hydrogenation of maleic anhydride by complex impregnation", INDUSTRIAL CATALYSIS, NORTHWEST RESEARCH INSTITUTE OF CHEMICAL INDUSTRY, CHINA, vol. 26, no. 2, 28 February 2018 (2018-02-28), China, pages 28 - 32, XP055855610, ISSN: 1008-1143, DOI: 10.3969/j.issn.1008-1143.2018.02.004 *
ZHANG YING: "Study on Copper/Manganese Oxide Adsorbents Sulfation Properties of Gamma-Al203 Carrier", JOURNAL OF SHANXI COAL-MINING ADMINISTRATORS COLLEGE, vol. 27, no. 1, 28 February 2014 (2014-02-28), XP055855600, ISSN: 1008-8881 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115555008A (zh) * 2022-10-28 2023-01-03 徐涵 一种低阻抗、高孔隙率的多相高级氧化催化滤料及应用

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