CN113634276A - Carrier modified catalyst, preparation method thereof and application thereof in wastewater treatment - Google Patents

Carrier modified catalyst, preparation method thereof and application thereof in wastewater treatment Download PDF

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CN113634276A
CN113634276A CN202110860158.6A CN202110860158A CN113634276A CN 113634276 A CN113634276 A CN 113634276A CN 202110860158 A CN202110860158 A CN 202110860158A CN 113634276 A CN113634276 A CN 113634276A
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catalyst
source
gel
preparing
roasting
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门孝平
王国方
王旭明
潘玉蕊
张宏伟
李建军
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Zhejiang NHU Co Ltd
Shandong Xinhecheng Fine Chemical Technology Co Ltd
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Zhejiang NHU Co Ltd
Shandong Xinhecheng Fine Chemical Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • B01J37/30—Ion-exchange
    • 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
    • C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • 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
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C02F2101/18—Cyanides

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

The invention discloses a carrier modified catalyst, a preparation method thereof and application thereof in wastewater treatment, wherein the preparation method of the catalyst comprises the following steps: (1) dissolving a silicon source, an aluminum source and an organic template agent in deionized water, stirring into uniform gel, and then carrying out gel aging; (2) adopting vermiculite to carry out gel treatment on the gel obtained in the step (1)Modifying, then carrying out hydrothermal crystallization, washing, drying and roasting to obtain a catalyst carrier ZSM-5/Vt; (3) and (3) carrying out ion exchange on the catalyst carrier ZSM-5/Vt obtained in the step (2) by adopting a solution containing a Cu source and a Ce source, and roasting to obtain the catalyst. The catalyst is used for containing CN‑And Cl‑When the high-salt organic wastewater is treated, the method has the advantages of high catalytic activity, low loss rate of active components and long service life.

Description

Carrier modified catalyst, preparation method thereof and application thereof in wastewater treatment
Technical Field
The invention belongs to the field of industrial wastewater treatment, and particularly relates to a carrier modified catalyst, a preparation method thereof and application thereof in wastewater treatment.
Background
In modern industrial production (such as fields of printing and dyeing, pesticides, medicines, petrochemical industry, paper making and the like), a large amount of industrial wastewater is generated, has the characteristics of high organic matter concentration and complex components, can generate great harm when being discharged into the environment, and needs to be subjected to harmless treatment in advance.
The existing industrial wastewater treatment method mainly comprises the following steps: physical, chemical and biological methods. Among them, the chemical method is a method of recovering soluble waste or colloidal substances by using a chemical reaction or a physicochemical action, for example, neutralizing acidic or alkaline waste water by a neutralization method; recovering phenols, heavy metals and the like by utilizing the distribution of soluble wastes with different solubilities in two phases through an extraction method; reducing or oxidizing pollutants in the wastewater are removed by an oxidation-reduction method, and pathogenic bacteria and the like in the natural water body are killed.
The catalytic wet oxidation is a novel high-efficiency treatment technology, and is particularly suitable for treating industrial wastewater with high concentration, complex components and difficult degradation compared with other sewage treatment technologies. The key point of the catalytic wet oxidation lies in the development of an efficient catalyst, the early-stage use of the catalyst is more homogeneous catalysts which comprise soluble transition metal salts such as Cu, Cr, Mo, Fe, Ni, Co, Mn and the like, and the catalyst has the advantages of high activity and high reaction speed, but can generate secondary pollution and needs further subsequent treatment, so that the treatment cost of the wastewater is increased. In order to reduce secondary pollution and cost, the heterogeneous catalyst is also used as a wet catalytic oxidation catalyst for treating wastewater.
Among the existing wet catalytic oxidation catalysts, the Cu modified heterogeneous catalyst has the advantages of low cost, high activity, high reaction rate and the like, is the catalyst which is most widely applied to wet catalytic oxidation, but is applied to high-salt organic wastewater, particularly CN (CN)-And Cl-In the wet catalytic oxidation of the wastewater, phenomena such as catalyst poisoning and active component loss are easy to occur, and the catalytic activity and the service life of the catalyst are influenced.
Chinese patent application CN 103041818A discloses a preparation method and application of a catalytic wet oxidation catalyst, the preparation method of the catalytic wet oxidation catalyst is as follows: (1) taking a porous inert material as a carrier, and adopting an organic acid solution for pre-impregnation treatment; (2) preparing an impregnation solution containing a transition metal element water-soluble compound and an auxiliary element water-soluble compound, impregnating the carrier treated in the step (1) with the impregnation solution, drying the carrier in the air with proper humidity for 12-48 hours in the shade, and drying and roasting to obtain the final catalyst, wherein the catalyst has good activity and stability for treating common organic wastewater, but has good activity and stability for high-salt wastewater, especially CN-containing wastewater-And Cl-In the treatment of high-salt wastewater, Cu is present2+The serious loss problem is solved, and the COD and the CN of the wastewater are aimed at-The removal rate of (a) is not sufficiently high.
In conclusion, the CN contained in the chemical production is treated-And Cl-The catalyst for the high-salt organic wastewater, in particular the catalyst with high catalytic activity, low loss rate of active components and low production cost is particularly important.
Disclosure of Invention
The invention provides a carrier modified catalyst, a preparation method thereof and application thereof in wastewater treatment.
A method of preparing a support-modified catalyst comprising the steps of:
(1) dissolving a silicon source, an aluminum source and an organic template agent in deionized water, stirring into uniform gel, and then carrying out gel aging;
(2) modifying the gel obtained in the step (1) by adopting vermiculite, and then carrying out hydrothermal crystallization, washing, drying and roasting to obtain a catalyst carrier ZSM-5/Vt (wherein ZSM-5/Vt represents ZSM-5 modified by vermiculite, and Vt represents vermiculite);
(3) and (3) carrying out ion exchange on the catalyst carrier ZSM-5/Vt obtained in the step (2) by adopting a solution containing a Cu source and a Ce source, and roasting to obtain the catalyst.
In the process of preparing the catalyst carrier ZSM-5/Vt, the vermiculite is adopted to modify the carrier so as to improve the ion exchange capacity of the carrier, and then the catalyst Cu/Ce/ZSM-5/Vt with more active metal centers and more stability is prepared by an ion exchange method-And Cl-The high-salt organic wastewater has higher catalytic activity in wet catalytic oxidation treatment, and the active metal Cu has lower metal loss rate and better stability through the synergistic fixation effect of vermiculite and rare earth metal Ce, prolongs the service life and widens the application field of Cu series catalysts.
Preferably, in the step (1), the silicon source is one or more of sodium metasilicate, silica sol, water glass and tetraethoxysilane, and more preferably tetraethoxysilane.
Preferably, in the step (1), the aluminum source is one or more of aluminum nitrate, aluminum sulfate, aluminum isopropoxide and sodium metaaluminate, and more preferably sodium metaaluminate.
Preferably, in step (1), the organic template is one or more of tetrapropylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, ethylenediamine, diethylamine and triethylamine, and more preferably tetrapropylammonium hydroxide.
Preferably, in step (1), the silicon source is SiO2Calculated as Al), an aluminum source (calculated as Al)2O3Calculated), the molar ratio of the organic template to the water is 100: 1-5: 4-20: 3000-4000;
the gel aging time is 12-36 h.
Preferably, in the step (2), the weight ratio of the gel to the vermiculite is 100: 10-30;
grinding vermiculite into powder of 100-200 meshes, and modifying the gel obtained in the step (1).
Preferably, in the step (2), the hydrothermal crystallization temperature is 130-180 ℃, and the hydrothermal crystallization time is 12-48 h; the roasting time is 3-8 h, the roasting temperature is 400-650 ℃, and the roasting temperature is preferably 550-650 ℃.
Preferably, in the step (3), the Cu source is a soluble Cu salt, preferably copper nitrate, and the concentration of the Cu source is 0.05-0.2 mol/L;
the Ce source is soluble Ce salt, preferably cerium nitrate, and the concentration of the Ce source is 0.05-0.2 mol/L.
Preferably, in the step (3), the temperature of the ion exchange is 20-60 ℃; the ion exchange time is 4-12 h; the ion exchange times are 1-3; the roasting time is 2-8 h; the roasting temperature is 400-650 ℃, preferably 550-650 ℃. Wherein, unlike the conventional impregnation method, the ion exchange is performed under stirring conditions so that the ion exchange process is sufficiently performed.
The invention also provides a catalyst obtained by the preparation method.
The invention further provides an application of the catalyst in organic wastewater treatment.
The organic wastewater is treated under the action of oxygen and the catalyst, and preferably, the organic wastewater contains CN-And/or Cl-。
Preferably, the initial COD concentration of the organic wastewater is: 1000-40000 mg/L; CN in waste water-The initial concentration is 10-2000 mg/L.
Preferably, the oxygen partial pressure is 0.5-2.5 MPa during treatment; the dosage of the catalyst in each L of wastewater is 0.05-3 g.
Preferably, the reaction temperature is 150-230 ℃, the reaction time is 30-180 min, and the stirring speed is 200-500 rpm.
Compared with the prior art, the invention has the beneficial effects that:
(1) vermiculite is used in ZSM-5 molecular sieve gel for modification, so that the catalyst carrier has high cation exchange capacity and high dispersibility;
(2) active metal Cu and rare earth Ce are loaded on a catalyst carrier with high ion exchange capacity by adopting an ion exchange method, the fixing capacity of the loaded catalyst to the active metal component Cu is greatly improved by the synergistic action of vermiculite and the rare earth Ce, and meanwhile, the loss rate of the active component Cu of the catalyst prepared by the ion exchange method is lower than that of the active component Cu of the catalyst prepared by an impregnation method;
(3) for containing CN-And Cl-The catalyst of the invention has higher catalytic activity, lower active component loss rate and longer service life.
Detailed Description
For further explanation of the present invention, the technical solutions of the present invention are described in detail below by examples, but the scope of the present invention is not limited to the following examples.
In the present invention, the test methods involved are as follows:
measuring COD content in the wastewater before and after the reaction by GB11914-89, and calculating the removal rate of COD in the wastewater after the reaction; CN before and after reaction is measured by a national standard method GB7486-87-Content of (C), calculating CN-The removal rate; the content of active metal Cu in the catalyst was measured by ICP, and Cu in the wastewater after the reaction was measured by ICP+To thereby calculate Cu2+The amount of run-off.
Example 1
(1) Preparation of catalyst carrier:
grinding vermiculite into 200 mesh powder, drying in oven at 120 deg.C for 2 hr, and mixing ethyl orthosilicate, sodium metaaluminate, tetrapropylammonium hydroxide (TPAOH) and water to obtain 500mL of a gel solution of ethyl orthosilicate (in SiO)2Calculated as Al), sodium metaaluminate (calculated as Al)2O3Calculated), the molar ratio of tetrapropylammonium hydroxide to water is 100: 1: 4: 3500, stirring uniformly, aging for 12h, adding vermiculite into the reaction gel according to the weight ratio of the gel to the vermiculite powder of 100:10, mixing uniformly, performing hydrothermal crystallization for 12h at 130 ℃, taking out a crystallized product, washing, drying, and roasting in a muffle furnace at 550 ℃ for 3h to obtain the catalyst carrier for later use.
(2) Preparing a catalyst:
taking 5g of a catalyst carrier, uniformly mixing the catalyst carrier in 100mL of ion exchange liquid with 0.05mol/L of both copper nitrate and cerium nitrate, stirring the mixture for 4 hours at the water bath temperature of 30 ℃ to ensure that metal ions and ion exchange sites on the catalyst carrier fully perform ion exchange, roasting the mixture for 3 times in a muffle furnace at the temperature of 550 ℃ to obtain a Cu/Ce/ZSM-5/Vt catalyst, measuring the content of Cu in the catalyst through ICP, and researching the influence of the load change of active components of the catalyst on the catalytic effect.
(3) Catalytic wet oxidation experiment:
taking a compound containing CN-And Cl-200mL of high-salt organic wastewater, wherein the initial concentration of COD is 40000 mg/L; CN-Initial concentration 2000mg/L, Cl-In the form of NaCl salt with a salt concentration of 10.2% and Cl-The content of (b) is 60153.85mg/L, the catalyst Cu/Ce/ZSM-5/Vt is added according to the adding amount of 0.1g/L, and the reaction conditions are as follows: the reaction temperature is 200 ℃, the oxygen partial pressure is 1.8MPa, the reaction time is 120min, and COD and CN in the wastewater after the reaction are measured-Content and Cu2+Content, calculating COD removal rate, CN-The removal rate is used for judging the catalytic activity of the catalyst and the stability of active metal components, and specific data are shown in table 1.
Example 2
(1) Preparation of catalyst carrier:
grinding vermiculite into 200 mesh powder, drying in oven at 120 deg.C for 2 hr, preparing 500mL gel solution from ethyl orthosilicate, sodium metaaluminate, tetrapropylammonium hydroxide and water, wherein n-propyl silicateEthyl silicate (in SiO)2Calculated as Al), sodium metaaluminate (calculated as Al)2O3Calculated), the molar ratio of tetrapropylammonium hydroxide to water is 100: 3: 10: 3500, stirring uniformly, aging for 24h, adding vermiculite into the reaction gel according to the weight ratio of the gel to the vermiculite powder of 100:20, mixing uniformly, performing hydrothermal crystallization for 24h at 150 ℃, taking out a crystallized product, washing, drying, and roasting in a muffle furnace at 600 ℃ for 3h to obtain the catalyst carrier for later use.
(2) Preparing a catalyst:
taking 5g of catalyst carrier, putting the catalyst carrier into 100mL of ion exchange liquid containing 0.1mol/L of copper nitrate solution and 0.05mol/L of cerium nitrate solution, uniformly mixing and stirring the mixture at the water bath temperature of 40 ℃ for 5 hours to ensure that metal ions and ion exchange sites on the catalyst carrier fully perform ion exchange, after 3 times of ion exchange, putting the catalyst carrier into a muffle furnace at 550 ℃ for roasting for 3 hours to obtain a catalyst Cu/Ce/ZSM-5/Vt, measuring the content of Cu in the catalyst through ICP, and researching the influence of the load change of active components of the catalyst on the catalytic effect.
(3) Catalytic wet oxidation experiment:
taking a compound containing CN-And Cl-200mL of high-salt organic wastewater, wherein the initial concentration of COD is as follows: 40000 mg/L; CN-Initial concentration 2000mg/L, Cl-In the form of NaCl salt with a salt concentration of 10.2% and Cl-The content of (b) is 60153.85mg/L, the catalyst Cu/Ce/ZSM-5/Vt is added according to the adding amount of 0.1g/L, and the reaction conditions are as follows: the reaction temperature is 200 ℃, the oxygen partial pressure is 1.8MPa, the reaction time is 120min, and COD and CN in the wastewater after the reaction are measured-Content and Cu2+Content, calculating COD removal rate, CN-The removal rate is used for judging the catalytic activity of the catalyst and the stability of active metal components, and specific data are shown in table 1.
Example 3
(1) Preparation of catalyst carrier:
grinding vermiculite into 200 mesh powder, drying in oven at 120 deg.C for 2 hr, preparing 500mL gel solution from ethyl orthosilicate, sodium metaaluminate, tetrapropylammonium hydroxide and water, whereinTetraethoxysilane (in SiO)2Calculated as Al), sodium metaaluminate (calculated as Al)2O3Calculated), the molar ratio of tetrapropylammonium hydroxide to water is 100: 5: 20: 3500, stirring uniformly, aging for 36h, adding vermiculite into the reaction gel according to the weight ratio of the gel to the vermiculite powder of 100:30, mixing uniformly, performing hydrothermal crystallization for 48h at 180 ℃, taking out a crystallized product, washing, drying, and roasting in a muffle furnace at 650 ℃ for 3h to obtain the catalyst carrier for later use.
(2) Preparing a catalyst:
taking 5g of catalyst carrier, putting the catalyst carrier into 100mL of ion exchange liquid containing 0.2mol/L of copper nitrate solution and 0.1mol/L of cerium nitrate solution, uniformly mixing and stirring the mixture at the water bath temperature of 60 ℃ for 12 hours to ensure that metal ions and ion exchange sites on the catalyst carrier fully perform ion exchange, after 3 times of ion exchange, putting the catalyst carrier into a 600 ℃ muffle furnace for roasting for 3 hours to obtain a catalyst Cu/Ce/ZSM-5/Vt, measuring the content of Cu in the catalyst through ICP, and researching the influence of the load change of active components of the catalyst on the catalytic effect.
(3) Catalytic wet oxidation experiment:
taking a compound containing CN-And Cl-200mL of high-salt organic wastewater, wherein the initial concentration of COD is as follows: 40000 mg/L; CN-Initial concentration 2000mg/L, Cl-In the form of NaCl salt with a salt concentration of 10.2% and Cl-The content of (b) is 60153.85mg/L, the catalyst Cu/Ce/ZSM-5/Vt is added according to the adding amount of 0.1g/L, and the reaction conditions are as follows: the reaction temperature is 200 ℃, the oxygen partial pressure is 1.8MPa, the reaction time is 120min, and COD and CN in the wastewater after the reaction are measured-Content and Cu2+Content, calculating COD removal rate, CN-The removal rate is used for judging the catalytic activity of the catalyst and the stability of active metal components, and specific data are shown in table 1.
Comparative example 1
(1) Preparation of catalyst carrier:
preparing 500mL of gel solution from tetraethoxysilane, sodium metaaluminate, tetrapropylammonium hydroxide and water, wherein tetraethoxysilane (SiO) is used2Calculated as Al), sodium metaaluminate (calculated as Al)2O3Calculated), the molar ratio of tetrapropylammonium hydroxide to water is 100: 5: 20: 3500, stirring evenly, aging for 36h, hydrothermal crystallizing for 48h at 180 ℃, taking out the crystallized product, washing, drying, and roasting in a muffle furnace at 650 ℃ for 3h to obtain the catalyst carrier for later use.
(2) Preparing a catalyst:
taking 5g of catalyst carrier, putting the catalyst carrier into 100mL of ion exchange liquid containing 0.2mol/L of copper nitrate solution and 0.1mol/L of cerium nitrate solution, uniformly mixing and stirring the mixture at the water bath temperature of 60 ℃ for 12 hours to ensure that metal ions and ion exchange sites on the catalyst carrier fully perform ion exchange, after 3 times of ion exchange, putting the catalyst carrier into a 600 ℃ muffle furnace for roasting for 3 hours to obtain a catalyst Cu/Ce/ZSM-5, measuring the content of Cu in the catalyst through ICP, and researching the influence of the load change of an active component of the catalyst on the catalytic effect.
(3) Catalytic wet oxidation experiment:
taking a compound containing CN-And Cl-200mL of high-salt organic wastewater, wherein the initial concentration of COD is as follows: 40000 mg/L; CN-Initial concentration 2000mg/L, Cl-In the form of NaCl salt with a salt concentration of 10.2% and Cl-The content of (b) is 60153.85mg/L, and the catalyst Cu/Ce/ZSM-5 is added according to the adding amount of 0.1g/L, and the reaction conditions are as follows: the reaction temperature is 200 ℃, the oxygen partial pressure is 1.8MPa, the reaction time is 120min, and COD and CN in the wastewater after the reaction are measured-Content and Cu2+Content, calculating COD removal rate, CN-The removal rate is used for judging the catalytic activity of the catalyst and the stability of active metal components, and specific data are shown in table 1.
Comparative example 2
(1) Preparation of catalyst carrier:
grinding vermiculite into 200 mesh powder, drying in oven at 120 deg.C for 2 hr, preparing 500mL gel solution from tetraethoxysilane (prepared from SiO), sodium metaaluminate, tetrapropylammonium hydroxide and water2Calculated as Al), sodium metaaluminate (calculated as Al)2O3Calculated), the molar ratio of tetrapropylammonium hydroxide to water is 100: 5: 20: 3500 stirringAfter being uniformly mixed, the mixture is aged for 36h, then vermiculite is added into the reaction gel according to the weight ratio of the gel to the vermiculite powder of 100:30, the mixture is subjected to hydrothermal crystallization for 48h at 180 ℃ after being uniformly mixed, a crystallized product is taken out, washed and dried, and then the crystallized product is roasted for 3h in a muffle furnace at 650 ℃ to obtain a catalyst carrier for later use.
(2) Preparing a catalyst:
taking 5g of catalyst carrier, placing the carrier in 100mL of impregnation liquid containing 0.2mol/L of copper nitrate solution and 0.1mol/L of cerium nitrate solution, standing and impregnating for 12h at the water bath temperature of 60 ℃ to fully load metal ions on the surface of the carrier, placing the carrier in a 600 ℃ muffle furnace for roasting for 3h to obtain the catalyst Cu/Ce/ZSM-5/Vt, measuring the content of Cu in the catalyst through ICP, and researching the influence of the change of the loading amount of active components of the catalyst on the catalytic effect.
(3) Catalytic wet oxidation experiment:
taking a compound containing CN-And Cl-200mL of high-salt organic wastewater, wherein the initial concentration of COD is as follows: 40000 mg/L; CN-Initial concentration 2000mg/L, Cl-In the form of NaCl salt with a salt concentration of 10.2% and Cl-The content of (b) is 60153.85mg/L, the catalyst Cu/Ce/ZSM-5/Vt is added according to the adding amount of 0.1g/L, and the reaction conditions are as follows: the reaction temperature is 200 ℃, the oxygen partial pressure is 1.8MPa, the reaction time is 120min, and COD and CN in the wastewater after the reaction are measured-Content and Cu2+Content, calculating COD removal rate, CN-The removal rate is used for judging the catalytic activity of the catalyst and the stability of active metal components, and specific data are shown in table 1.
Comparative example 3
Spherical gamma-Al was prepared according to the method in CN 103041818A2O3Pre-drying the carrier in an oven, pre-soaking in citric acid solution with concentration of 0.1mol/L for 60min, drying in the oven in air atmosphere at 80 deg.C for 30min, and drying with gamma-Al2O3Soaking the carrier in water solution prepared from copper nitrate and cerium nitrate with Cu content of 5% and Ce content of 3% for 15min, drying in the air at 20 deg.C with humidity of 45% for 20 hr, and oven drying in an air oven at 80 deg.C for 2 timesDrying at 120 ℃ for 2 hours, and finally roasting in a muffle furnace at 350 ℃ for 5 hours in an air atmosphere to obtain the catalytic wet oxidation catalyst Cu/Ce/gamma-Al2O3And measuring the content of Cu in the catalyst by ICP (inductively coupled plasma), and researching the influence of the change of the loading amount of the active component of the catalyst on the catalytic effect.
Taking a compound containing CN-And Cl-200mL of high-salt organic wastewater, wherein the initial concentration of COD is 40000 mg/L; CN-Initial concentration 2000mg/L, Cl-In the form of NaCl salt with a salt concentration of 10.2% and Cl-The content of (b) is 60153.85mg/L, and the catalyst Cu/Ce/gamma-Al is added according to the adding amount of 0.1g/L2O3The reaction conditions are as follows: the reaction temperature is 200 ℃, the oxygen partial pressure is 1.8MPa, the reaction time is 120min, and COD and CN in the wastewater after the reaction are measured-Content and Cu2+Content, calculating COD removal rate, CN-The removal rate is used for judging the catalytic activity of the catalyst and the stability of active metal components, and specific data are shown in table 1.
Table 1 catalyst evaluation data
Figure BDA0003185410070000091
As can be seen from the catalyst evaluation results, the catalyst prepared by the present invention was used for treating CN-containing gas-And Cl-The highest COD removal rate of the high-salt organic wastewater can reach more than 95 percent, and CN-The removal effect of (2) is maintained at a high level, wherein the active metal is loaded on the vermiculite modified catalyst carrier by adopting an ion exchange method, the loading amount of Cu is higher, and particularly compared with the catalyst prepared in a comparative example 3, when the catalyst is used for treating specific wastewater, the catalytic activity is higher, the loss rate of the active metal is reduced, and the stability of the catalyst is improved.

Claims (15)

1. A method for preparing a support-modified catalyst, comprising the steps of:
(1) dissolving a silicon source, an aluminum source and an organic template agent in deionized water, stirring into uniform gel, and then carrying out gel aging;
(2) modifying the gel obtained in the step (1) by adopting vermiculite, and then carrying out hydrothermal crystallization, washing, drying and roasting to obtain a catalyst carrier ZSM-5/Vt;
(3) and (3) carrying out ion exchange on the catalyst carrier ZSM-5/Vt obtained in the step (2) by adopting a solution containing a Cu source and a Ce source, and roasting to obtain the catalyst.
2. The method for preparing the catalyst according to claim 1, wherein in the step (1), the silicon source is one or more of sodium metasilicate, silica sol, water glass and tetraethoxysilane.
3. The method for preparing a catalyst according to claim 1, wherein in the step (1), the aluminum source is one or more of aluminum nitrate, aluminum sulfate, aluminum isopropoxide and sodium metaaluminate.
4. The method for preparing the catalyst according to claim 1, wherein in the step (1), the organic template is one or more of tetrapropylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, ethylenediamine, diethylamine and triethylamine.
5. The method for preparing a catalyst according to claim 1, wherein in the step (1), the molar ratio of the silicon source, the aluminum source, the organic template and the water is 100: 1-5: 4-20: 3000-4000;
the gel aging time is 12-36 h.
6. The method for preparing the catalyst according to claim 1, wherein in the step (2), the weight ratio of the gel to the vermiculite is 100: 10-30;
grinding vermiculite into powder of 100-200 meshes, and modifying the gel obtained in the step (1).
7. The method for preparing the catalyst according to claim 1, wherein in the step (2), the hydrothermal crystallization temperature is 130 to 180 ℃, and the hydrothermal crystallization time is 12 to 48 hours;
the roasting time is 3-8 h, and the roasting temperature is 400-650 ℃.
8. The method for preparing the catalyst according to claim 1, wherein in the step (3), the Cu source is a soluble Cu salt, preferably copper nitrate, and the concentration of the Cu source is 0.05-0.2 mol/L;
the Ce source is soluble Ce salt, preferably cerium nitrate, and the concentration of the Ce source is 0.05-0.2 mol/L.
9. The preparation method of the catalyst according to claim 1, wherein in the step (3), the ion exchange is carried out under stirring conditions, the temperature of the ion exchange is 20-60 ℃, the ion exchange time is 4-12 h, and the ion exchange frequency is 1-3 times;
the roasting time is 2-8 h, and the roasting temperature is 400-650 ℃.
10. A catalyst obtained by the production method according to any one of claims 1 to 9.
11. Use of a catalyst according to claim 10 in the treatment of organic waste water.
12. Use according to claim 11, wherein the treatment of the organic waste water is carried out under the action of oxygen and the catalyst.
13. Use according to claim 11, wherein the organic waste water contains CN-And/or Cl-。
14. Use according to claim 13, characterized in that the organic waste water isThe initial COD concentration is 1000-40000 mg/L; CN in waste water-The initial concentration is 10-2000 mg/L.
15. Use according to any one of claims 11 to 14, wherein the partial pressure of oxygen during the treatment is between 0.5 and 2.5 MPa; the dosage of the catalyst is 0.05-3 g per L of wastewater.
CN202110860158.6A 2021-07-28 2021-07-28 Carrier modified catalyst, preparation method thereof and application thereof in wastewater treatment Pending CN113634276A (en)

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Publication number Priority date Publication date Assignee Title
US4496785A (en) * 1983-09-28 1985-01-29 Standard Oil Company (Indiana) Process for reacting alcohols and olefins
CN101259428A (en) * 2008-04-24 2008-09-10 福州大学 Preparation of catalyst for processing industrial wastewater and using method thereof
CN109012740A (en) * 2018-08-22 2018-12-18 国家能源投资集团有限责任公司 Molecular sieve catalyst, preparation method and application for microwave catalysis oxidation processing organic wastewater

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