CN115228495A - Calcium-based carbon-coated ozone oxidation catalyst for advanced treatment of salt-containing organic wastewater - Google Patents
Calcium-based carbon-coated ozone oxidation catalyst for advanced treatment of salt-containing organic wastewater Download PDFInfo
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- 239000011575 calcium Substances 0.000 title claims abstract description 76
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 66
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 55
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 51
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 48
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
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Classifications
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
-
- B01J35/60—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
Abstract
The invention relates to a calcium-based carbon-coated ozone oxidation catalyst for advanced treatment of salt-containing organic wastewater, which consists of a carrier and metal active components loaded on the carrier, wherein the metal active components are calcium oxide and calcium nitride, and the carrier is formed by surface modification and carbon coating of a porous carrier; surface modification is carried out on polydopamine formed by dopamine hydrochloride self-polymerization and an active amine compound to carry out polymerization coating on the surface of a porous carrier, so that a polymerization coating layer containing hydroxyl and amino with stronger anchoring and traction effects on calcium ions is formed on the surface of the porous carrier; the carbon coating is to calcine the modified porous carrier which is formed on the surface and contains the polymerization coating of hydroxyl and amido which have stronger anchoring and traction effects on calcium ions, so that the polymerization coating is carbonized to form the carbon coating with Ca, N and O sites, and the activity of the catalyst is higher and more stable. The catalyst does not contain toxic organic matters and heavy metals in the preparation process, and does not cause secondary pollution due to metal loss after long-term use.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and relates to a calcium-based carbon-coated ozone oxidation catalyst for advanced treatment of salt-containing organic wastewater, and a preparation method and application thereof.
Background
The salt-containing organic wastewater is discharged after centralized treatment of various chemical enterprises such as petrifaction enterprises, textile printing and dyeing enterprises and the like. The wastewater has the characteristics of complex water quality components and large fluctuation of water quality and water quantity due to different production processes. The organic wastewater contains various pollutants including various toxic and non-degradable organic matters such as esters, phenols and aldehydes, has the characteristic of high salt content, and belongs to typical non-degradable industrial wastewater.
At present, biochemical treatment and other methods adopted by sewage treatment plants are difficult to reach the discharge standard. Therefore, the secondary biochemical effluent of the traditional wastewater treatment plant needs to be further deeply treated. As an advanced oxidation technology, by adding an ozone catalyst, hydroxyl free radicals (. OH, the oxidation-reduction potential is as high as 2.8 eV) and other active oxygen with strong oxidizing property are generated, so that organic matters can be rapidly oxidized and decomposed, and the method is a green, efficient and secondary-pollution-free wastewater treatment method. The design, synthesis and preparation of the green and efficient catalyst are key.
Active components used by the prior heterogeneous catalyst in catalytic ozonation are mainly transition metals and oxides thereof, including manganese oxide, iron oxide, and bimetallic/multi-metal oxides such as Mn-M oxide, and the like, which have high catalytic activity, multiple valence states and high stability, and are widely researched in a heterogeneous catalytic ozonation system. However, the water quality components in an actual wastewater system are complex, the catalyst is easily blocked and hindered by various components to reduce the catalytic activity, the catalyst is easily leached and secondarily polluted by metal components after being exposed in ozone, active oxygen and wastewater for a long time, and meanwhile, the high-salt environment can also cause inorganic salt to deposit on the surface of the catalyst to quickly deactivate the catalyst, and the application of the ozone catalytic oxidation technology in the deep treatment of high-salt organic wastewater is severely restricted by the factors. Therefore, the design and development of a novel green and efficient ozone oxidation catalyst are urgently needed.
The calcium compound has wide sources and low cost, calcium ions basically have no pollution to water environment, and the calcium compound contains strong alkaline sites, and can be used as a green and efficient metal active component to replace a conventional transition metal oxide to be used as an active center for catalytic oxidation of ozone. At present, there is little research on calcium compounds as ozone catalysts, and there are reports that calcium hydroxide is mainly used as a catalyst auxiliary to slow down the quenching effect of carbonate on hydroxyl free radicals or as a pH regulator to promote ozone to generate active free radicals, such as Ca (OH) in Chinese patent CN103351051A 2 As an auxiliary agent for catalyzing ozone oxidation, the method carries out advanced treatment on biochemical effluent of landfill leachate. The preparation of the heterogeneous ozone catalyst needs to enhance the interaction between the active component and the carrier, improve the dispersibility of the active component on the surface of the catalyst, reduce the leaching of the active component and enhance the catalytic activity of the catalyst; meanwhile, the salt resistance of the catalyst needs to be improved so as to prevent the deactivation of the catalyst caused by salt deposition and improve the stability of the catalyst.
Disclosure of Invention
One of the purposes of the invention is to provide a calcium-based carbon-coated ozone oxidation catalyst for advanced treatment of organic wastewater containing salt aiming at the problems in the prior art; 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 invention also aims to provide a preparation method of the calcium-based carbon-coated ozone oxidation catalyst for the advanced treatment of the salt-containing organic wastewater, the calcium-based carbon-coated ozone oxidation catalyst for the advanced treatment of the salt-containing organic wastewater is prepared by the method, the preparation process is simple, and the prepared catalyst is high in catalytic efficiency and stability and can be recycled.
To this end, the invention provides a calcium-based carbon-coated ozone oxidation catalyst for advanced treatment of organic wastewater containing salt, which is composed of a carrier and metal active components loaded on the carrier, wherein the metal active components are calcium oxide and calcium nitride, and the carrier is formed by surface modification and carbon coating of a porous carrier; the surface modification is that polydopamine formed by dopamine hydrochloride self-polymerization and an active amine compound are polymerized and coated on the surface of a porous carrier, so that a polymerized coating layer containing hydroxyl and amino which have stronger anchoring and traction effects on calcium ions is formed on the surface of the porous carrier; the carbon coating is to calcine a modified porous carrier of a polymerization coating layer which is formed on the surface and contains hydroxyl and amino and has stronger anchoring and traction effects on calcium ions, so that the polymerization coating layer is carbonized, and the carbon coating layer with Ca, N and O sites is formed.
According to the invention, the active amine compound comprises one or more of polyethyleneimine, urea, melamine and polyaniline.
In a second aspect, the present invention provides a method for preparing a calcium-based carbon-coated ozone oxidation catalyst according to the first aspect of the present invention, comprising:
step A, carrying out pretreatment on the porous carrier through water washing, drying and calcining to obtain a pretreated porous carrier;
step B, placing the pretreated porous carrier in a modified mixed solution, oscillating, filtering, washing and drying to obtain a surface-modified porous carrier;
step C, placing the porous carrier with the modified surface in Ca 2+ In the solution, oscillating, standing, aging and filtering to obtain a catalyst precursor;
d, washing the catalyst precursor, drying, calcining at constant temperature, and naturally cooling to obtain the calcium-based carbon-coated ozone oxidation catalyst;
the modified mixed solution is formed by mixing polydopamine formed by self-polymerization of dopamine hydrochloride and an active amine compound in a buffer solution; preferably, the active amine compound comprises one or more of polyethyleneimine, urea, melamine and polyaniline.
In some embodiments of the present invention, the mass ratio of the active amine compound to the dopamine hydrochloride in the modified mixed solution is 1.
According to the invention, the mass volume ratio of the dopamine hydrochloride to the buffer solution is 0.005-0.05 g/mL; preferably, the buffer solution is a Tris-HCl buffer solution with a pH of 0.5-2.0 mM and a pH of 7.5-9.0.
In some embodiments of the invention, the ratio of the amount of the modified mixed solution to the amount of the pretreated porous carrier is 2.0 to 8.0ml/g.
According to the invention, in step A, drying is carried out under vacuum conditions, wherein the drying temperature is 50-90 ℃.
According to the invention, in step A, the temperature of the calcination is between 300 and 400 ℃.
In some embodiments of the invention, in step C, ca is contained 2+ Ca in solution 2+ The concentration is 0.01-0.5 mol/L; preferably, it contains Ca 2+ The dosage ratio of the solution to the surface modified porous carrier is 1.0-6.0 ml/g.
In some embodiments of the invention, in step D, the washing with water is performed 5 to 10 times.
According to the invention, in the step D, the drying temperature is 60-80 ℃, and the drying time is 6-12 h.
In some embodiments of the invention, in step D, calcining is carried out in an inert gas atmosphere, the temperature rise speed is 2-7 ℃/min, and the calcining temperature is 600-800 ℃; and/or the calcining time is 2-6 h.
The third aspect of the invention provides the application of the calcium-based carbon-coated ozone oxidation catalyst according to the first aspect of the invention or the calcium-based carbon-coated 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; preferably, the application comprises the steps of filling a calcium-based carbon-coated ozone oxidation catalyst in a wastewater treatment device, introducing wastewater, introducing ozone, and performing ozone oxidation treatment on the wastewater to obtain oxidized effluent meeting the discharge standard.
The invention has the following beneficial effects:
in the preparation process of the ozone catalyst, the surface of the porous carrier is modified by using the active amine compound-polydopamine surface modification mixed solution, so that an active layer with strong structural stability and abundant active groups such as amido and hydroxyl which are beneficial to anchoring metal is formed on the surface of the carrier, a uniformly dispersed environment is provided for the subsequent loading of the metal active component, the interaction between the active component and the carrier is facilitated to be enhanced, and the dispersibility of the active component on the surface of the carrier is improved. In addition, the surface modification such as coating and the like is carried out on the surface of the porous carrier by adopting the surface modified mixed solvent, so that the synergistic effect of metal/nonmetal active sites is realized, the salt resistance is improved by regulating and controlling the electronegativity of the surface of the catalyst, the deposition of inorganic salt is slowed down, the leaching of active components is reduced, and the activity and the stability of the catalyst are enhanced.
The ozone catalyst disclosed by the invention takes Ca, N and O as active sites, so that the metal/nonmetal active site synergistic effect is realized, no noble metal is involved in the preparation process, the preparation cost is reduced, the preparation process is more environment-friendly, and the problem of secondary pollution caused by metal leaching is avoided. Compared with the traditional single metal oxide catalyst, the calcium-based carbon-coated ozone catalyst has the advantages of high catalytic efficiency, high stability, simplicity and convenience in preparation and the like, and can show better catalytic activity and stability in catalytic ozonation treatment of actual wastewater such as salt-containing organic wastewater.
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 shows the external shape and internal structure of the calcium-based carbon-coated ozonation catalyst in the present invention.
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 of
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 dissolved matter 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 "Ca-containing" as used in the present invention 2+ Solution "refers to a calcium chloride solution.
The term "water" as used herein means deionized water, distilled water or ultrapure water unless otherwise specified.
Embodiments II
As mentioned above, at present, the preparation of heterogeneous ozone catalysts requires enhancing the interaction between the active component and the carrier, improving the dispersibility of the active component on the surface of the catalyst, reducing the leaching of the active component, and enhancing the catalytic activity of the catalyst; meanwhile, the salt resistance of the catalyst needs to be improved to prevent the deactivation of the catalyst caused by salt deposition and improve the stability of the catalyst. In order to improve the performances of the catalyst, the inventor considers that the catalyst with high catalytic activity and strong stability prepared by a surface modification method can be more efficiently applied to the advanced treatment process for catalyzing ozone oxidation of salt-containing organic wastewater through a large amount of research.
The research of the inventor discovers that poly-dopamine and active amine compounds formed by self-polymerization of dopamine hydrochloride are subjected to surface modification by polymerization coating on active carbon, aluminum oxide, molecular sieve, medical stone or other porous carriers, and a novel green and efficient Ca-based carbon-coated ozone oxidation catalyst can be prepared by taking Ca salt as a metal active component.
Therefore, the calcium-based carbon-coated ozone oxidation catalyst for advanced treatment of organic wastewater containing salt in the first aspect of the invention is composed of a carrier and a metal active component loaded on the carrier.
The calcium-based carbon-coated ozonation catalyst provided herein is a heterogeneous catalyst in which Ca-N sites are present in addition to Ca-O sites, i.e., the metal active components are calcium oxide and calcium nitride, and the catalytic activity is higher than that of a conventional CaO catalyst. The catalyst has high catalytic efficiency and high stability, and can be recycled.
According to the present invention, the support is formed of a porous support through surface modification and carbon coating. Preferably, the surface modification is to carry out polymerization coating on the surface of the porous carrier by polydopamine and active amine compounds formed by dopamine hydrochloride self-polymerization, so that a polymerization coating layer containing hydroxyl and amino groups with strong anchoring and traction effects on calcium ions is formed on the surface of the porous carrier.
Further preferably, the carbon coating is to calcine a modified porous carrier of a polymeric coating layer formed on the surface and containing hydroxyl and amino which have strong anchoring and traction effects on calcium ions, so that the polymeric coating layer is carbonized to form a carbon coating layer with Ca, N and O sites, and the catalyst has better catalytic activity and stability.
The catalyst can be expressed as a Ca-active amine compound-PDA-porous carrier.
In the invention, the porous carrier comprises porous carriers with strong stability and large specific surface area, such as aluminum oxide, active carbon, molecular sieve, zeolite and the like, and the porous carriers are preferably aluminum oxide.
The second aspect of the present invention relates to a method for preparing a calcium-based carbon-coated ozone oxidation catalyst according to the first aspect of the present invention (see fig. 1):
step A, pretreating a porous carrier through water washing, drying and calcining to obtain a pretreated porous carrier;
step B, placing the pretreated porous carrier in the surface modification mixed solution, oscillating, filtering, washing and drying to obtain the surface modified porous carrier;
step C, placing the porous carrier with the modified surface in Ca 2+ In the solution, oscillating, standing, aging, fully reacting to realize uniform loading of the metal active component, and filtering to obtain a catalyst precursor;
d, washing the catalyst precursor, drying, calcining at constant temperature, and naturally cooling to obtain the calcium-based carbon-coated ozone oxidation catalyst;
the modified mixed solution is formed by mixing polydopamine formed by self-polymerization of dopamine hydrochloride and an active amine compound in a buffer solution; preferably, the active amine compound comprises one or more of polyethyleneimine, urea, melamine and polyaniline.
The porous carrier pretreatment process of the present invention is based on water washing, drying and calcining processes. In the step A, the porous carrier is fully washed by deionized water for 5-10 times to remove impurities on the surface of the porous carrier, dried in a vacuum drying oven at 50-90 ℃ for 6-12 h, dried, calcined in a muffle furnace at 300-400 ℃ for 3-4 h to remove organic impurities on the surface of the porous carrier and dredge the pore channel of the porous carrier, so that the pretreated porous carrier is obtained.
As a further improvement of the invention, the inventor researches and designs the surface modification of the porous carrier in the preparation process of the catalyst, and the used surface modification method is based on that dopamine hydrochloride is self-polymerized in an alkaline solution to form polydopamine, and the polydopamine and active amine substances such as polyethyleneimine, urea, melamine, polyaniline and the like are subjected to Schiff base reaction and Michael addition reaction to realize the coating and surface modification of the porous carrier, so that a large number of hydroxyl groups and amino groups are uniformly distributed on the surface of the modified porous carrier, and the modified porous carrier has a strong anchoring effect on metal ions such as calcium and the like, provides a uniformly dispersed environment for the loading of metal active components, is favorable for enhancing the interaction of the catalyst active components and the carrier, and improves the stability and the activity of the catalyst.
Specifically, in the step B, dissolving Polyethyleneimine (PEI) in a Tris-HCl buffer solution, stirring, adding dopamine hydrochloride, and continuously stirring to obtain the surface modified mixed solution of the active amine compound and Polydopamine (PDA). And then placing the pretreated porous carrier in the mixed solution and fully oscillating. The oscillating speed is 120-180 rpm, the oscillating time is 4-12 h, and the oscillating temperature is 20-30 ℃.
Preferably, the buffer solution is a Tris-HCl buffer solution with a ph of 0.5 to 2.0mm, 7.5 to 9.0, preferably 8.5 to 9.0, and more preferably 8.5; this concentration and pH of the Tris-HCl buffer solution facilitates the self-polymerization of dopamine hydrochloride.
More preferably, in the mixed solution of the active amine compound and the polydopamine for surface modification, the mass ratio of the active amine compound to the dopamine hydrochloride is 1. The surface modification of the porous carrier by the active amine compound-polydopamine mixed solution is more uniform and sufficient than that of the active amine compound-polydopamine mixed solution.
In some embodiments of the present invention, the amount ratio of the surface modification mixed solution of the active amine compound and polydopamine to the carrier is 2.0 to 8.0ml/g.
As a further improvement of the invention, in the preparation process of the heterogeneous catalyst, ca metal salt is used as a metal precursor to construct a main active site, and the metal loading process of the porous carrier is based on the strong interaction between amino groups, hydroxyl groups and other groups on the surface of the porous carrier after surface modification and metal ions.
Specifically, in step C, the surface-modified porous carrier is placed in a Ca-containing atmosphere 2+ Oscillating in the solution, carrying out metal loading, wherein the oscillating speed is 120-180 rpm, the oscillating time is 4-12 h, the oscillating temperature is 20-30 ℃, and the standing aging time is 8-12 h.
Containing Ca 2+ The dosage ratio of the solution to the porous carrier after surface modification is 1.0-6.0 ml/g.
In the present invention, the Ca is contained 2+ The solution is prepared by dissolving anhydrous calcium chloride in water.
Preferably, the Ca is contained 2+ The molar concentration of the solution is 0.01-0.5 mol/L, and Ca is contained in the solution according to the molar concentration 2+ When the solution is loaded, the obtained catalyst has better catalytic effect.
Specifically, in the step D, the loaded porous carrier is fully washed for 5-10 times by using deionized water, the components which are easy to fall off on the surface of the loaded porous carrier are removed, the carrier is dried for 6-12 h at the temperature of 60-80 ℃ in a vacuum drying oven, and the carrier is heated to 600-800 ℃ at the heating rate of 2-7 ℃/min under the inert gas atmosphere in a tubular furnace and calcined for 2-6 h after being dried.
The third aspect of the invention provides the application of the calcium-based carbon-coated ozone oxidation catalyst according to the first aspect of the invention or the calcium-based carbon-coated 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 may be understood as a method for advanced treatment of wastewater using the calcium-based carbon-coated ozone oxidation catalyst according to the first aspect of the present invention or the calcium-based carbon-coated 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 a calcium-based carbon-coated 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 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: chemical Oxygen Demand (COD) of the wastewater: 100 to 117mg/L, total Dissolved Solids (TDS): 5100-5400mg/L, the initial pH of the wastewater is = 6.4-8.5, the flow rate of ozone is 0.02-0.04L/min, the loading amount of the catalyst is 300-500 g/L, the reaction time is 40-60 min, and the adding ratio of the ozone is 2.0-5.0.
The calcium-based carbon-coated ozone oxidation catalyst for advanced treatment of salt-containing organic wastewater provided by the invention is prepared by taking calcium as a metal active component, performing surface modification on a porous carrier by using a surface-modified mixed solution of dopamine, an active amine compound and the like, and enhancing the interaction between the carrier and the active component, and can be efficiently used for advanced treatment of salt-containing organic wastewater. The calcium-based carbon-coated ozone oxidation catalyst disclosed by the invention takes Ca, N and O as active sites, realizes the synergistic effect of metal/nonmetal active sites, high dispersibility of the active sites and better self-salt resistance of the surface of the catalyst, and has better catalytic effect and stability in the deep treatment of salt-containing organic wastewater. Toxic organic matters and heavy metals are not involved in the preparation process of the calcium-based carbon-coated ozone oxidation catalyst, the process is green, the operation is simple, the problem of secondary pollution caused by metal loss after the catalyst is used for a long time is solved, and the calcium-based carbon-coated ozone oxidation catalyst belongs to a novel green and efficient calcium-based carbon-coated ozone oxidation catalyst.
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, the porous support was pretreated by the following method:
and (3) putting the porous carrier into deionized water, fully washing for 3 times, removing dust, drying in a vacuum drying oven at 80 ℃ for 12 hours, calcining in a tubular furnace at 300 ℃ for 4 hours, and removing organic impurities in pore channels and surfaces to obtain the pretreated porous carrier.
In the following examples, COD determination was performed using a DR5000 uv spectrophotometer (hashes) after digestion with a hashcod reagent on a hashdrb 200 digestor (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 -COD After oxidation )/COD Original ×100％
Example 1:
with alumina as a porous carrier, the embodiment prepares a calcium-based carbon-coated ozonation catalyst Ca-PEI-PDA/Al 2 O 3 And the catalytic performance is tested, and the specific process is as follows:
adding polyethyleneimine and dopamine hydrochloride (0.0025 g/ml of polyethyleneimine and 0.01g/ml of dopamine hydrochloride) into 150ml of Tris-HCl buffer solution, and uniformly stirring to obtain a polyethyleneimine-polydopamine surface modification mixed solution. And (3) placing 30g of the pretreated aluminum oxide carrier in the polyethyleneimine-polydopamine surface modification mixed solution, and oscillating for 8 hours at the normal temperature of 180rpm in a shaking table. The solution was filtered off and washed with water and dried in a vacuum oven at 80 ℃ for 12h. Drying the obtained modified aluminum oxide (PEI-PDA/Al) 2 O 3 ) Placing in 100ml Ca-containing solution with a molar concentration of 0.125mol/L 2+ In the solution, shaking the solution in a shaking table at 120rpm at normal temperature for 8h, and then standing and aging the solution for 8h. Filtering to remove maceration extract, washing, and vacuum oven drying at 80 deg.CDrying for 12h, placing into a tube furnace after drying, heating to 800 ℃ at a heating rate of 5 ℃/min under the protection of argon, keeping the temperature for 2h, and naturally cooling to obtain Ca-PEI-PDA/Al 2 O 3 (PEI: PDA = 0.25) calcium-based carbon-coated ozonation catalyst.
Example 2:
with alumina as a porous carrier, the embodiment prepares a calcium-based carbon-coated ozonation catalyst Ca-PEI-PDA/Al 2 O 3 And testing the catalytic performance of the catalyst, wherein the specific process is as follows:
adding polyethyleneimine and dopamine hydrochloride (0.005 g/ml of polyethyleneimine and 0.01g/ml of dopamine hydrochloride) into 150ml of Tris-HCl buffer solution, and uniformly stirring to obtain a polyethyleneimine-polydopamine surface modification mixed solution. And (3) placing 30g of the pretreated aluminum oxide carrier in the polyethyleneimine-polydopamine surface modification mixed solution, and oscillating for 8 hours at the normal temperature of 180rpm in a shaking table. After filtering off the solution and washing with water, it was dried in a vacuum oven at 80 ℃ for 12h. Drying to obtain PEI-PDA/Al 2 O 3 Placing in 100ml Ca-containing solution with a molar concentration of 0.125mol/L 2+ In the solution, the solution is shaken in a shaking table at 120rpm at normal temperature for 8 hours, and then is kept stand and aged for 8 hours. Filtering to remove the maceration extract, washing, drying in a vacuum oven at 80 deg.C for 12h, oven drying, placing into a tube furnace, heating to 800 deg.C at a heating rate of 5 deg.C/min under the protection of argon gas, keeping the temperature for 2h, and naturally cooling to obtain Ca-PEI-PDA/Al 2 O 3 (PEI: PDA = 0.5) calcium-based carbon-coated ozonation catalyst.
Example 3:
in this example, a calcium-based carbon-coated ozonation catalyst Ca-PEI-PDA/Al was prepared using aluminum oxide as a porous carrier 2 O 3 And testing the catalytic performance of the catalyst, wherein the specific process is as follows:
adding polyethyleneimine and dopamine hydrochloride (0.0075 g/ml of polyethyleneimine and 0.01g/ml of dopamine hydrochloride) into 150ml of Tris-HCl buffer solution, and uniformly stirring to obtain a polyethyleneimine-polydopamine surface modification mixed solution. Placing 30g of pretreated aluminum oxide carrier on the surface of polyethyleneimine-polydopamineIn the mixed solution, the solution was shaken at 180rpm for 8 hours at room temperature in a shaker. The solution was filtered off and washed with water and dried in a vacuum oven at 80 ℃ for 12h. Drying to obtain PEI-PDA/Al 2 O 3 Placing in 100ml Ca-containing solution with a molar concentration of 0.125mol/L 2+ In the solution, the solution is shaken at normal temperature of 120rpm in a shaking table for 8 hours, and then is kept stand and aged for 8 hours. Filtering to remove the maceration extract, washing, drying in a vacuum oven at 80 deg.C for 12h, oven drying, placing into a tube furnace, heating to 800 deg.C at a heating rate of 5 deg.C/min under the protection of argon gas, keeping the temperature for 2h, and naturally cooling to obtain Ca-PEI-PDA/Al 2 O 3 (PEI: PDA = 0.75) calcium-based carbon-coated ozonation catalyst.
Example 4:
with alumina as a porous carrier, the embodiment prepares a calcium-based carbon-coated ozonation catalyst Ca-PEI-PDA/Al 2 O 3 And testing the catalytic performance of the catalyst, wherein the specific process is as follows:
adding polyethyleneimine and dopamine hydrochloride (0.01 g/ml of polyethyleneimine and 0.01g/ml of dopamine hydrochloride) into 150ml of Tris-HCl buffer solution, and uniformly stirring to obtain a polyethyleneimine-polydopamine surface modification mixed solution. And (3) placing 30g of the pretreated aluminum oxide carrier in the polyethyleneimine-polydopamine surface modification mixed solution, and oscillating for 8h at the normal temperature of 180rpm in a shaking table. After filtering off the solution and washing with water, it was dried in a vacuum oven at 80 ℃ for 12h. Drying to obtain PEI-PDA/Al 2 O 3 Placing in 100ml Ca-containing solution with a molar concentration of 0.125mol/L 2+ In the solution, the solution is shaken at normal temperature of 120rpm in a shaking table for 8 hours, and then is kept stand and aged for 8 hours. Filtering to remove maceration extract, washing, drying in 80 deg.C vacuum oven for 12 hr, oven drying, placing into tube furnace, heating to 800 deg.C at a heating rate of 5 deg.C/min under the protection of argon gas, keeping the temperature for 2 hr, and naturally cooling to obtain Ca-PEI-PDA/Al 2 O 3 (PEI: PDA = 1) calcium-based carbon-coated ozonation catalyst.
Example 5:
in the embodiment, the calcium-based carbon-coated ozonation catalyst Ca-PEI-PDA/Al is prepared by using aluminum oxide as a porous carrier 2 O 3 This example tested itThe catalytic performance comprises the following specific processes:
adding polyethyleneimine and dopamine hydrochloride (0.0125 g/ml polyethyleneimine and 0.01g/ml dopamine hydrochloride) into 150ml Tris-HCl buffer solution, and uniformly stirring to obtain a polyethyleneimine-polydopamine surface modification mixed solution. And (3) placing 30g of the pretreated aluminum oxide carrier in the polyethyleneimine-polydopamine surface modification mixed solution, and oscillating for 8h at the normal temperature of 180rpm in a shaking table. The solution was filtered off and washed with water and dried in a vacuum oven at 80 ℃ for 12h. Drying to obtain PEI-PDA/Al 2 O 3 Placing in 100ml Ca-containing solution with a molar concentration of 0.125mol/L 2+ In the solution, the solution is shaken for 8 hours at the normal temperature of 120rpm in a shaking table, and then is kept stand and aged for 8 hours. Filtering to remove the maceration extract, washing, drying in a vacuum oven at 80 deg.C for 12h, oven drying, placing into a tube furnace, heating to 800 deg.C at a heating rate of 5 deg.C/min under the protection of argon gas, keeping the temperature for 2h, and naturally cooling to obtain Ca-PEI-PDA/Al 2 O 3 (PEI: PDA = 1.25) calcium-based carbon-coated ozonation catalyst.
Calcium-based carbon-coated ozone oxidation catalyst (Ca-PEI-PDA/Al) prepared in examples 1 to 5 2 O 3 ) The method comprises the following steps of carrying out advanced treatment on actual wastewater in a chemical industrial park through a catalytic ozone oxidation process: the specific method is to mix 20g Ca-PEI-PDA/Al 2 O 3 The ozone catalyst is added into 50ml of wastewater, the flow rate of ozone is 0.03L/min, the loading of the catalyst is 400g/L, the reaction time is 60min, and the ozone adding ratio is 3.6.
The water quality parameters of the actual wastewater in the chemical industrial park are as follows: chemical Oxygen Demand (COD): 100-117mg/L, total Dissolved Solids (TDS): 5100-5400mg/L, initial pH of wastewater =8.3.
Ca-PEI-PDA/Al with different PEI dosage 2 O 3 The calcium-based carbon-coated ozone oxidation catalyst has a good COD removal effect on the catalytic ozone oxidation of actual wastewater in a chemical industrial park, and the COD removal efficiency can be higher than 50%. Ca-PEI-PDA/Al when PEI: PDA =1 2 O 3 The catalytic activity of the calcium-based carbon-coated ozone oxidation catalyst is optimal, the reaction is 60min, the COD removal efficiency reaches 65.66 percent
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 in relation to an exemplary embodiment, and it is understood that 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 (8)
1. A calcium-based carbon-coated ozone oxidation catalyst for advanced treatment of organic wastewater containing salt is composed of a carrier and metal active components loaded on the carrier, wherein the metal active components are calcium oxide and calcium nitride, and the carrier is formed by a porous carrier through surface modification and carbon coating; the surface modification is that polydopamine formed by dopamine hydrochloride self-polymerization and an active amine compound are polymerized and coated on the surface of a porous carrier, so that a polymerized coating layer containing hydroxyl and amino which have stronger anchoring and traction effects on calcium ions is formed on the surface of the porous carrier; the carbon coating is to calcine the modified porous carrier of the polymerization coating layer which is formed on the surface and contains hydroxyl and amido with stronger anchoring and traction effects on calcium ions, so that the polymerization coating layer is carbonized to form the carbon coating layer with Ca, N and O sites.
2. The calcium-based carbon-coated ozonation catalyst according to claim 1, wherein the active amine compound comprises one or more of polyethyleneimine, urea, melamine, and polyaniline.
3. The method for preparing a calcium-based carbon-coated ozonation catalyst according to any one of claims 1 to 2, comprising:
step A, carrying out pretreatment on the porous carrier through water washing, drying and calcining to obtain a pretreated porous carrier;
step B, placing the pretreated porous carrier in a modified mixed solution, oscillating, filtering, washing with water, and drying to obtain a surface-modified porous carrier;
step C, placing the surface modified porous carrier in Ca 2+ In the solution, oscillating, standing, aging and filtering to obtain a catalyst precursor;
d, washing the catalyst precursor, drying, calcining at constant temperature, and naturally cooling to obtain the calcium-based carbon-coated ozone oxidation catalyst;
the modified mixed solution is formed by mixing polydopamine formed by self-polymerization of dopamine hydrochloride and an active amine compound in a buffer solution; preferably, the active amine compound comprises one or more of polyethyleneimine, urea, melamine and polyaniline.
4. The preparation method according to claim 3, wherein the mass ratio of the active amine compound to the dopamine hydrochloride in the modified mixed solution is 1; the dosage ratio of the dopamine hydrochloride to the buffer solution is 0.005-0.05 g/mL; preferably, the buffer solution is a Tris-HCl buffer solution with the concentration of 0.5-2.0 mM and the pH of 7.5-9.0; and/or in the step B, the dosage ratio of the modified mixed solution to the pretreated porous carrier is 2.0-8.0 ml/g.
5. The method according to claim 3, wherein in the step A, the drying is carried out under vacuum at a temperature of 50 to 90 ℃; and/or the calcining temperature is 300-400 ℃.
6. The method according to claim 3, wherein in the step C, ca is contained 2+ Ca in solution 2+ The concentration is 0.01-0.5 mol/L; preferably, it contains Ca 2+ The dosage ratio of the solution to the surface modified porous carrier is 1.0-6.0 ml/g.
7. The method according to claim 3, wherein in the step D, the washing is carried out 5 to 10 times with water; and/or the drying temperature is 60-80 ℃, and the drying time is 6-12 h; calcining in an inert gas atmosphere at a temperature rise rate of 2-7 ℃/min and a calcining temperature of 600-800 ℃; and/or the calcining time is 2-6 h.
8. Use of the calcium-based carbon-coated ozone oxidation catalyst according to any one of claims 1 to 2 or the calcium-based carbon-coated ozone oxidation catalyst prepared by the preparation method according to any one of claims 3 to 7 in the advanced treatment of salt-containing organic wastewater; preferably, the application comprises the steps of filling a calcium-based carbon-coated ozone oxidation catalyst in a wastewater treatment device, introducing wastewater, introducing ozone, and performing ozone oxidation treatment on the wastewater to obtain oxidized effluent meeting the discharge standard.
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