CN114405494A - Ozone oxidation catalyst for advanced treatment of salt-containing organic wastewater and preparation thereof - Google Patents

Ozone oxidation catalyst for advanced treatment of salt-containing organic wastewater and preparation thereof Download PDF

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CN114405494A
CN114405494A CN202210112168.6A CN202210112168A CN114405494A CN 114405494 A CN114405494 A CN 114405494A CN 202210112168 A CN202210112168 A CN 202210112168A CN 114405494 A CN114405494 A CN 114405494A
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catalyst
carrier
ozone oxidation
drying
ozone
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CN114405494B (en
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任钟旗
涂玉明
周智勇
屈一新
田世超
张帆
陈健杰
邵高燕
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Beijing University of Chemical Technology
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • 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
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • 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
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • 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
    • 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
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/38—Gas flow rate

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Abstract

The invention relates to an ozone oxidation catalyst for advanced treatment of organic wastewater containing salt, which consists of a carrier and a metal active component loaded on the carrier, wherein the metal active component is calcium oxide. The invention also relates to a preparation method of the catalyst, which mainly improves the dispersion degree of the metal active component by a surface modification method and enhances the interaction of the active component and the carrier, thereby obtaining the catalyst with high activity and good stability. The catalyst is prepared by performing surface modification on active carbon, aluminum oxide, a molecular sieve, medical stone or other carriers and taking Ca salt as a metal active component. The process flow for preparing the catalyst is simple, the rapid preparation of the catalyst can be realized by adopting a conventional impregnation method, the deep treatment of the organic wastewater containing salt is oriented, the catalyst has good catalytic performance, and the method is suitable for industrial popularization.

Description

Ozone oxidation catalyst for advanced treatment of salt-containing organic wastewater and preparation thereof
Technical Field
The invention belongs to the technical field of wastewater treatment, relates to an ozone oxidation catalyst for advanced treatment of salt-containing organic wastewater and a preparation method thereof, and particularly relates to an ozone oxidation catalyst for advanced treatment of salt-containing organic wastewater and a preparation method and an application thereof.
Background
The salt-containing organic wastewater is from high water consumption industries such as petrifaction industry, textile printing and dyeing industry and the like, and has the characteristics of high salt content, high toxicity, difficult degradation and the like. In 2021, 11 months and 11 days, ten committees such as a development and improvement committee jointly issue guidance opinions (development and improvement capital [ 2021 ] 13 ]) about promoting the resource utilization of sewage, and the opinions emphasize that the industrial wastewater recycling is implemented for high water consumption industries such as petrifaction, papermaking, printing and dyeing, the recycling rate is improved, and near zero emission is realized. In addition, the country of 4 months in 2015 has issued the action plan for water pollution prevention and control, the country of 4 months in 2018 has implemented the environmental protection tax law, and meanwhile, some water shortage areas have correspondingly made the requirement of zero emission according to the characteristics of local water quality and water quantity, and the emission standard is gradually upgraded and becomes stricter. In conclusion, the research of advanced treatment of organic wastewater containing salt has become an important research direction and development trend in the field of environmental protection, and is in line with the important strategic demand of China for building beautiful China. The salt-containing organic wastewater has complex water quality, high chromaticity, high Chemical Oxygen Demand (COD) and Biochemical Oxygen Demand (BOD) and great difficulty in degradation, belongs to the industrial wastewater which is difficult to treat and has three-cause toxicity, seriously threatens the water environment safety, and the advanced treatment technology thereof is widely concerned and researched by domestic and foreign water treatment workers.
The heterogeneous catalysis ozone oxidation technology is strong in oxidizability, simple to operate and small in occupied area, is one of effective modes for advanced treatment of salt-containing organic wastewater, can effectively catalyze ozone to generate free radicals to achieve mineralization of difficultly-degraded organic matters, and meanwhile overcomes the problems that a catalyst is not easy to recover and easily causes secondary pollution and the like caused by homogeneous catalysis. Therefore, the key of the heterogeneous catalysis ozone oxidation process is a high-efficiency catalyst, and extensive researchers at home and abroad make extensive research on the catalyst.
The heterogeneous catalysts commonly used at present are various in types, and mainly include single-metal or multi-metal oxide catalysts containing Fe, Mn, Ce, Zn, Ti and the like, carbon-based non-metal catalysts containing N, F and other elements, MOF and other catalysts. Containing metal sites (typically multivalent metal ions such as Ce)3+/Ce4+Etc.) provide electrons to promote the decomposition into active radicals mainly through the conversion between multi-valence metal ions, and the catalyst containing non-metal sites, such as N, F, S and other doped carbon nanotubes, graphene-based materials and the like, realizes the conversion of ozone molecules into active radicals through graphitizing N, thiophene S and other defect sites. In addition to this, the carbon-based material is also capable of effecting oxidative degradation of organic pollutants by surface adsorbed active oxygen species.
The metal oxide catalyst is most widely applied due to the advantages of low cost, simple and convenient synthesis and the like, but the problem of secondary pollution caused by loss of active metal components of the catalyst mainly exists at present: in the roasting process of the metal oxide catalyst, agglomeration phenomena of different degrees exist on the surface of the catalyst due to an Ostwald ripening mechanism, and the bonding degree of the active component and the carrier is weak. In the catalytic oxidation process, due to factors such as collision, unreliable combination degree and the like, the metal active components can be separated from the surface of the carrier, so that loss in different degrees is caused, secondary pollution is formed, and the difficulty is increased for subsequent treatment. To is directed atIn view of enhancing the degree of bonding between the metal component and the carrier, researchers have been actively exploring the influence of different synthetic methods, such as an impregnation method, a hydrothermal method, a coprecipitation method, a sol-gel method, a template method, etc., on the stability of the catalyst. For example Chen[4]Et al (Chen Weirii, etc. Mineralisation of salicylic acid via catalytic catalysis with Fe-Cu @ SiO)2core-shell catalyst: A two-stage first order reaction. Chemosphere,2019,235:470-2Interfacial coupling between iron oxide and copper oxide and SiO2The strong interaction of the shell with the metal improves the stability of the catalyst. Compared with a single-metal Fe or Cu oxide catalyst, the catalyst activity is further improved, and Fe-Cu @ SiO2The TOC removal rate of the catalyst is Cu @ SiO21.1 times of (1), Fe @ SiO21.5 times of the total weight of the powder. And Fe-Cu @ SiO2Metal ion concentration ratio of catalyst leaching to single metal Cu @ SiO2、Fe@SiO2The catalyst is reduced by more than one time. At the same time, researchers have attempted to modify the catalyst accordingly. Such as Li et al (Li Shangyi, etc. Mechanism of synergistic effect on electron transfer Co-Ce/MCM-48 reduction catalysis of pharmaceutical in water. ACS Applied Materials)&Interfaces,2019,11(27): 23957-. Moussavi et al (Moussavigholanza, etc. the catalytic reduction of the inorganic tetracyclic by sulfur-doped naphthalene oxide (S-MgO) nanoparticles. journal of Environmental Management,2018,210: 131-. Compared with MgO catalyst, S element greatly increases the oxygen vacancy quantity of MgO catalyst, and the TOC removal rate is improved by nearly 70%. Therefore, improving the catalyst synthesis method and modifying the catalyst are effective ways to further improve the catalyst performance, but no matter the metal element or the nonmetal element is introduced, the agglomeration phenomenon on the surface of the metal oxidation catalyst and the metal componentThe leaching still exists, so the problem of loss of active components of the catalyst cannot be fundamentally solved by only introducing metal or nonmetal elements.
In addition, due to factors such as collision and the like in the long-period ozone catalytic oxidation process, active components of the catalyst can be leached in trace, and if the active components are accumulated in water, the water environment is still damaged, so that a green and efficient metal component replacing a conventional transition metal oxide is urgently needed to be found as an active center of ozone catalytic oxidation. The calcium compound is cheap and easy to obtain, calcium ions basically have no pollution to a water environment, and the calcium compound contains strong alkaline sites and can be used as a green and efficient metal active component. At present, the calcium compound is less relevant to research on the use of the calcium compound as an ozone catalyst, and is mainly used as a catalyst auxiliary agent for improving stability or a calcium hydroxide as a pH regulator for promoting the generation of active free radicals by ozone. For example, Marcio et al (Cintia Andreia noves Pereira, Marcio Barreto-Rodrigues, etc. application of Zero Value Iron (ZVI) immibilized in Ca-Alginate beads for C.I. reactive Red 195catalytic degradation in an air lift exact with in. journal of Yeast Materials,2021,401:123275) and Ca2+The ozone catalyst taking zero-valent iron as an active center is prepared as a cross-linking agent, and ozone is converted into active free radicals under the action of the zero-valent iron to realize the oxidative degradation of organic pollutants. Patent CN103351051A in the form of Ca (OH)2As an ozone catalyst in a liquid phase, biochemical effluent of a certain waste incineration power plant is degraded, and the removal rate is 58%. It is mainly produced by Ca (OH)2Dissociation to OH-To form an alkaline environment to promote ozone to generate active free radicals to degrade pollutants, and Ca2+Formation of CaCO with carbonate in waste water3Precipitate, Ca2+Does not act as an active center in the process to promote the generation of active radicals by ozone; and, it has Ca2+The loss problem can increase the hardness of the wastewater and bring difficulty to subsequent treatment; at the same time, Ca (OH) is continuously added2And cannot be reused.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide an ozone oxidation catalyst for advanced treatment of organic wastewater containing salt; compared with the traditional single metal oxide catalyst, the catalyst has high catalytic efficiency and high stability, and can obviously reduce the treatment cost of an ozone method.
The second purpose of the invention is to provide a preparation method of the ozone oxidation catalyst for the advanced treatment of the organic wastewater containing salt, the ozone oxidation catalyst for the advanced treatment of the organic wastewater containing salt is prepared by the method, the preparation process is simple, and the prepared catalyst has high catalytic efficiency and high stability and can be recycled.
To this end, the invention provides an ozone oxidation catalyst for advanced treatment of organic wastewater containing salt, which comprises a carrier and a metal active component loaded on the carrier, wherein the metal active component is calcium oxide.
According to the invention, the support is surface-modified; preferably, the surface modification is based on coating polymerization of a modifier on the surface of the carrier, and a group with stronger anchoring traction effect on calcium ions is formed on the surface of the carrier; further preferably, the group having strong anchoring traction effect on calcium ions comprises amino and/or hydroxyl; still further preferably, the modifying agent comprises one or more of dopamine hydrochloride, chitosan and gelatin.
In some embodiments of the invention, the specific surface area of the ozone oxidation catalyst is 140-160m2Per g, pore volume of 0.4-0.6cm3/g。
In a second aspect, the present invention provides a method for preparing an ozone oxidation catalyst according to the first aspect of the present invention, comprising:
step A, fully washing a carrier with water, drying and roasting to obtain a pretreated carrier;
step B, placing the pretreated carrier in a buffer solution, stirring, adding a modifier, oscillating, filtering, washing and drying to obtain a surface-modified carrier;
step C, placing the modified carrier in a carrier containing Ca2+In the solution of (1), shaking and standingAging to obtain a catalyst precursor;
and D, drying the catalyst precursor, and roasting to obtain the ozone oxidation catalyst.
According to the invention, in the step A, drying is carried out under vacuum conditions, wherein the drying temperature is 120 ℃, and the drying time is 6-12 h; and/or the roasting temperature is 350 ℃, and the roasting time is 2-5 h.
In some embodiments of the invention, in step B, the mass ratio of the modifying agent to the carrier is 1: 20; and/or the stirring time is 2-12 h; and/or oscillating in a shaking table at the temperature of 20-35 ℃ for 2-12 h; and/or drying under vacuum condition, wherein the drying temperature is 40-80 ℃, and the drying time is 6-12 h.
In some embodiments of the invention, in step C, Ca is contained2+Ca in solution of (2)2+The concentration is 0.05-0.3 mol/L; preferably, the modified vector is mixed with Ca2+The dosage ratio of the solution of (1) is 0.3 g/mL; and/or the oscillation time is 6-12 h; and/or the standing and aging time is 2-24 h.
In some embodiments of the present invention, in step D, the calcination is performed under an inert gas atmosphere, and the calcination temperature is 600-1000 ℃; and/or the roasting time is 1-5 h.
In a third aspect, the invention provides the use of the ozone oxidation catalyst according to the first aspect of the invention or the ozone oxidation catalyst prepared by the preparation method according to the second aspect of the invention in the advanced treatment of salt-containing organic wastewater.
Preferably, the application comprises filling an ozone oxidation catalyst in the wastewater treatment device, introducing wastewater, introducing ozone, and performing ozone oxidation treatment on the wastewater to obtain oxidized effluent meeting the discharge standard.
In some embodiments of the invention, the reaction conditions of the ozonation process are: COD of the wastewater: 140-160mg/L, TDS: 3430 and 3450mg/L of ammonia, the pH value is 7, the ozone flow is 0.03L/min, the catalyst loading is 400g/L, the reaction time is 60min, and the ozone adding ratio is 0.6-4.2.
The invention has the following beneficial effects:
compared with the traditional single metal oxide catalyst, the Ca-based metal oxide ozone catalyst prepared on the basis of carrier surface modification has the advantages of high catalytic efficiency, high stability, simple and convenient preparation and the like, and can obviously reduce the treatment cost of an ozone method. In addition, the porous material used by the catalyst carrier has a high specific surface area, a large pore volume and good adsorption capacity, and can obviously assist the catalytic oxidation reaction by enriching pollutants on the surface of the catalyst.
Drawings
The invention is described in further detail below with reference to the attached drawing figures:
fig. 1 shows a catalyst preparation scheme.
FIG. 2 is a graph showing the COD removal performance of the catalyst.
Detailed Description
In order that the invention may be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. However, before the invention is described in detail, it is to be understood that this invention is not limited to particular embodiments described. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.
Unless otherwise defined, all terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention, the preferred methods and materials are now described.
Term (I)
As used herein, the term "TDS" (Total dissolved solids), also known as Total dissolved solids, measured in milligrams per liter (mg/L) indicates how many milligrams of dissolved solids are dissolved in 1 liter of water. Higher TDS values indicate more solutes in the water. Total dissolved solids refers to the total amount of total solutes in the water, including both inorganic and organic content. Generally, the salt content of the solution is known approximately by the conductivity value, and generally, the higher the conductivity, the higher the salt content, and the higher the TDS. Thus, TDS also reflects the salt level in the wastewater.
The term "advanced wastewater treatment" in the present invention generally refers to a treatment of the secondary effluent after biochemical treatment or the like, and further using advanced oxidation or other technologies to treat the residual organic matters.
The term "PDA" as used herein refers to polydopamine formed by polymerization of dopamine hydrochloride under alkaline conditions.
The term "water" as used herein means deionized water, distilled water or ultrapure water unless otherwise specified.
Embodiments II
As mentioned above, the existing ozone oxidation catalysts are not satisfactory and there are always problems such as the presence of Ca2+The loss problem can increase the hardness of the wastewater and bring difficulty to subsequent treatment; at the same time, Ca (OH) is continuously added2Inability to be recycled, etc.; in view of the above, the present inventors have conducted extensive studies on the ozone oxidation technology for advanced treatment of salt-containing organic wastewater.
The research of the inventor finds that the surface modification is carried out on the active carbon, the aluminum oxide, the molecular sieve, the medical stone or other carriers, the Ca salt is used as the metal active component, the green and efficient novel Ca-based ozone oxidation catalyst can be prepared, the catalyst can be used for the advanced treatment of salt-containing organic wastewater, and has the advantages of good catalytic performance, high catalytic efficiency, high stability and repeated recycling.
Therefore, the ozone oxidation catalyst for the advanced treatment of the organic wastewater containing salt according to the first aspect of the invention is composed of a carrier and a metal active component loaded on the carrier, wherein the metal active component is calcium oxide.
The Ca-based catalysts provided herein are heterogeneous catalysts that have higher catalytic activity than conventional CaO catalysts by having Ca-N sites in addition to Ca-O sites. In this catalyst, the calcium oxide may be represented as CaO, where the active sites of the catalyst are Ca-Oy-Nx-C (x + y ═ 4) where x is the number of N atoms coordinated to the Ca atom, values ranging from 0 to 4; y is the number of O atoms coordinated with the Ca atom and takes a value of 0-4. The catalyst has high catalytic efficiency and high stability, and can be recycled.
According to the invention, the support is surface-modified; preferably, the surface modification is based on coating polymerization of a modifier on the surface of the carrier, and a group with stronger anchoring traction effect on calcium ions is formed on the surface of the carrier; further preferably, the group having strong anchoring traction effect on calcium ions comprises amino and/or hydroxyl; still further preferably, the modifying agent comprises one or more of dopamine hydrochloride, chitosan and gelatin.
The above catalyst can be represented by the carrier-amino compound and/or hydroxy compound-CaO; preferably, the catalyst can be represented by the carrier-PDA-CaO.
In the invention, the carrier comprises one or more of active carbon, aluminum oxide, molecular sieve, medical stone and other carriers.
In some embodiments of the invention, the specific surface area of the ozone oxidation catalyst is 140-160m2Per g, preferably from 145.74 to 160m2Per g, pore volume of 0.4-0.6cm3Per g, preferably 0.45-0.6cm3/g。
The second aspect of the present invention relates to a method for producing an ozone oxidation catalyst according to the first aspect of the present invention, comprising (see fig. 1):
step A, fully washing a carrier with water, drying and roasting to obtain a pretreated carrier;
step B, placing the pretreated carrier in a buffer solution, stirring, adding a modifier, oscillating, filtering, washing and drying to obtain a surface-modified carrier;
step C, placing the modified carrier in a carrier containing Ca2+Oscillating, standing and aging the solution to obtain a catalyst precursor;
and D, drying the catalyst precursor, and roasting to obtain the ozone oxidation catalyst.
According to the invention, in the step A, drying is carried out under vacuum conditions, wherein the drying temperature is 120 ℃, and the drying time is 6-12 h; the roasting temperature is 350 ℃, and the roasting time is 2-5 h.
Specifically, the pretreatment process of the carrier of the present invention is based on the washing, drying and roasting processes: the catalyst carrier is placed in a beaker, fully washed for 1-3 times by using deionized water to remove surface impurities, dried for 6-12 hours at 60-120 ℃ in a vacuum drying box, and then placed in a muffle furnace for roasting at 200-350 ℃ for 1-5 hours to realize the dredging of carrier pore channels and the removal of organic impurities.
As a further improvement of the invention, the surface modification of the carrier is proposed in the preparation process of the catalyst, and groups with metal ion complexing action, such as amino, hydroxyl and the like, are utilized to pull and anchor metal ions, so that a uniformly dispersed environment is provided for the loading of metal active components, the interaction between the catalyst active components and the carrier is favorably enhanced, and the stability and the activity of the catalyst are improved.
In some embodiments of the invention, in step B, the mass ratio of the modifying agent to the carrier is 1: 20; the stirring time is 2-12 h; oscillating in a shaking table at the temperature of 20-35 ℃ for 2-12 h; drying under vacuum condition at 40-80 deg.C for 6-12 h.
Specifically, the carrier surface modification process of the present invention is based on the polymerization process of dopamine in alkaline solution (the formed polymeric chain has amino and hydroxyl groups, etc.): dispersing the pretreated catalyst carrier in Tri-HCl solution, fully stirring for 2-12h, adding dopamine hydrochloride into a conical flask, oscillating for 2-12h at 20-35 ℃ in a shaking table, filtering, washing with water and ethanol, and drying in a vacuum drying oven at 40-80 ℃ for 6-12h to obtain a surface-modified carrier; preferably, the molar ratio of dopamine hydrochloride to carrier is (10-100): (1-10).
As a further improvement of the invention, the Ca metal salt is used as a metal precursor to construct a main active site in the preparation process of the heterogeneous catalyst, and the adding concentration is 0.05-0.5 mol/L.
In the present invention, the component containing Ca2+The solution of (a) is prepared by dissolving anhydrous calcium chloride in water.
In some embodiments of the invention, in step C, Ca is contained2+Ca in solution of (2)2+The concentration is 0.05-0.3 mol/L; preferably, the modified vector is mixed with Ca2+The dosage ratio of the solution of (1) is 0.3 g/mL; and/or the oscillation time is 6-12 h; standing and aging for 2-24 h.
In still other embodiments of the present invention, in step D, the calcination is performed under an inert gas atmosphere, and the calcination temperature is 600-1000 ℃; the roasting time is 1-5 h.
The third aspect of the invention provides the use of the ozone oxidation catalyst according to the first aspect of the invention or the ozone oxidation catalyst prepared by the preparation method according to the second aspect of the invention in the advanced treatment of salt-containing organic wastewater; it may be understood as a method for advanced treatment of wastewater using the ozone oxidation catalyst according to the first aspect of the present invention or the ozone oxidation catalyst prepared by the preparation method according to the second aspect of the present invention.
Specifically, the application comprises the steps of filling an ozone oxidation catalyst in a wastewater treatment device, introducing wastewater, introducing ozone, and carrying out ozone oxidation treatment on the wastewater to obtain oxidized effluent meeting the discharge standard.
The salt-containing organic wastewater in the present invention includes, but is not limited to, petrochemical wastewater, biochemical effluent and/or chemical wastewater.
In some embodiments of the invention, the reaction conditions of the ozonation process are: COD of the wastewater: 140-160mg/L, TDS: 3430 and 3450mg/L of ammonia, the pH value is 7, the ozone flow is 0.03L/min, the catalyst loading is 400g/L, the reaction time is 60min, and the ozone adding ratio is 0.6-4.2.
The invention mainly improves the dispersion degree of the metal active component by a surface modification method and enhances the interaction of the active component and the carrier, thereby obtaining the catalyst with high activity and good stability. The catalyst is prepared by performing surface modification on active carbon, aluminum oxide, a molecular sieve, medical stone or other carriers and taking Ca salt as a metal active component. The catalyst is prepared by a simple process flow, can be quickly prepared by a conventional impregnation method, has good catalytic performance for the deep treatment of the salt-containing organic wastewater, is good in stability and reusable, does not observe the reduction of activity within 20 cycles, and is suitable for industrial popularization.
Examples
The present invention is further illustrated by the following figures and examples. The experimental methods described below are, unless otherwise specified, all routine laboratory procedures. The experimental materials described below, unless otherwise specified, are commercially available.
In the following examples, COD determination was performed using a DR5000 uv spectrophotometer (hashes) after digestion with a hashed COD reagent on a hashdrb 200 digester (hashes). TDS measurement was carried out using a model DDSJ-319L conductivity meter (Shanghai Reye instruments Co., Ltd.). The COD removal rate was calculated according to the following formula:
COD removal rate (COD)Original-CODAfter oxidation)/CODOriginal×100％
Example 1:
the preparation and performance measurement of the catalyst are carried out by using medical stone (1-3mm) as a carrier.
(1) Putting medical stone into deionized water, fully washing for 3 times, removing dust, drying in a vacuum drying oven at 120 ℃ for 6 hours, roasting in a muffle furnace at 350 ℃ for 5 hours, and removing organic impurities in pore passages and surfaces to obtain a pretreated carrier;
(2) placing the pretreated medical stone in a Tri-HCl buffer solution of 5mmol/L, fully stirring for 1h, adding 0.1mol of dopamine hydrochloride into a conical flask, oscillating for 12h at 25 ℃ in a shaking table, filtering, washing with water and ethanol, and drying in a vacuum drying oven at 80 ℃ for 12h to obtain a surface-modified carrier;
(3) placing the modified Maifanitum in Ca-containing solution2+In solution of (2), Ca2+The concentration is 0.1mol/L, and the mixture is fully oscillated for 12 hours;
(4) and drying the catalyst, placing the dried catalyst in a tubular furnace in an inert gas atmosphere, and roasting the catalyst for 2 hours at 800 ℃ to obtain a medical stone-PDA-CaO catalyst sample.
Reaction conditions are as follows: biochemical effluent of petrochemical wastewater, COD: 140-160mg/L, TDS: 3430-3450mg/L, volume of wastewater: 50mL, pH 7, ozone flow rate of 0.03L/min, catalyst loading of 600g/L, reaction time of 60min, and ozone addition ratio of 2.9.
The experiment result shows that the removal rate of the COD of the medical stone-PDA-CaO catalyst is 46.7%.
Example 2:
and (3-5mm) aluminum oxide is used as a carrier for catalyst preparation and performance measurement.
(1) Putting aluminum oxide into deionized water, fully washing for 3 times to remove dust, drying in a vacuum drying oven at 120 ℃ for 6-10h, then roasting in a muffle furnace at 350 ℃ for 2-5h, and removing organic impurities in a pore channel and the surface to obtain a pretreated carrier;
(2) placing the pretreated carrier in a Tri-HCl buffer solution of 5-50mmol/L, fully stirring for 0.5-5h, adding 0.05-0.5mol dopamine hydrochloride into a conical flask, oscillating for 2-12h at 20-35 ℃ in a shaking table, filtering, washing with water and ethanol, and drying for 6-12h at 40-80 ℃ in a vacuum drying oven to obtain a surface-modified carrier;
(3) placing the modified carrier in a carrier containing Ca2+In solution of (2), Ca2+The concentration is between 0.05 and 0.3mol/L, after fully oscillating for 6 to 12 hours, standing and aging for 2 to 24 hours;
(4) drying the catalyst, placing the dried catalyst in a tubular furnace in an inert gas atmosphere, and roasting at the temperature of 600-1000 ℃ for 1-5h to obtain Al2O3Samples of PDA-CaO catalyst.
Reaction conditions are as follows: biochemical effluent of petrochemical wastewater, COD: 140-160mg/L, TDS: 3430-3450mg/L, volume of wastewater: 50mL, pH 7, ozone flow rate of 0.03L/min, catalyst loading of 400g/L, reaction time of 60min, and ozone addition ratio of 0.6-4.2.
The experimental result shows that Al2O3The COD removal rate of the PDA-CaO catalyst is between 48.1 and 55 percent, and when the adding ratio is 2.9, Al is added2O3The highest COD removal rate of the PDA-CaO catalyst is 55 percent. When the adding ratio is 0.6, the COD removal rate can still reach 48.1 percent.
Example 3:
and (3-5mm) aluminum oxide is used as a carrier for catalyst preparation and performance measurement.
(1) Putting aluminum oxide into deionized water, fully washing for 3 times to remove dust, drying in a vacuum drying oven at 120 ℃ for 6-12h, then roasting in a muffle furnace at 350 ℃ for 2-5h, and removing organic impurities in a pore channel and the surface to obtain a pretreated carrier;
(2) placing the pretreated carrier in a Tri-HCl buffer solution of 5-50mmol/L, fully stirring for 0.5-5h, adding 0.05-0.5mol dopamine hydrochloride into a conical flask, oscillating for 2-12h at 20-35 ℃ in a shaking table, filtering, washing with water and ethanol, and drying for 6-12h at 40-80 ℃ in a vacuum drying oven to obtain a surface-modified carrier;
(3) placing the modified carrier in a carrier containing Ca2+In solution of (2), Ca2+The concentration is between 0.05 and 0.3mol/L, after fully oscillating for 6 to 12 hours, standing and aging for 2 to 24 hours;
(4) drying the catalyst, placing the dried catalyst in a tubular furnace in an inert gas atmosphere, and roasting at the temperature of 600-1000 ℃ for 1-5h to obtain Al2O3Samples of PDA-CaO catalyst.
Reaction conditions are as follows: biochemical effluent of petrochemical wastewater, COD: 140-160mg/L, TDS: 3430-3450mg/L, volume of wastewater: 50mL, pH 7, ozone flow rate of 0.03L/min, catalyst loading of 100-.
The experimental result shows that Al2O3The COD removal rate of the PDA-CaO catalyst is between 7.8 and 56 percent, when the adding amount of the catalyst is 400-g/L, the COD removal rate is increased along with the increase of the adding amount of the catalyst, and when the adding amount of the catalyst is 400-g/L, the adding amount is further increased, and the COD removal rate is basically unchanged, mainly because after the adding amount of the catalyst is increased, the active sites are increased, and meanwhile, the contact time with ozone molecules is longer, so that the adsorption conversion of ozone is facilitated. When the adding amount of the catalyst is 100g/L, the removal rate of COD is lower and is 7.8 percent,the reason for this is that the residence time of ozone in the catalyst layer is short, not contributing to the decomposition and conversion of ozone, in addition to the small number of active sites. Therefore, the dosage is 400g/L, and the COD removal rate is 56%.
Example 4:
and (3-5mm) aluminum oxide is used as a carrier for catalyst preparation and performance measurement.
(1) Putting aluminum oxide into deionized water, fully washing for 3 times to remove dust, drying in a vacuum drying oven at 120 ℃ for 6-12h, then roasting in a muffle furnace at 350 ℃ for 2-5h, and removing organic impurities in a pore channel and the surface to obtain a pretreated carrier;
(2) placing the pretreated carrier in a Tri-HCl buffer solution of 5-50mmol/L, fully stirring for 0.5-5h, adding 0.05-0.5mol dopamine hydrochloride into a conical flask, oscillating for 2-12h at 20-35 ℃ in a shaking table, filtering, washing with water and ethanol, and drying for 6-12h at 40-80 ℃ in a vacuum drying oven to obtain a surface-modified carrier;
(3) placing the modified carrier in a carrier containing Ca2+In solution of (2), Ca2+The concentration is between 0.05 and 0.3mol/L, after fully oscillating for 6 to 12 hours, standing and aging for 2 to 24 hours;
(4) drying the catalyst, placing the dried catalyst in a tubular furnace in an inert gas atmosphere, and roasting at the temperature of 600-1000 ℃ for 1-5h to obtain Al2O3Samples of PDA-CaO catalyst.
Reaction conditions are as follows: biochemical effluent of petrochemical wastewater, COD: 140-160mg/L, TDS: 3430-3450mg/L, volume of wastewater: 50mL, 3-9 pH, 0.03L/min ozone flow, 400g/L catalyst loading, 60min reaction time, and 2.9 ozone addition ratio.
The experimental result shows that the pH has great influence on the removal rate of COD, and Al2O3The COD removal rate of the PDA-CaO catalyst is between 26.3 and 58.1 percent. The COD removal rate gradually increased with increasing pH, indicating that the alkaline environment favors the conversion of ozone to active free radicals. Because the original pH value of the wastewater is about 7, the ozone catalysis process is facilitated, so that the ozone catalysis reaction is carried out under the original pH value without adding a pH regulator, and the COD removal rate is 56-62%.
It was examined that the specific surface area of the ozone oxidation catalyst prepared in the above examples 1 to 4 was 140-160m2Per g, pore volume of 0.4-0.6cm3/g。
Example 5:
two commercially available catalysts (3-5mm, Mn/ceramsite catalyst and Ni-Mn/Al)2O3Catalyst) is reacted with Al under the same reaction conditions2O3Comparison of COD removal Performance of PDA-CaO catalyst (catalyst obtained according to the preparation procedure of example 4, COD removal rate between 56% and 62%).
Reaction conditions are as follows: biochemical effluent of petrochemical wastewater, COD: 140-160mg/L, TDS: 3430-3450mg/L, volume of wastewater: 50mL, pH 7, ozone flow rate of 0.03L/min, catalyst loading of 400g/L, reaction time of 60min, and ozone addition ratio of 2.9.
As shown in FIG. 2, Al is comparable to the commercial catalyst2O3The PDA-CaO catalyst has good COD removal performance, the COD removal rate is 62% aiming at biochemical effluent of petrochemical wastewater, the PDA-CaO catalyst has good stability and activity, the PDA-CaO catalyst can be repeatedly used, and no activity reduction is observed in 20 cycles.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims (10)

1. An ozone oxidation catalyst for advanced treatment of organic wastewater containing salt comprises a carrier and a metal active component loaded on the carrier, wherein the metal active component is calcium oxide.
2. The ozone oxidation catalyst according to claim 1, wherein the carrier is surface-modified; preferably, the surface modification is based on coating polymerization of a modifier on the surface of the carrier, and a group with stronger anchoring traction effect on calcium ions is formed on the surface of the carrier; further preferably, the group having strong anchoring traction effect on calcium ions comprises amino and/or hydroxyl; still further preferably, the modifying agent comprises one or more of dopamine hydrochloride, chitosan and gelatin.
3. The ozonation catalyst of claim 2, wherein the specific surface area of the ozonation catalyst is 140-160m2Per g, pore volume of 0.4-0.6cm3/g。
4. The method for producing an ozone oxidation catalyst according to any one of claims 1 to 3, comprising:
step A, fully washing a carrier with water, drying and roasting to obtain a pretreated carrier;
step B, placing the pretreated carrier in a buffer solution, stirring, adding a modifier, oscillating, filtering, washing and drying to obtain a surface-modified carrier;
step C, placing the modified carrier in a carrier containing Ca2+Oscillating, standing and aging the solution to obtain a catalyst precursor;
and D, drying the catalyst precursor, and roasting to obtain the ozone oxidation catalyst.
5. The preparation method according to claim 4, wherein in the step A, the drying is carried out under vacuum, the drying temperature is 120 ℃, and the drying time is 6-12 h; and/or the roasting temperature is 350 ℃, and the roasting time is 2-5 h.
6. The method according to claim 4, wherein in step B, the ratio of the modifying agent to the carrier is 1:20 by mass; and/or the stirring time is 2-12 h; and/or oscillating in a shaking table at the temperature of 20-35 ℃ for 2-12 h; and/or drying under vacuum condition, wherein the drying temperature is 40-80 ℃, and the drying time is 6-12 h.
7. The method according to claim 4, wherein in the step C, Ca is contained2+Ca in solution of (2)2+The concentration is 0.05-0.3 mol/L; preferably, the modified vector is mixed with Ca2+The dosage ratio of the solution of (1) is 0.3 g/mL; and/or the oscillation time is 6-12 h; and/or the standing and aging time is 2-24 h.
8. The preparation method as claimed in claim 4, wherein in step D, the roasting is carried out under an inert gas atmosphere, and the roasting temperature is 600-1000 ℃; and/or the roasting time is 1-5 h.
9. Use of the ozone oxidation catalyst according to any one of claims 1 to 3 or the ozone oxidation catalyst prepared by the preparation method according to any one of claims 4 to 8 in the advanced treatment of salt-containing organic wastewater; preferably, the application comprises filling an ozone oxidation catalyst in the wastewater treatment device, introducing wastewater, introducing ozone, and performing ozone oxidation treatment on the wastewater to obtain oxidized effluent meeting the discharge standard.
10. The use according to claim 9, wherein the reaction conditions of the ozone oxidation treatment are: COD of the wastewater: 140-160mg/L, TDS: 3430 and 3450mg/L of ammonia, the pH value is 7, the ozone flow is 0.03L/min, the catalyst loading is 400g/L, the reaction time is 60min, and the ozone adding ratio is 0.6-4.2.
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