CN113546632A - Catalyst for treating phenolic wastewater by wet oxidation method and preparation method thereof - Google Patents

Catalyst for treating phenolic wastewater by wet oxidation method and preparation method thereof Download PDF

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CN113546632A
CN113546632A CN202110844962.5A CN202110844962A CN113546632A CN 113546632 A CN113546632 A CN 113546632A CN 202110844962 A CN202110844962 A CN 202110844962A CN 113546632 A CN113546632 A CN 113546632A
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王有倩
李国强
王宏宇
柴思琪
张国杰
张永发
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Taiyuan University of Technology
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Abstract

The invention discloses a catalyst for treating phenolic wastewater by wet oxidation and a preparation method thereof, wherein the catalyst comprises an active component and a carrier, wherein the active component comprises Cu and modified metal Ce, the carrier is biomass, and carbonization and activation are carried out after loading; wherein the loading amount of the active component is 2-6% of the mass of the carrier. And (3) impregnating the biomass with a copper ammonia solution, roasting at high temperature, and modifying Ce to obtain the catalyst. The catalyst prepared by the invention can stabilize the degradation rate of phenol to about 95.1% in a long time.

Description

Catalyst for treating phenolic wastewater by wet oxidation method and preparation method thereof
Technical Field
The invention relates to a catalyst for treating phenolic wastewater by a wet oxidation method and a preparation method thereof, belonging to the fields of water treatment technology and environmental protection.
Background
Phenol-containing wastewater contains high concentrations of phenolic compounds, which pose a threat to the ecosystem even at low concentrations due to their toxicity, and must be removed prior to discharge into the water system. The development of a technology for effectively removing or neutralizing phenol and derivatives thereof and the adoption of a proper sewage treatment strategy have important significance for solving the environmental problems. The method for treating the phenol-containing wastewater mainly comprises three major methods, namely a physical separation method, a biological degradation method and a chemical oxidation method. The method for treating the phenolic wastewater in the physical separation method is mainly extraction, the secondary pollution phenomenon is easy to occur due to solvent mixing in the treatment process, the chemical oxidation method is generally used for treating the phenolic wastewater with high concentration, and the biological degradation method is suitable for treating the phenolic wastewater with medium and low concentration.
Among chemical oxidation processes, Advanced Oxidation Processes (AOPs) such as Fenton's method, ozonization, photocatalytic ozonization, and the like are widely used for low-concentration organic matter, and incineration is suitable for high-concentration organic matter (COD is not less than 100 g/L). However, the use of incineration has not been encouraged in recent years, since it is not an eco-friendly process and other harmful compounds may be produced in the reaction. The wet oxidation method is generally suitable for the treatment of wastewater having an initial COD in the range of 20 to 200 g/L, and therefore, the process is a practical treatment method for wastewater that cannot be concentrated to be incinerated or diluted to AOPs. The wet oxidation (WAO) is to oxidize organic substances in wastewater into CO by using oxygen under the conditions of high temperature (400-573K) and high pressure (0.5-20 MPa)2And H2O or a biodegradable small molecule acid. The wet oxidation process can realize self-sufficiency of reaction heat, which means that the wet oxidation method is an effective method for treating high concentrationThe economically feasible technology of organic matters generally requires higher reaction temperature and pressure in order to realize the complete oxidation of organic pollutants into carbon dioxide and water, and the treatment process often generates acidic intermediate oxidation products, so that the removal rate of TOC is reduced, and the development and application of wet oxidation technology are severely limited. To address these problems, researchers added the catalyst during the experiment. This process is known as catalytic wet oxidation (CWAO). The use of the catalyst in the catalytic wet oxidation can enable the reaction to be carried out efficiently and favorably, reduce the reaction conditions and equipment requirements in the operation to a certain extent, shorten the reaction time and improve the oxidation efficiency of organic matters, so that the organic matters are widely researched and applied. The development of catalytic wet oxidation catalysts has greatly promoted the improvement of catalytic efficiency over the last two decades.
The catalysts required for the catalytic wet oxidation reaction can be classified into homogeneous catalytic wet oxidation and heterogeneous catalytic wet oxidation according to the phase of the catalyst used. Cu for homogeneous catalytic wet oxidation2+、Fe2+Soluble transition metal ions are used as a catalyst, so that the degradation efficiency of phenol at low temperature can be obviously improved, the catalyst has specific selectivity, secondary pollution is caused by precipitation under an alkaline condition, and the metal ion catalyst is difficult to recover. In contrast, heterogeneous catalysts can overcome these disadvantages and have the advantages of good stability, low cost, high activity and easy separation, so that more researchers are focused on the development and improvement of heterogeneous catalytic wet oxidation catalysts.
The active centers of the catalytic wet oxidation catalysts are roughly divided into two types, namely, noble metals and transition metals, the noble metals are usually Pd, Rh, Pt, Ir and the like, the noble metal catalysts are heterogeneous catalytic wet oxidation catalysts with the best catalytic performance, the catalytic effect is good, active components are not easy to lose, but the noble metals are expensive and resources are scarce, and the transition metal oxide catalysts of oxides such as Cu, Fe, Mn, Ni and the like are widely used for treating various organic pollutants in order to reduce the process cost. The transition metal oxide catalyst is easy to prepare, high in catalytic activity, low in price, good in catalytic effect on organic matters such as phenols and the like, and economical efficiency and high efficiency are both considered.
The most commonly used supports for heterogeneous catalysts are metal oxides, molecular sieves and carbon materials. The active carbon has high specific surface area and developed pore structure, is a good catalyst carrier choice, and is widely applied to the preparation of various catalysts due to the advantages of high thermal stability, high mechanical strength, good chemical inertness, low price, easily available raw materials and the like. Common carbon materials include activated carbon, graphite, carbon nanotubes, carbon nanofibers, and the like. The main raw materials of the activated carbon are wood, coal and other substances, but the resources are limited and the price is higher.
Chinese patent CN 112191244 a discloses "an activated carbon-supported gold-based catalyst and a preparation method and application thereof in acetylene hydrogenation", which is to impregnate activated carbon with a nitric acid aqueous solution, then to impregnate the treated activated carbon into a mixed solution of diphenyl sulfide, urea and ethanol, to obtain a required activated carbon carrier through processes of ultrasound, drying, carbonization, and the like, to prepare the catalyst, wherein the obtained catalyst shows high activity and stability in the aspect of acetylene conversion, but the catalyst carrier used in the preparation process is activated carbon modified by a series of activations, so that the loss of active components is easy to occur in the catalysis process, which affects the service life of the catalyst and causes the waste of precious metal resources.
Chinese patent CN 108452812B discloses a supported metal sulfide catalyst, a preparation method and an application thereof, in which coconut shell activated carbon is added into a metal nitrate solution in proportion after being subjected to acid treatment, and the supported metal sulfide catalyst is obtained by stirring, ultrasound, aging, drying and constant temperature vulcanization, and combines the properties of activated carbon and metal sulfide, so that the NO conversion rate at 250 ℃ can reach 99.04% in a catalytic reduction NO denitration reaction, and the biomass such as coconut shells is low in price and wide in source, has strong practicability, and the coconut shell activated carbon used in the preparation is wide in source and low in cost, but the loss condition of active components is still easy to occur in a carrier, and the prepared catalyst is often deficient in hardness and cohesiveness, is not easy to recover in use and is easy to lose.
Chinese patent CN 109465008A discloses 'a catalytic wet oxidation catalyst and a preparation method and application thereof', in the catalyst, Au and Pd are used as active components and are loaded by an impregnation method, and a carrier can be active carbon, MgO, ZnO, BaO and TiO2Or CeO2And the carrier is required to be impregnated in a salt solution of the modified metal Pd and then roasted before being loaded. Although the catalyst can ensure the advantages of high stability, high catalytic activity, high selectivity and the like, Au and Pd are rare in resources and expensive, and are not suitable for mass production.
Chinese patent CN 107790152B discloses "a catalyst for removing harmful gases and a preparation method and application thereof", which uses activated carbon as a carrier, utilizes biomass to prepare activated carbon, activates the activated carbon with hydrogen peroxide to load copper and strong metal oxides, and the activated carbon has higher specific surface area and higher porosity, and the obtained catalyst has low cost and higher stability, is used for removing harmful gases such as formaldehyde and the like, and can effectively improve the removal rate. However, in the preparation process, the biomass is firstly used for preparing the active carbon, and then the active carbon is modified, so that the catalyst prepared by the preparation method is not firm in active component loading, and is easy to separate from the carrier in the reaction to cause a large amount of loss.
Chinese patent CN 108014806B discloses a method for preparing a wet catalytic oxidation catalyst by using a waste catalytic cracking catalyst, wherein a carrier is obtained by impregnating materials such as activated carbon and the like with a liquid with a copper source, and active components are rare earth metal elements. The waste gas catalyst used in the preparation process can be easily deactivated and has low catalyst selectivity in the catalytic wet oxidation process, and the continuous and efficient reaction can not be ensured.
In the existing preparation process of a catalyst taking an active component as a carrier and precious metal or filter metal as an active component, activated carbon is usually from anoxic combustion of wood, coal and the like, a large amount of resources are consumed in the preparation process, and in the use process, the activated carbon is usually used as the catalyst carrier after being activated and modified, so that the preparation method has the problems of easy loss of the active component, poor stability of the catalyst and the like.
Disclosure of Invention
The invention aims to provide a catalyst for treating phenolic wastewater by a wet oxidation method and a preparation method thereof, wherein the obtained catalyst is a copper-based supported catalyst, and a carrier with the advantages of high specific surface area, high porosity, high formability, low price, easy obtainment, rich resources and the like is adopted, so that the catalyst has the advantages of high activity, high selectivity, high stability, simple preparation method and large-scale industrial application.
According to the invention, transition metals Cu and Ce are selected as active components, biomass is used as a precursor, the biomass is used for impregnation loading and then carbonization, activation and other treatments are carried out, oxygen-containing and nitrogen-containing groups rich in the biomass are fully utilized, the firm combination of the transition metals and the biomass is realized, the preparation cost of the catalyst is reduced, the service life of the catalyst is effectively prolonged, and the problems of high cost, poor stability and the like in the traditional catalyst preparation process by using an impregnation method with activated carbon as a carrier are effectively solved.
The invention provides a catalyst for wet oxidation treatment of phenol-containing wastewater, which comprises an active component and a carrier, wherein the active component comprises Cu and modified metal Ce; the carrier is biomass; wherein the loading mass of the active components is 2-6% of the mass of the carrier, and the ratio of the loading amounts of the two active components is 1-5: 1-5.
The invention provides a preparation method of the catalyst for treating phenolic wastewater by wet oxidation, which comprises the following steps:
(1) preparing a copper ammonia solution: dropwise adding a sodium hydroxide solution into a saturated copper sulfate solution until the pH value is =10-12, filtering, and dropwise adding concentrated ammonia water into filter residues until the concentrated ammonia water is completely dissolved to obtain a copper ammonia solution;
the specific preparation process of the cuprammonium solution comprises the following steps: dropwise adding a sodium hydroxide solution with the mass fraction of 10% into a saturated copper sulfate solution until the pH of the system is =12, filtering to obtain a precipitate, washing with water for 3-4 times, filtering, taking filter residue, drying for 12 hours at the temperature of 60 ℃ and under the vacuum degree of 0.06MPa, and dropwise adding concentrated ammonia water until the concentrated ammonia water is completely dissolved to obtain a copper ammonia solution;
(2) preparing a needed carrier, and marking as AC;
the precursor of the carrier is one of walnut shells, coconut shells, grape seeds, corncobs and peanut shells;
the needed carrier is obtained by washing biomass with deionized water for 3-4 times, drying at 90-110 ℃ for 12-24h, and grinding to 12-16 meshes;
(3) soaking 1g of carrier in 1-5ml of copper ammonia solution, stirring, filtering and drying; the mass fraction of Cu in the cuprammonium solution is 1-5%, the temperature is 10-40 ℃, the stirring time is 12-24h, the drying temperature is 100-;
(4) carbonizing, activating, cooling, washing and drying the dried material to obtain a required catalyst which is named as Cu/AC;
in the step (4), the carbonization temperature is 600-; the activated gas is CO2The activation temperature is 700-; the carbonization temperature is increased to 800 ℃ from room temperature at the speed of 5-10 ℃/min, and the temperature rising and cooling processes need to be protected by inert gas in the period;
(5) the method comprises the steps of (1) soaking Cu/AC in a cerous nitrate solution, stirring, filtering, drying, roasting, cooling, washing with water and drying to obtain a Ce modified catalyst, which is named as CeCu/AC;
in the step (5), the cerium nitrate solution and the Cu/AC are impregnated according to the proportion that 1g of carrier is impregnated by 1-5ml of cerium nitrate solution, wherein the mass fraction of Ce in the cerium nitrate solution is 1-5%, the impregnation temperature is 10-40 ℃, the stirring time is 12-24h, the drying temperature is 100-120 ℃, and the drying time is 12-24 h; the roasting temperature is 350-450 ℃, and the time is 1-2 h.
The active component copper comes from copper element in the cuprammonium solution;
the modified metal participates in modification after Cu loading is finished;
the modified metal Ce single element load mass fraction is 1% -5%.
The invention provides a preparation method of the catalyst for treating phenolic wastewater by wet oxidation, which comprises the following specific steps:
(1) preparing a copper ammonia solution: dropwise adding a sodium hydroxide solution with the mass fraction of 10% into a saturated copper sulfate solution until the pH of the system is =12, filtering to obtain a precipitate, washing with water for 3-4 times, filtering, taking filter residues, drying for 12 hours at the temperature of 60 ℃ and under the vacuum degree of 0.06MPa, and dropwise adding concentrated ammonia water until the concentrated ammonia water is completely dissolved;
(2) preparing a carrier: respectively washing walnut shells or coconut shells with tap water and distilled water for three times, drying at 110 ℃ for 24 hours, crushing, grinding to 12-16 meshes, and marking as AC;
(3) preparation of Cu/AC: mixing 40g of walnut shell particles with copper ammonia solution, wherein the volume of the copper ammonia solution required by 40g of walnut shell particles is 40-200ml, stirring, soaking for 24h, filtering, and then adding 110 g of the copper ammonia solutionoAnd C, drying for 24 hours. The sample was placed in a high temperature activation furnace at N2Under atmosphere 10oC/min heating to 800oAnd C, carbonizing for 2 hours at constant temperature. Then N is added2Switching to CO2At 800oActivating at constant temperature for 2h under C, stopping heating, and activating at N2The atmosphere was cooled to room temperature and the final product was washed with deionized water. After filtration at 105oDrying for 12h under C to obtain a Cu/AC catalyst;
(4) CeCu/AC preparation: weighing 3.72g of cerium nitrate, and dissolving the cerium nitrate in a certain amount of 150ml of secondary deionized water to prepare a precursor solution; soaking 10 g of Cu/AC in the solution for 24h under stirring, filtering, drying at 110 deg.C for 12h to obtain sample, and adding N2Roasting for 2h at 450 ℃ in the atmosphere, cooling to room temperature, washing for a plurality of times, and drying to obtain Ce modified Cu/AC, which is named as CeCu/AC.
The invention has the beneficial effects that: according to the invention, the biomass is used as the source of the active carbon carrier, so that the preparation cost of the catalyst can be greatly reduced, the transition metal is used as the active center, the loss of noble metal is reduced while the catalytic activity is ensured, and in the preparation process, the method of directly loading the active center by the biomass and then preparing the active carbon supported Cu-based catalyst by activating and carbonizing the obtained sample can be adopted, so that the condition that active components are easy to lose in the method of firstly carbonizing to obtain the active carbon and then loading the active carbon can be improved.
Drawings
FIG. 1 is a graph showing the effect of catalytic wet oxidative degradation of phenol wastewater by catalysts of comparative example 1 and comparative example 2: (a) the conversion rate of phenol; (b) COD conversion rate.
FIG. 2 shows the performances of the catalysts obtained in comparative example 1 and example 1 in catalyzing wet oxidative degradation of phenol wastewater: (a) the conversion rate of phenol; (b) COD conversion rate chart.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1:
the method comprises the following steps:
the preparation process of the copper ammonia solution comprises the following steps: dropwise adding a sodium hydroxide solution with the mass fraction of 10% into a saturated copper sulfate solution until the pH of the system is =12, filtering to obtain a precipitate, filtering after 3-4 times of water system, taking filter residue, drying for 12 hours at the temperature of 60 ℃ and under the vacuum degree of 0.06MPa, and dropwise adding concentrated ammonia water until the concentrated ammonia water is completely dissolved to obtain a copper ammonia solution;
step two:
washing walnut shells with tap water and distilled water respectively for three times, drying at 110 ℃ for 24 hours, crushing, grinding, and sieving with a 14-mesh sieve, and marking as AC; taking 40g of walnut shell particles, taking copper ammonia solution with 3% of Cu mass fraction, stirring and soaking the walnut shell particles and the walnut shell for 24 hours, filtering, and then soaking the walnut shell particles at 110 DEGoAnd C, drying for 24 hours. Accurately weighing a certain amount of cerium nitrate (Ce (NO)3)3·6H2O), dissolving the walnut shell particles in quantitative secondary deionized water, soaking the walnut shell particles treated by cuprammonium in 150ml of cerium nitrate solution with the Ce mass fraction of 3%, stirring for 24h, filtering, and obtaining the product of 110%oAnd C, drying for 24 hours. The sample was placed in a high temperature activation furnace at N2Under atmosphere 10oC/min heating to 800oAnd C, carbonizing for 2 hours at constant temperature. Will N2Switching to CO2At 800oActivating at constant temperature for 2h under C, and then activating at N2The atmosphere was cooled to room temperature and the final product was washed three times with deionized water. After filtration at 105oAnd C, drying for 12h to obtain the Ce modified Cu/AC catalyst prepared by the precursor method, and recording as CeCu/AC. .
Example 2: the method is adopted to prepare the CeCu/AC catalyst
The method comprises the following steps:
the preparation process of the copper ammonia solution comprises the following steps: dropwise adding a sodium hydroxide solution with the mass fraction of 10% into a saturated copper sulfate solution until the pH of the system is =12, filtering to obtain a precipitate, filtering after 3-4 times of water system, taking filter residue, drying for 12 hours at the temperature of 60 ℃ and under the vacuum degree of 0.06MPa, and dropwise adding concentrated ammonia water until the concentrated ammonia water is completely dissolved to obtain a copper ammonia solution;
step two:
washing walnut shells with tap water and distilled water respectively for three times, drying at 110 ℃ for 24 hours, crushing, grinding, and sieving with a 16-mesh sieve, and marking as AC; diluting copper ammonia solution with Cu mass fraction of 3% to 150ml, soaking with 40g walnut shell under stirring for 24 hr, filtering, and soaking at 110%oAnd C, drying for 24 hours. Accurately weighing a certain amount of cerium nitrate (Ce (NO)3)3·6H2And O), dissolving the walnut shell particles in quantitative secondary deionized water to prepare a cerium nitrate solution with the Ce mass fraction of 3%, impregnating the walnut shell particles treated by cuprammonium with 150ml of the cerium nitrate solution, stirring for 24 hours, filtering, and drying at 110 ℃ for 24 hours. The sample was placed in a high temperature activation furnace at N2Heating to 800 ℃ at a speed of 10 ℃/min under the atmosphere, and carbonizing for 2h at constant temperature. Will N2Switching to CO2Activating at 800 deg.C for 2h, and then activating in N2The atmosphere was cooled to room temperature and the final product was washed three times with deionized water. After filtration, drying at 110 ℃ for 12h gave the Ce modified Cu/AC catalyst, noted CeCu/AC.
Comparative example 1:
the method comprises the following steps:
the preparation process of the copper ammonia solution comprises the following steps: dropwise adding a sodium hydroxide solution with the mass fraction of 10% into a saturated copper sulfate solution until the pH of the system is =12, filtering to obtain a precipitate, filtering after 3-4 times of water system, taking filter residue, drying for 12 hours at the temperature of 60 ℃ and under the vacuum degree of 0.06MPa, and dropwise adding concentrated ammonia water until the concentrated ammonia water is completely dissolved to obtain a copper ammonia solution;
step two:
washing walnut shells with tap water and distilled water respectively for three times, drying at 110 ℃ for 24 hours, crushing, grinding, and sieving with a 14-mesh sieve, and marking as AC; taking 40g walnut shell particles, taking copper ammonia solution with the Cu content of 1%, 3% and 5% by mass, stirring and soaking the walnut shell particles and the walnut shell for 24 hours, filtering, and then adding the mixture to the mixture at 110 DEGoAnd C, drying for 24 hours. The sample was placed in a high temperature activation furnace at N2Under atmosphere 10oC/min heating to 800oAnd C, carbonizing for 2 hours at constant temperature. Then N is added2Switching to CO2At 800oActivating at constant temperature for 2h under C, stopping heating, and activating at N2The atmosphere was cooled to room temperature and the final product was washed with deionized water. After filtration at 105oAnd drying for 12h under the condition of C to obtain the Cu/AC catalyst, wherein the load amounts of the Cu/AC catalyst are marked as PI-1, PI-3 and PI-5.
Comparative example 2:
washing walnut shell with tap water and distilled water for three times, drying at 110 deg.C for 24 hr, pulverizing, grinding to 12-16 mesh, placing in high temperature activation furnace, and activating in N2Under atmosphere 10oC/min heating to 800oAnd C, carbonizing for 2 hours at constant temperature. Then N is added2Switching to CO2At 800oActivating at constant temperature for 2h under C, stopping heating, and activating at N2Cooling to room temperature in the atmosphere, washing the un-impregnated walnut shells by deionized water, carbonizing under the preparation conditions, and activating to obtain blank activated carbon, which is marked as AC. Soaking a certain amount (10 g) of AC in 150ml of cuprammonium solution with the mass fraction of Cu of 3%, stirring and soaking at room temperature for 24h, filtering, and soaking at 110%oDrying for 12h at C to obtain sample in N2Atmosphere, 350oRoasting for 4 hours under C, and cooling to room temperature to prepare Cu/AC catalysts prepared by other methods, which are marked as ACI-1, ACI-3 and ACI-5;
the phenol conversion presented in fig. 1- (a) shows that both Cu/AC catalysts show better activity in catalyzing the wet oxidative degradation of phenol, the conversion being determined by the catalyst preparation method and the impregnation ratio. Therefore, the catalytic activity change law is as follows: PI-3 > PI-5 > ACI-3 > ACI-1 > PI-1. The phenol degradation rate of the Cu/AC catalyst can reach more than 96% in the initial stage of the reaction, but after the reaction is carried out for 1.5 h, the phenol degradation rates of the ACI-3, ACI-1 and PI-1 catalysts begin to decline sharply, and all decline to 88% in the reaction time of 8.5 h. The phenol degradation rates of the PI-3, PI-5 and ACI-5 catalysts are slightly reduced, but are respectively maintained at 95.1%, 95.5% and 93.3% when the reaction time is 8.5 h. Phenol is partially oxidized during the oxidation process, producing many intermediates and by-products, with the difficult-to-oxidize small organic acids contributing to the residual COD value. The curve of the change of the COD conversion rate in the graph 1- (b) shows the same change rule as the phenol degradation rate, after the reaction is carried out for 8.5 hours, the catalysts of PI-3, PI-5 and ACI-5 reach similar COD conversion rates, and the COD conversion rates of the catalysts of ACI-3, ACI-1 and PI-1 are sharply reduced to about 77 percent. It can be seen that, under the same impregnation ratio, the Cu/AC catalyst prepared by the PI method exhibits higher catalytic activity than the Cu/AC catalyst prepared by the comparative example 1, which is attributed to the precursor impregnation method capable of bringing a large specific surface area, a high Cu content, uniform distribution of active components, and a uniform crystal structure to the final Cu/AC catalyst. Therefore, the invention selects a precursor dipping method for preparation.
As can be seen from FIG. 2- (a), the Cu/AC catalyst shows better activity in catalyzing wet oxidation degradation of phenol, the phenol degradation rate reaches more than 95% in the initial stage, and as the reaction proceeds, the catalytic activity of Cu/AC is slightly increased after being reduced, and is still maintained at about 95% after 5 hours of reaction.
After the addition of the auxiliary agent Ce, the catalytic activity of the CeCu/AC-II is obviously improved, the phenol degradation rate reaches 98.0% at the beginning of the reaction, and the phenol degradation rate is kept above 99.5% in the subsequent reaction time. As can be seen from FIG. 2- (b), the COD degradation rate of Cu/AC in the initial stage of reaction can reach 96.7%, but after 1h of reaction, the COD degradation rate gradually decreases with the progress of reaction and tends to stabilize at about 92%. While the CeCu/AC-II can always keep high COD conversion rate (97.5-99.1%) within 5 h of reaction.
The result shows that the introduction of the auxiliary agent Ce by adopting the method of the invention can obviously improve the Cu on the surface of the catalyst+Content and chemisorbed oxygen content, enhancing the redox capability of the catalyst.

Claims (8)

1. A catalyst for wet oxidation treatment of phenolic wastewater is characterized in that: the catalyst comprises an active component and a carrier, wherein the active component comprises Cu and a modified metal Ce; the carrier is biomass, and is carbonized and activated after being loaded; wherein the loading amount of the active components is 2-6% of the mass of the carrier, and the ratio of the loading amounts of the two active components is 1-5: 1-5.
2. A method for preparing the catalyst for wet oxidation treatment of phenol-containing wastewater according to claim 1, characterized by comprising the steps of:
(1) preparing a copper ammonia solution: dropwise adding a sodium hydroxide solution into a saturated copper sulfate solution until the pH value is =12, filtering, and dropwise adding concentrated ammonia water into filter residues until the concentrated ammonia water is completely dissolved to obtain a copper ammonia solution;
(2) preparing a needed carrier, and marking as AC;
washing biomass with deionized water for 3-4 times, drying at 90-110 deg.C for 12-24 hr, pulverizing, and grinding to 12-16 mesh to obtain required carrier;
(3) dipping, stirring, filtering and drying 1g of carrier by using 1-5ml of copper ammonia solution;
(4) carbonizing, activating, cooling, washing and drying the material obtained in the step (3) to obtain a required catalyst which is named as Cu/AC;
(5) and (3) soaking the Cu/AC in a cerous nitrate solution, stirring, filtering, drying, roasting, cooling, washing with water and drying to obtain the Ce modified catalyst, which is named as CeCu/AC.
3. The method according to claim 2, wherein the catalyst for wet oxidation treatment of phenol-containing wastewater comprises: the specific preparation process of the cuprammonium solution comprises the following steps: dropwise adding a sodium hydroxide solution with the mass fraction of 10% into a saturated copper sulfate solution until the pH of the system is =12, filtering to obtain a precipitate, washing with water for 3-4 times, filtering, taking filter residue, drying at 60-80 ℃ under the vacuum degree of 0.06MPa for 12-24 hours, and dropwise adding concentrated ammonia water until the concentrated ammonia water is completely dissolved to obtain a copper ammonia solution.
4. The method according to claim 2, wherein the catalyst for wet oxidation treatment of phenol-containing wastewater comprises: the biomass comprises one of walnut shells, coconut shells, grape seeds, corncobs and peanut shells.
5. The method according to claim 2, wherein the catalyst for wet oxidation treatment of phenol-containing wastewater comprises: in the step (3), the mass fraction of Cu in the impregnation liquid is 1-5%, the temperature is 10-40 ℃, the stirring time is 12-24h, the drying temperature is 100-120 ℃, and the drying time is 12-24 h.
6. The method according to claim 2, wherein the catalyst for wet oxidation treatment of phenol-containing wastewater comprises: in the step (4), the carbonization temperature is 600-; the activated gas is CO2The activation temperature is 700-; the carbonization temperature is increased from room temperature to 600-800 ℃ at the speed of 5-10 ℃/min, and the temperature rising and cooling processes need to be protected by inert gas.
7. The method according to claim 2, wherein the catalyst for wet oxidation treatment of phenol-containing wastewater comprises:
in the step (5), 1g of carrier is impregnated by 1-5ml of cuprammonium solution, the mass fraction of Ce in the cerous nitrate solution is 1% -5%, the temperature is 10-40 ℃, the stirring time is 12-24h, the drying temperature is 100-; the roasting temperature is 350-450 ℃, and the time is 1-2 h.
8. The method according to claim 2, wherein the catalyst for wet oxidation treatment of phenol-containing wastewater comprises: the preparation process comprises the following steps:
(1) preparing a copper ammonia solution: dropwise adding a sodium hydroxide solution with the mass fraction of 10% into a saturated copper sulfate solution until the pH of the system is =12, filtering to obtain a precipitate, washing with water for 3-4 times, filtering, taking filter residues, drying for 12 hours at the temperature of 60 ℃ and under the vacuum degree of 0.06MPa, and dropwise adding concentrated ammonia water until the concentrated ammonia water is completely dissolved;
(2) preparing a carrier: respectively washing walnut shells or coconut shells with tap water and distilled water for three times, drying at 110 ℃ for 24 hours, crushing, grinding to 12-16 meshes, and marking as AC;
(3) preparation of Cu/AC: mixing 40g of walnut shell particles with copper ammonia solution, wherein the volume of the copper ammonia solution required by 40g of walnut shell powder is 40-200ml, stirring, soaking for 24h, filtering, and then adding 110 g of the mixtureoC, drying for 24 hours; the sample obtainedThe product is placed in a high temperature activation furnace in N2Under atmosphere 10oC/min heating to 800oC, carbonizing for 2 hours at constant temperature; then N is added2Switching to CO2At 800oActivating at constant temperature for 2h under C, stopping heating, and activating at N2Cooling to room temperature in the atmosphere, and washing the final product with deionized water; after filtration at 105oDrying for 12h under C to obtain a Cu/AC catalyst;
(4) CeCu/AC preparation: weighing 3.72g of cerium nitrate, and dissolving the cerium nitrate in 150ml of secondary deionized water to prepare a precursor solution; soaking 10 g of Cu/AC in the precursor solution, stirring and soaking for 24h, filtering, drying at 110 ℃ for 12h to obtain a sample, and adding N2Roasting for 2h at 450 ℃ in the atmosphere, cooling to room temperature, washing for a plurality of times, and drying to obtain Ce modified Cu/AC, which is named as CeCu/AC.
CN202110844962.5A 2021-07-26 2021-07-26 Catalyst for treating phenolic wastewater by wet oxidation method and preparation method thereof Pending CN113546632A (en)

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