CN114405494B - 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 PDFInfo
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- CN114405494B CN114405494B CN202210112168.6A CN202210112168A CN114405494B CN 114405494 B CN114405494 B CN 114405494B CN 202210112168 A CN202210112168 A CN 202210112168A CN 114405494 B CN114405494 B CN 114405494B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 148
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000002351 wastewater Substances 0.000 title claims abstract description 56
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 51
- 230000003647 oxidation Effects 0.000 title claims abstract description 50
- 150000003839 salts Chemical class 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000011575 calcium Substances 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 30
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000292 calcium oxide Substances 0.000 claims abstract description 20
- 230000004048 modification Effects 0.000 claims abstract description 11
- 238000012986 modification Methods 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims description 45
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- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical group Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 10
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- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910001424 calcium ion Inorganic materials 0.000 claims description 7
- 238000004873 anchoring Methods 0.000 claims description 6
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- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
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- 108700028369 Alleles Proteins 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910003286 Ni-Mn Inorganic materials 0.000 description 1
- 238000001016 Ostwald ripening Methods 0.000 description 1
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- 229940072056 alginate Drugs 0.000 description 1
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- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
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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
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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
- B01J35/60—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
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- 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
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- 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 salt-containing organic wastewater, 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 between the active component and the carrier, thereby obtaining the catalyst with high activity and good stability. The catalyst is prepared by carrying out surface modification on active carbon, aluminum oxide, molecular sieve, medical stone or other carriers and taking Ca salt as a metal active component. The preparation method of the catalyst has simple process flow, can realize the rapid preparation of the catalyst by adopting a conventional impregnation method, is oriented to the advanced treatment of the organic wastewater containing salt, has good catalytic performance, and is suitable for industrialized popularization.
Description
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 preparation thereof, and in particular relates to an ozone oxidation catalyst for advanced treatment of salt-containing organic wastewater and a preparation method and application thereof.
Background
The organic wastewater containing salt is derived from the high-consumption water industries such as petrifaction, textile printing and dyeing and the like, and has the characteristics of high salt content, high toxicity, difficult degradation and the like. The ten committees such as the committee for improvement of the industry and the like jointly release guiding opinion (annular resource (2021) 13) on the resource utilization of the advanced wastewater, and the opinion focuses on the recycling of industrial wastewater in the high-consumption water industries such as petrifaction, papermaking, printing and dyeing, improves the recycling rate and realizes near zero emission. In addition, the country of 4 months in 2015 goes out of the water pollution control action plan, the country of 4 months in 2018 carries out the environmental protection tax law, and meanwhile, the 'zero emission' requirement is correspondingly made in some water-deficient areas according to the characteristics of the local water quality and water quantity, and the emission standard is gradually upgraded and is more strict. In summary, the research on advanced treatment of the organic wastewater containing salt has become an important research direction and development trend in the field of environmental protection, and meets the important strategic requirement of the country of 'building beautiful China'. The organic wastewater containing salt has complex water quality, high chromaticity, high Chemical Oxygen Demand (COD) and Biochemical Oxygen Demand (BOD) and high degradation difficulty, belongs to the industrial wastewater with three-cause toxicity which is difficult to treat, seriously threatens the safety of water environment, and the advanced treatment technology of the wastewater has been widely focused and researched by water treatment workers at home and abroad.
The heterogeneous catalytic ozone oxidation technology has strong oxidizing property, simple operation and small occupied area, is one of the effective modes of advanced treatment of the organic wastewater containing salt, can effectively catalyze ozone to generate free radicals to realize mineralization of organic matters difficult to degrade, and simultaneously overcomes the problems that a catalyst is not easy to recover and is easy to cause secondary pollution and the like caused by homogeneous catalysis, ozone molecules are mainly adsorbed by active sites on the surface of the catalyst, and are decomposed into active free radicals such as hydroxyl free radicals or superoxide free radicals with stronger oxidizing property to react with organic pollutants adsorbed on the surface of the catalyst or in a water body, so that mineralization of the organic pollutants is realized. Therefore, the key of the heterogeneous catalytic ozonation process is a high-efficiency catalyst, and extensive researchers at home and abroad have conducted extensive research on the catalyst.
The heterogeneous catalysts commonly used at present are various, and mainly comprise a single-metal or multi-metal oxide catalyst containing Fe, mn, ce, zn, ti and the like, a carbon-based non-metal catalyst containing N, F and the like, and a catalyst such as MOF and the like. Metal-containing sites (metal ions of generally multivalent form, e.g. Ce 3+ /Ce 4+ Etc.) is predominantly obtained by polyvalent metal ionThe conversion between the molecules provides electrons for ozone molecules to promote the ozone molecules to be decomposed into active free radicals, and the catalyst containing nonmetallic sites such as N, F, S and the like doped carbon nano tubes, graphene-based materials and the like realize the conversion of the ozone molecules into the active free radicals through graphitizing N, thiophene S alleles or other defect sites. In addition, carbon-based materials are also capable of achieving oxidative degradation of organic contaminants by surface adsorbed reactive oxygen species.
The metal oxide catalyst has the most widely applied advantages of low cost, simple synthesis and the like, but the problem of secondary pollution caused by loss of metal active components of the catalyst exists at present: during the roasting process of the metal oxide catalyst, the Ostwald ripening mechanism has agglomeration phenomena with different degrees on the surface of the catalyst, so that the combination degree of the active component and the carrier is weak. In the catalytic oxidation process, due to factors such as collision, infirm combination degree and the like, the metal active components can be separated from the surface of the carrier, so that loss of different degrees is caused, secondary pollution is formed, and the subsequent treatment is difficult. In view of this problem, researchers have been actively exploring the influence of different synthesis methods on the stability of the catalyst, such as impregnation, hydrothermal, coprecipitation, sol-gel, template, etc., from the viewpoint of enhancing the degree of bonding between the metal component and the support. For example Chen [4] Et al (Chen Weirui, etc. minimization of salicylic acid via catalytic ozonation with Fe-Cu@SiO) 2 core-shell catalyst: A two-stage first order reaction. Chemosphere,2019, 235:470-480) synthesizes Fe-Cu@SiO by a template method 2 Interfacial coupling between iron oxide and copper oxide and SiO 2 The 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@SiO 2 The TOC removal rate of the catalyst is Cu@SiO 2 1.1 times of Fe@SiO 2 1.5 times of (2). And Fe-Cu@SiO 2 Concentration of metal ion leached by catalyst is higher than that of single metal Cu@SiO 2 、Fe@SiO 2 The catalyst is reduced by more than one time. At the same time, researchers have attempted to modify catalysts accordingly.For example Li et al (Li Shangyi, etc. mechanism of synergistic effect on electron transfer over Co-Ce/MCM-48during ozonation of pharmaceuticals in water.ACS Applied Materials)&Interface, 2019,11 (27): 23957-23971) Co ions are introduced by an impregnation method to modify the Ce/MCM-48 catalyst, so that the COD removal rate is improved and the metal leaching rate of the catalyst is reduced. Moussavig et al (Moussavigholamreza, etc. the catalytic destruction of antibiotic tetracycline by sulfur-doped manganese oxide (S-MgO) nanoparticles. Journal of Environmental Management,2018, 210:131-138) prepared an S-MgO catalyst by introducing the S element into MgO, 100% removal of tetracycline and 86.4% TOC removal can be achieved in 60 min. Compared with MgO catalyst, the S element greatly increases the oxygen vacancy number of the MgO catalyst, and the TOC removal rate is improved by nearly 70%. Therefore, the improvement of the catalyst synthesis method and the catalyst modification are effective ways for further improving 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 leaching of the metal component still exist, so the problem of the loss of the active component of the catalyst cannot be fundamentally solved by simply introducing the metal or the nonmetal element.
In addition, during the long-period ozone catalytic oxidation process, due to factors such as collision, the active components of the catalyst can be leached in a trace amount, if the active components are accumulated in water and damage to the water environment is still caused, so that a green and efficient metal component needs to be searched for to replace a conventional transition metal oxide to serve as an active center of the ozone catalytic oxidation. The calcium compound is cheap and easy to obtain, the calcium ion has no pollution to water environment basically, contains strong alkaline sites, and can be used as a green and efficient metal active component. At present, the related research on the calcium compound as an ozone catalyst is less, and the calcium compound is mainly used as a catalyst auxiliary agent to improve the stability or the hydroxide of the calcium is used as a pH regulator to promote the ozone to generate active free radicals. For example Marcio et al (CintiaAndreia Alves Pereira, marcioBarrett-Rodrigues, etc. application of Zero Valent Iron (ZVI) immobilized in Ca-Alginate beads for C.I. reactive Red 195catalytic degradation in an air lift reactor operated with ozone.Journal of Hazardous Materials,2)021, 401:123275) with Ca 2+ The cross-linking agent is used for preparing an ozone catalyst with zero-valent iron as an active center, and ozone is converted into active free radicals mainly through the action of the zero-valent iron so as to realize the oxidative degradation of organic pollutants. Patent CN103351051A with Ca (OH) 2 As an ozone catalyst in the liquid phase, the biochemical effluent of a certain garbage incineration power plant is degraded, and the removal rate is 58%. It is mainly made up of Ca (OH) 2 Dissociation to produce OH - Forming alkaline environment, promoting ozone to generate active free radical to realize pollutant degradation, while Ca 2+ CaCO formation with carbonate in wastewater 3 Precipitation, ca 2+ Does not act as an active center in the process to promote ozone to generate active free radicals; and, it has Ca 2+ The problem of loss can increase the hardness of the wastewater, and the subsequent treatment is difficult; meanwhile, ca (OH) needs to be continuously added 2 And cannot be reused.
Disclosure of Invention
One of the purposes of the invention is to provide an ozone oxidation catalyst for advanced treatment of salt-containing organic wastewater, aiming at the problems existing in the prior art; compared with the traditional single metal oxide catalyst, the catalyst has high catalytic efficiency and high stability, and can remarkably 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 saline organic wastewater, the ozone oxidation catalyst for the advanced treatment of the saline organic wastewater 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 first aspect of the present invention provides an ozone oxidation catalyst for advanced treatment of salt-containing organic wastewater, which is composed of a carrier, and a metal active component supported on the carrier, wherein the metal active component is calcium oxide.
According to the invention, the carrier is modified via a surface; preferably, the surface modification is based on coating polymerization of a modifier on the surface of a carrier, and a group with strong anchoring traction effect on calcium ions is formed on the surface of the carrier; further preferably, the group having a strong anchoring traction on calcium ions includes amino and/or hydroxyl; still more preferably, the modifier comprises one or more of dopamine hydrochloride, chitosan and gelatin.
In some embodiments of the invention, the ozone oxidation catalyst has a specific surface area of 140-160m 2 Per gram, pore volume of 0.4-0.6cm 3 /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 the 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 carrier with a modified surface;
step C, placing the modified carrier in a carrier containing Ca 2+ Oscillating, standing and aging to obtain a catalyst precursor;
and D, drying the catalyst precursor, and roasting to obtain the ozone oxidation catalyst.
According to the invention, in step A, drying is carried out under vacuum, the drying temperature is 120 ℃, and the drying time is 6-12 hours; and/or the roasting temperature is 350 ℃, and the roasting time is 2-5h.
In some embodiments of the invention, in step B, the mass ratio of the modifier to the carrier is 1:20; and/or the stirring time is 2-12h; and/or oscillating in a shaking table, wherein the oscillating temperature is 20-35 ℃ and the oscillating time is 2-12 hours; and/or drying under vacuum, wherein the drying temperature is 40-80 ℃, and the drying time is 6-12h.
In some embodiments of the invention, in step C, ca is contained 2+ Ca in solution of (C) 2+ The concentration is 0.05-0.3mol/L; preferably, the modified vector is combined with a Ca-containing vector 2+ The dosage ratio of the solution of (2) is 0.3g/mL; and/or, oscillating for 6-12h; and/or, standing and aging for a period of time of2-24h。
In some embodiments of the invention, in step D, firing is performed under an inert gas atmosphere, the firing temperature being 600-1000 ℃; and/or, the roasting time is 1-5h.
In a third aspect, the invention provides the use of an ozone oxidation catalyst according to the first aspect of the invention or prepared by a preparation method according to the second aspect of the invention in the deep treatment of salty 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 emission standard.
In some embodiments of the invention, the reaction conditions for the ozone oxidation treatment are: COD of the wastewater: 140-160mg/L, TDS:3430-3450mg/L, pH=7, ozone flow of 0.03L/min, catalyst loading of 400g/L, reaction time of 60min, ozone addition ratio of 0.6-4.2.
The beneficial effects of the invention are as follows:
the Ca-based metal oxide ozone catalyst prepared based on the surface modification of the carrier has the advantages of high catalytic efficiency, high stability, simple preparation and the like compared with the traditional single metal oxide catalyst, and can remarkably reduce the treatment cost of an ozone method. In addition, the porous material used for the catalyst carrier has higher specific surface area and larger pore volume, has good adsorption capacity, enriches pollutants on the surface of the catalyst, and can obviously assist in the catalytic oxidation reaction.
Drawings
The invention is described in further detail below with reference to the accompanying drawings:
fig. 1 shows a catalyst preparation flow.
FIG. 2 is a graph showing the comparison of the removal performance of COD of the catalyst.
Detailed Description
In order that the invention may be readily understood, a detailed description of the invention will be provided below with reference to the accompanying drawings and examples. Before the present 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 defined otherwise, all terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. 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.
I terminology
The term "TDS" (Total dissolved solids ), also known as total dissolved solids, as used herein is measured in milligrams per liter (mg/L), which indicates how much milligrams of dissolved solids are dissolved in 1 liter of water. The higher the TDS value, the more dissolved substances contained in the water. Total dissolved solids refers to the total amount of all solutes in water, including both inorganic and organic content. The conductivity value is generally used to approximate the salt content of the solution, and in general, the higher the conductivity, the higher the TDS. Thus, TDS also reflects the salt level in the wastewater.
The term "advanced wastewater treatment" as used herein generally refers to a treatment of secondary effluent after biochemical treatment or the like by further treating the remaining organic matter by a technique such as advanced oxidation or the like.
The term "PDA" as used herein refers to polydopamine formed by polymerization of dopamine hydrochloride under alkaline conditions.
The term "water" as used herein refers to deionized water, distilled water or ultrapure water unless otherwise specified.
II. Embodiment
As mentioned above, existing ozone oxidation catalysts are not satisfactory and there are always one or more problems, such as the presence of Ca 2+ The problem of loss can increase the hardness of the wastewater, and the subsequent treatment is difficult; meanwhile, ca (OH) needs to be continuously added 2 Cannot be reused, etc.; in view of this, the present inventors have conducted a great deal of ozone oxidation technology for advanced treatment of salt-containing organic wastewaterIs a study of (a).
The inventor researches and discovers that the novel green and efficient Ca-based ozone oxidation catalyst can be prepared by carrying out surface modification on activated carbon, aluminum oxide, molecular sieve, medical stone or other carriers and taking Ca salt as a metal active component, and 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 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 supported on the carrier, wherein the metal active component is calcium oxide.
The Ca-based catalysts provided herein are heterogeneous catalysts having Ca-N sites in addition to Ca-O sites, and have higher catalytic activity than conventional CaO catalysts. In the catalyst, the calcium oxide may be expressed as CaO, wherein the active site of the catalyst is Ca-O y -N x -C (x+y=4), wherein x is the number of N atoms coordinated with Ca atoms, and has a value of 0 to 4; y is the number of O atoms coordinated with Ca atoms, and the value is 0-4. The catalyst has high catalytic efficiency and high stability, can be recycled and reused.
According to the invention, the carrier is modified via a surface; preferably, the surface modification is based on coating polymerization of a modifier on the surface of a carrier, and a group with strong anchoring traction effect on calcium ions is formed on the surface of the carrier; further preferably, the group having a strong anchoring traction on calcium ions includes amino and/or hydroxyl; still more preferably, the modifier comprises one or more of dopamine hydrochloride, chitosan and gelatin.
The above catalyst may be expressed as a carrier-amino compound and/or hydroxy compound-CaO; preferably, the above catalyst may be expressed as a support-PDA-CaO.
In the invention, the carrier comprises one or more of active carbon, aluminum oxide, molecular sieve, medical stone and other carriers.
In the present inventionIn some embodiments, the ozone oxidation catalyst has a specific surface area of 140-160m 2 /g, preferably 145.74-160m 2 Per gram, pore volume of 0.4-0.6cm 3 Preferably 0.45-0.6 cm/g 3 /g。
The preparation method of the ozone oxidation catalyst according to the first aspect of the invention according to the second aspect of the invention comprises (see fig. 1):
step A, fully washing the 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 carrier with a modified surface;
step C, placing the modified carrier in a carrier containing Ca 2+ Oscillating, standing and aging to obtain a catalyst precursor;
and D, drying the catalyst precursor, and roasting to obtain the ozone oxidation catalyst.
According to the invention, in step A, drying is carried out under vacuum, the drying temperature is 120 ℃, and the drying time is 6-12 hours; the roasting temperature is 350 ℃, and the roasting time is 2-5h.
Specifically, the carrier pretreatment process of the invention is based on the water washing, drying and roasting processes: placing the catalyst carrier in a beaker, fully washing the catalyst carrier with deionized water for 1-3 times, removing surface impurities, drying the catalyst carrier in a vacuum drying oven at 60-120 ℃ for 6-12 hours, and then placing the catalyst carrier in a muffle furnace for roasting at 200-350 ℃ for 1-5 hours to realize carrier pore channel dredging and organic impurity removal.
As a further improvement of the invention, the surface modification of the carrier is proposed in the preparation process of the catalyst, and the groups with metal ion complexation such as amino, hydroxyl and the like are utilized to drag and anchor metal ions, so that a uniformly dispersed environment is provided for the loading of the metal active components, the interaction between the catalyst active components and the carrier is 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 modifier to the carrier is 1:20; the stirring time is 2-12h; oscillating in a shaking table, wherein the oscillating temperature is 20-35 ℃, and oscillating for 2-12h; drying under vacuum, wherein the drying temperature is 40-80 ℃, and the drying time is 6-12h.
Specifically, the carrier surface modification process of the present invention is based on the polymerization process of dopamine in an alkaline solution (the formed polymeric chain has amino groups, hydroxyl groups, etc.): dispersing the pretreated catalyst carrier in a 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 for 6-12h at 40-80 ℃ in a vacuum drying oven to obtain a carrier with a modified surface; preferably, the molar ratio of dopamine hydrochloride to carrier is (10-100): (1-10).
As a further improvement of the invention, in the preparation process of the heterogeneous catalyst, the main active site is creatively constructed by taking Ca metal salt as a metal precursor, and the adding concentration is 0.05-0.5mol/L.
In the present invention, the Ca-containing material 2+ Is prepared by dissolving anhydrous calcium chloride in water.
In some embodiments of the invention, in step C, ca is contained 2+ Ca in solution of (C) 2+ The concentration is 0.05-0.3mol/L; preferably, the modified vector is combined with a Ca-containing vector 2+ The dosage ratio of the solution of (2) is 0.3g/mL; and/or, oscillating for 6-12h; the standing aging time is 2-24h.
In still other embodiments of the present invention, in step D, the firing is performed under an inert gas atmosphere, the firing temperature being 600-1000 ℃; the roasting time is 1-5h.
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 deep treatment of salt-containing organic wastewater; it is understood as a method for the 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 emission standard.
The organic wastewater containing salt in the invention comprises, but is not limited to biochemical effluent of petrochemical wastewater and/or chemical wastewater.
In some embodiments of the invention, the reaction conditions for the ozone oxidation treatment are: COD of the wastewater: 140-160mg/L, TDS:3430-3450mg/L, pH=7, ozone flow of 0.03L/min, catalyst loading of 400g/L, reaction time of 60min, ozone addition ratio of 0.6-4.2.
The invention improves the dispersion degree of the metal active component by a surface modification method and enhances the interaction between the active component and the carrier, thereby obtaining the catalyst with high activity and good stability. The catalyst is prepared by carrying out surface modification on active carbon, aluminum oxide, molecular sieve, medical stone or other carriers and taking Ca salt as a metal active component. The preparation method of the catalyst has simple process flow, can realize rapid preparation of the catalyst by adopting a conventional impregnation method, is oriented to advanced treatment of the organic wastewater containing salt, has good catalytic performance, has good catalyst stability, can be repeatedly used, does not observe activity reduction in 20 cycles, and is suitable for industrialized popularization.
Examples
The invention is further illustrated by the following figures and examples. The experimental methods described below, unless otherwise specified, are all laboratory routine methods. The experimental materials described below, unless otherwise specified, are commercially available.
In the following examples, COD measurement was performed using a DR5000 ultraviolet spectrophotometer (american hashing company) after digestion on a hash DRB200 digestion instrument (american hashing company) using a hash COD reagent. TDS determination was performed using a DDSJ-319L conductivity meter (Shanghai Lei Ci instruments Co., ltd.). The COD removal rate was calculated according to the following formula:
COD removal Rate= (COD Original, original -COD After oxidation )/COD Original, original ×100％
Example 1:
the preparation and performance measurement of the catalyst are carried out by taking medical stone (1-3 mm) as a carrier.
(1) Placing medical stone in deionized water for full 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 on the pore channels and the surfaces to obtain a pretreated carrier;
(2) Placing pretreated medical stone into 5mmol/L of Tri-HCl buffer solution, 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 for 12h at 80 ℃ in a vacuum drying oven to obtain a carrier with a modified surface;
(3) Placing modified Maifanitum into a solution containing Ca 2+ Ca in the solution of (2) 2+ The concentration is 0.1mol/L, and the mixture is fully oscillated for 12 hours;
(4) And drying the catalyst, and then placing the catalyst in a tube furnace under an inert gas atmosphere, and roasting for 2 hours at 800 ℃ to obtain a medical stone-PDA-CaO catalyst sample.
Reaction conditions: biochemical effluent of petrochemical wastewater, COD:140-160mg/L, TDS:3430-3450mg/L, waste water volume: 50mL, pH=7, ozone flow of 0.03L/min, catalyst loading of 600g/L, reaction time of 60min, ozone addition ratio of 2.9.
Experimental results show that the COD removal rate of the medical stone-PDA-CaO catalyst is 46.7%.
Example 2:
alumina (3-5 mm) is used as a carrier for catalyst preparation and performance measurement.
(1) Placing aluminum oxide in deionized water for full washing for 3 times, removing dust, drying in a vacuum drying oven at 120 ℃ for 6-10h, roasting in a muffle furnace at 350 ℃ for 2-5h, removing pore channels and organic impurities on the surface, and obtaining a pretreated carrier;
(2) Placing the pretreated carrier in 5-50mmol/L of Tri-HCl buffer solution, fully stirring for 0.5-5h, adding 0.05-0.5mol of 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 the carrier with modified surface;
(3) Placing the modified carrier in a carrier containing Ca 2+ Ca in the solution of (2) 2+ The concentration is between 0.05 and 0.3mol/L, and after the full oscillation is carried out for 6 to 12 hours, the mixture is stood for aging for 2 to 24 hours;
(4) Drying the catalyst, placing in a tube furnace under inert gas atmosphere, and roasting at 600-1000 ℃ for 1-5h to obtain Al 2 O 3 PDA-CaO catalyst sample.
Reaction conditions: biochemical effluent of petrochemical wastewater, COD:140-160mg/L, TDS:3430-3450mg/L, waste water volume: 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.
Experimental results show that Al 2 O 3 The removal rate of the COD of the PDA-CaO catalyst is between 48.1 and 55 percent, and when the addition ratio is 2.9, the Al 2 O 3 The highest removal rate of COD of the PDA-CaO catalyst is 55 percent. When the addition ratio is 0.6, the COD removal rate still can reach 48.1 percent.
Example 3:
alumina (3-5 mm) is used as a carrier for catalyst preparation and performance measurement.
(1) Placing aluminum oxide in deionized water for full washing for 3 times, removing dust, drying in a vacuum drying oven at 120 ℃ for 6-12h, roasting in a muffle furnace at 350 ℃ for 2-5h, removing pore channels and organic impurities on the surface, and obtaining a pretreated carrier;
(2) Placing the pretreated carrier in 5-50mmol/L of Tri-HCl buffer solution, fully stirring for 0.5-5h, adding 0.05-0.5mol of 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 the carrier with modified surface;
(3) Placing the modified carrier in a carrier containing Ca 2+ Ca in the solution of (2) 2+ The concentration is between 0.05 and 0.3mol/L, and after the full oscillation is carried out for 6 to 12 hours, the mixture is stood for aging for 2 to 24 hours;
(4) Drying the catalyst, placing in a tube furnace under inert gas atmosphere, and roasting at 600-1000 ℃ for 1-5h to obtain Al 2 O 3 PDA-CaO catalyst sample.
Reaction conditions: biochemical effluent of petrochemical wastewater, COD:140-160mg/L, TDS:3430-3450mg/L, waste water volume: 50mL, pH=7, ozone flow rate of 0.03L/min, catalyst loading of 100-500g/L, reaction time of 60min, and ozone addition ratio of 2.9.
Experimental results show that Al 2 O 3 The COD removal rate of the PDA-CaO catalyst is between 7.8 and 56 percent, when the catalyst addition amount is 100 to 400g/L, the COD removal rate is increased along with the increase of the catalyst addition amount, and when the catalyst addition amount is 400 to 500g/L, the addition amount is further increased, and the COD removal rate is basically unchanged, mainly because after the catalyst addition amount is increased, the active site is increased, and the contact time with ozone molecules is longer, thereby being beneficial to the adsorption conversion of ozone. When the adding amount of the catalyst is 100g/L, the COD removal rate is lower and is 7.8%, and the reason is that the residence time of ozone in the catalyst layer is shorter except for few active sites, so that the decomposition and conversion of ozone are not facilitated. Therefore, the addition amount is 400g/L, and the COD removal rate is 56%.
Example 4:
alumina (3-5 mm) is used as a carrier for catalyst preparation and performance measurement.
(1) Placing aluminum oxide in deionized water for full washing for 3 times, removing dust, drying in a vacuum drying oven at 120 ℃ for 6-12h, roasting in a muffle furnace at 350 ℃ for 2-5h, removing pore channels and organic impurities on the surface, and obtaining a pretreated carrier;
(2) Placing the pretreated carrier in 5-50mmol/L of Tri-HCl buffer solution, fully stirring for 0.5-5h, adding 0.05-0.5mol of 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 the carrier with modified surface;
(3) Placing the modified carrier in a carrier containing Ca 2+ Ca in the solution of (2) 2+ The concentration is between 0.05 and 0.3mol/L,fully oscillating for 6-12h, standing and aging for 2-24h;
(4) Drying the catalyst, placing in a tube furnace under inert gas atmosphere, and roasting at 600-1000 ℃ for 1-5h to obtain Al 2 O 3 PDA-CaO catalyst sample.
Reaction conditions: biochemical effluent of petrochemical wastewater, COD:140-160mg/L, TDS:3430-3450mg/L, waste water volume: 50mL, pH=3-9, ozone flow of 0.03L/min, catalyst loading of 400g/L, reaction time of 60min, and ozone addition ratio of 2.9.
Experimental results show that the pH has a larger influence on the COD removal rate, al 2 O 3 The COD removal rate of the PDA-CaO catalyst is between 26.3% and 58.1%. As the pH increases, the COD removal rate increases gradually, and the results indicate that the alkaline environment favors the conversion of ozone to reactive radicals. The original pH value of the wastewater is about 7, which is beneficial to the ozone catalytic process, so that the pH regulator is not added, the ozone catalytic reaction is carried out under the original pH value, and the COD removal rate is 56-62%.
The ozone oxidation catalyst prepared in examples 1 to 4 above had a specific surface area of 140 to 160m 2 Per gram, pore volume of 0.4-0.6cm 3 /g。
Example 5:
two commercial catalysts (3-5 mm, mn/ceramsite catalyst and Ni-Mn/Al) 2 O 3 Catalyst) is reacted with Al under the same reaction conditions 2 O 3 The PDA-CaO catalyst (catalyst obtained according to the preparation procedure of example 4, with COD removal rate between 56% and 62%) was subjected to COD removal performance comparison.
Reaction conditions: biochemical effluent of petrochemical wastewater, COD:140-160mg/L, TDS:3430-3450mg/L, waste water volume: 50mL, pH=7, ozone flow of 0.03L/min, catalyst loading of 400g/L, reaction time of 60min, ozone addition ratio of 2.9.
As shown in FIG. 2, al is compared with the commercially available catalyst 2 O 3 The PDA-CaO catalyst has good COD removal performance, has good stability and activity aiming at biochemical effluent of petrochemical wastewater, has a COD removal rate of 62 percent, can be reused and has 20 cyclesNo decrease in activity was observed.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (8)
1. An ozone oxidation catalyst for advanced treatment of salt-containing organic wastewater consists of a carrier and a metal active component loaded on the carrier, wherein the metal active component is calcium oxide;
the carrier is modified via a surface; the surface modification is based on coating polymerization of a modifier on the surface of a carrier, and a group with a strong anchoring traction effect on calcium ions is formed on the surface of the carrier; the group with strong anchoring traction effect on calcium ions comprises amino and hydroxyl; the modifier is dopamine hydrochloride;
the active site of the catalyst is Ca-O y -N x -C, x+y=4, wherein x is the number of N atoms coordinated with Ca atoms, taking values from 0 to 4 and not 0 and 4; y is the number of O atoms coordinated with Ca atoms, and has a value of 0-4 and is not 0 and 4;
the preparation method of the ozone oxidation catalyst for the advanced treatment of the saline organic wastewater comprises the following steps:
step A, fully washing the 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 carrier with a modified surface;
step C, willPlacing the modified carrier in a carrier containing Ca 2+ Oscillating, standing and aging to obtain a catalyst precursor;
step D, drying the catalyst precursor, and roasting to obtain an ozone oxidation catalyst;
in step B, the mass ratio of the modifier to the carrier is 1:20;
in step C, ca is contained 2+ Ca in solution of (C) 2+ The concentration is 0.05-0.3mol/L; modified vector and Ca-containing vector 2+ The dosage ratio of the solution of (2) is 0.3g/mL;
in the step D, roasting is carried out in an inert gas atmosphere, wherein the roasting temperature is 600-1000 ℃; and/or, the roasting time is 1-5h.
2. The ozone oxidation catalyst according to claim 1, characterized in that the specific surface area of the ozone oxidation catalyst is 140-160m 2 Per gram, pore volume of 0.4-0.6cm 3 /g。
3. A method for preparing an ozone oxidation catalyst for advanced treatment of salt-containing organic wastewater, which comprises the following steps:
step A, fully washing the 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 carrier with a modified surface;
step C, placing the modified carrier in a carrier containing Ca 2+ Oscillating, standing and aging to obtain a catalyst precursor;
step D, drying the catalyst precursor, and roasting to obtain an ozone oxidation catalyst;
in step B, the mass ratio of the modifier to the carrier is 1:20;
in step C, ca is contained 2+ Ca in solution of (C) 2+ The concentration is 0.05-0.3mol/L; modified vector and Ca-containing vector 2+ The dosage ratio of the solution was 0.3g/mL.
4. A method according to claim 3, wherein in step a, drying is performed under vacuum, the drying temperature being 120 ℃, the drying time being 6-12 hours; and/or the roasting temperature is 350 ℃, and the roasting time is 2-5h.
5. A method according to claim 3, wherein in step B, the stirring time is 2 to 12 hours; and/or oscillating in a shaking table, wherein the oscillating temperature is 20-35 ℃ and the oscillating time is 2-12 hours; and/or drying under vacuum, wherein the drying temperature is 40-80 ℃, and the drying time is 6-12h.
6. A method according to claim 3, wherein in step C, the time of oscillation is 6-12 hours; and/or, standing and aging for 2-24h.
7. A method according to claim 3, wherein in step D, the firing is performed under an inert gas atmosphere at a temperature of 600-1000 ℃; and/or, the roasting time is 1-5h.
8. Use of the ozone oxidation catalyst for advanced treatment of salt-containing organic wastewater according to claim 1 or 2 or the ozone oxidation catalyst for advanced treatment of salt-containing organic wastewater prepared by the preparation method according to any one of claims 3 to 7 in advanced treatment of salt-containing organic wastewater; 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 emission standard;
the reaction conditions of the ozone oxidation treatment are as follows: COD of the wastewater: 140-160mg/L, TDS:3430-3450mg/L, pH=7, ozone flow of 0.03L/min, catalyst loading of 400g/L, reaction time of 60min, ozone addition ratio of 0.6-4.2.
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