Oxidation catalyst for degrading organic matters and preparation method thereof

Abstract

The invention provides an oxidation catalyst for degrading organic matters and a preparation method of the oxidation catalyst, and the preparation method comprises the following steps: modifying activated carbon by using an oxidizing agent, and then sequentially soaking in metal salt, ammonia water and metal salt for treatment to obtain the catalyst enriched with various active component forms. The catalyst has high activity and long service life, the catalyst components do not fall off in the use process, and the stability of the activity of the catalyst is kept. The catalyst disclosed by the invention is simple in preparation process, mild in condition, high in activity and long in service life, has a very high catalytic oxidation degradation rate on organic matters, and has a good application prospect.

Description

Technical Field

[0001] The invention belongs to the technical field of catalyst preparation technology, and specifically relates to a high-activity and long-life oxidation catalyst for degrading organic matter and a preparation method thereof. Background Art

[0002] Organic matter in wastewater is the main substance of COD and the main reason why wastewater cannot be discharged. Its main harm is to cause eutrophication of water bodies and seriously affect the ecological balance of water bodies.

[0003] At present, there are many treatment technologies for organic wastewater. According to different treatment principles, they are mainly divided into three categories: physicochemical method, chemical method and biochemical method. Physicochemical method mainly includes adsorption method, extraction method, membrane separation method, coagulation method, flotation method and ion exchange method. Chemical method mainly includes iron-carbon electrolysis method and advanced oxidation technology. Biological method is divided into three types: aerobic biological treatment method, anaerobic biological treatment method and aerobic-anaerobic combined treatment method. These methods have achieved good results for specific organic wastewater, but these methods all have certain limitations. In contrast, biological method has been widely used due to its low cost, mature technology and wide application range. However, biological method is powerless to treat organic wastewater that restricts and harms the growth and metabolism of microorganisms. Advanced oxidation technology makes up for the shortcomings of biological method in this regard. Advanced oxidation technology uses free radicals with extremely strong oxidative activity to degrade organic pollutants in wastewater, and ultimately converts pollutants into CO 2 , H 2 O and some inorganic ions. Advanced oxidation technologies include photocatalytic oxidation, ozone oxidation, Fenton oxidation, wet oxidation, supercritical water oxidation, etc. Among them, ozone oxidation and Fenton oxidation are the most commonly used. Advanced oxidation technology is a clean and effective technology for treating organic wastewater, but the method currently has the disadvantages of high treatment cost, selectivity for reaction and low treatment rate. Summary of the invention

[0004] In order to overcome the shortcomings of existing organic wastewater treatment technology and achieve the purpose of low cost and wide application, the present invention provides a high-activity and long-life organic catalytic oxidation degradation catalyst and a preparation method thereof. The catalyst uses activated carbon as a carrier, and the surface of the activated carbon with the characteristics of being porous, large specific surface area, acid and alkali resistant is modified to load metal ion components with different forms of activity on the carrier. The activated carbon carrier has a good enrichment effect on active components of different forms, and some active components of different forms are firmly bound to the inner surface of the catalyst. The excess catalyst active components that are not firmly bound are removed by washing with water. The activated carbon carrier has a certain amount of firmly binding to active components of one form, but it can also firmly bind active components of other forms. The catalyst enriched with multiple active component forms obtained in this way not only has high activity and long life, but also the catalyst components do not fall off during use, and the catalyst activity is kept stable.

[0005] The catalyst of the present invention has a simple preparation process, mild conditions, high activity and long life, has a high catalytic oxidation degradation rate for organic matter in wastewater, and has good application prospects. The catalyst is used for the degradation of organic matter in wastewater, and the degradation rate of organic matter can reach up to 100%.

[0006] To achieve the above object, the present invention adopts the following technical solution: A method for preparing an oxidation catalyst for degrading organic matter comprises the following steps: (1) placing activated carbon in an oxidant solution, heating and refluxing, modifying the surface of the activated carbon, and then washing and drying to obtain a carrier; (2) immersing the carrier in a solution of a first metal salt so that the first metal salt is adsorbed on the surface of the carrier, and then washing to remove excess first metal salt on the surface of the carrier; (3) immersing the carrier treated in step (2) in an aqueous ammonia solution, and washing to remove excess ammonia on the surface of the carrier after the reaction; (4) Immersing the carrier treated in step (3) in a solution of a second metal salt so that the second metal salt is adsorbed on the surface of the carrier, and then washing to remove excess second metal salt on the surface of the carrier to obtain the catalyst.

[0007] Preferably, the first metal salt or the second metal salt is one or a mixture of more than one of cobalt salt, manganese salt, iron salt, chromium salt, nickel salt or copper salt.

[0008] More preferably, the first metal salt or the second metal salt is a cobalt salt or a manganese salt.

[0009] More preferably, the first metal salt and the second metal salt are both cobalt salts.

[0010] Preferably, the concentration of the oxidant solution in step (1) is less than 2 mol / L.

[0011] Preferably, the oxidant in step (1) is a mixture of one or more of potassium permanganate, potassium chlorate, potassium dichromate, hydrogen peroxide, hypochlorous acid, nitric acid, nitrous acid or sulfuric acid.

[0012] Preferably, the activated carbon in step (1) is a mixture of one or more of wood activated carbon, coconut shell activated carbon, coal activated carbon, fruit shell activated carbon, bone activated carbon or silver-loaded activated carbon.

[0013] Preferably, the heating reflux time in step (1) is less than 6 hours.

[0014] Preferably, the concentration of the first metal salt solution in step (2) or the second metal salt solution in step (4) is less than 240 g / L.

[0015] Preferably, the concentration of the aqueous ammonia in step (3) is below 28 wt %.

[0016] Preferably, the immersion time in the ammonia solution in step (3) is less than 12 hours.

[0017] The ammonia treatment can convert the metal ions adsorbed by the activated carbon into hydroxides and complexes with catalytic activity. The treated activated carbon can adsorb metal ions again, and the adsorbed metal ions are not easy to fall off from the surface of the activated carbon, so as to prepare a catalyst with high activity and good stability.

[0018] Preferably, the preparation method comprises the following steps: (1) placing powdered wood activated carbon in a 0.01-2 mol / L potassium permanganate solution, heating and refluxing for 0.1-4 h, then washing and drying to obtain a carrier; (2) immersing the support obtained in step (1) in an aqueous solution of 0.1 to 20 g / L cobalt acetate for 1 to 24 h, and then washing to remove excess cobalt acetate; (3) Soaking the carrier treated in step (2) in ammonia water with a concentration of less than 28 wt % for 1 to 4 h, and then washing until it becomes neutral; (4) The carrier treated in step (3) is immersed in a 0.1-20 g / L aqueous solution of cobalt acetate for 1-24 h, then washed to remove excess cobalt acetate, and dried to obtain the catalyst.

[0019] The second object of the present invention is to provide a catalyst prepared by the above preparation method.

[0020] The third object of the present invention is to provide an application of the catalyst prepared by the above preparation method in the degradation of organic matter in wastewater, the application comprising: The catalyst, oxygen and wastewater are placed in a reactor for reaction, the reaction temperature is 20-70°C, the oxygen reaction pressure is 0.1-2MPa, the catalyst dosage is 0.1wt%-5wt% (based on the amount of wastewater), preferably 5%-20%, most preferably 10%, and the reaction time is 0.5-8 h.

[0021] The catalyst of the present invention has the following advantages: (1) The catalyst preparation process is simple and easy to control; (2) The catalyst has high activity, long life, and can be used repeatedly and for a long time; (3) The active components on the catalyst are not easy to fall off and will not be transferred to the reaction liquid, which will not affect the subsequent process treatment. DETAILED DESCRIPTION

[0022] The present invention will be described in more detail below by way of examples, which are not intended to limit the scope of protection of the present invention.

[0023] Comparative Example 1 Weigh a certain amount of coconut shell activated carbon particles, add them to deionized water that can completely immerse the activated carbon, heat and boil for 1 hour, filter the activated carbon after cooling, and dry it for later use. Prepare a 10g / L cobalt acetate aqueous solution, add the treated activated carbon, and soak it for 5 hours. Filter the activated carbon from the cobalt acetate aqueous solution and wash the activated carbon with water until the washed liquid is colorless. The activated carbon obtained by drying is a catalyst that adsorbs and fixes a certain amount of metal ions, which is stored for later use. The obtained catalyst is used for the degradation of organic matter in wastewater. The reaction temperature is 60°C, the oxygen pressure is 0.25MPa, and the reaction is carried out in a high-pressure reactor for 2 hours, and the organic matter degradation rate is 82%.

[0024] Comparative Example 2 Weigh a certain amount of granular fruit shell activated carbon, add it to a 2mol / L nitric acid solution, heat and reflux for 2h, filter out the activated carbon after cooling, wash with a certain amount of deionized water and dry. Prepare an aqueous solution containing 12g / L of copper acetate, add the treated activated carbon, and soak for 5h. Filter the activated carbon from the copper acetate aqueous solution and wash the activated carbon with water until the washed liquid is colorless. The activated carbon obtained by drying is a catalyst that adsorbs and fixes a certain amount of metal ions, which is stored for later use. The obtained catalyst is used for the degradation of organic matter in wastewater. At a reaction temperature of 50°C, an oxygen pressure of 0.1MPa, and a high-pressure reactor for 6h, the organic matter degradation rate is 59%.

[0025] Comparative Example 3 Weigh a certain amount of powdered coal-based activated carbon, add it to a 1.5mol / L potassium dichromate solution, heat and reflux for 4h, filter out the activated carbon after cooling, wash with a certain amount of deionized water, and dry it. Prepare an aqueous solution containing 20g / L of ferric acetate, add the treated activated carbon, and soak it for 12h. Filter the activated carbon from the ferric acetate aqueous solution, wash the activated carbon with water until the washed liquid is colorless. The activated carbon obtained by drying is a catalyst that adsorbs and fixes a certain amount of metal ions, which is stored for later use. The obtained catalyst is used for the degradation of organic matter in wastewater. At a reaction temperature of 55°C, an oxygen pressure of 1MPa, and a high-pressure reactor for 3h, the degradation rate of organic matter is 83%.

[0026] Comparative Example 4 Weigh a certain amount of coconut shell activated carbon particles and add them to 1 mol / L KMnO 4 The solution was heated to reflux for 0.5h, and the activated carbon was filtered out after cooling, and then washed and dried with a certain amount of deionized water. Prepare an aqueous solution of cobalt acetate containing 20g / L, add the treated activated carbon, and soak for 5h. Filter the activated carbon from the aqueous solution of cobalt acetate, and wash the activated carbon with water until the washed liquid is colorless. The activated carbon obtained by drying is a catalyst that adsorbs and fixes a certain amount of metal ions, which is stored for later use. The obtained catalyst is used for the degradation of organic matter in wastewater. The reaction temperature is 60℃, the oxygen pressure is 0.25MPa, and the reaction is carried out in a high-pressure reactor for 2h, and the organic matter degradation rate is 87%.

[0027] Comparative Example 5 Weigh a certain amount of wood activated carbon particles, add them to a 0.5mol / L hydrogen peroxide solution, heat and reflux for 1h, filter out the activated carbon after cooling, wash with a certain amount of deionized water, and dry. Prepare a 5g / L manganese acetate aqueous solution, add the treated activated carbon, and soak for 8h. Filter the activated carbon from the manganese acetate aqueous solution, wash the activated carbon with water until the washed liquid is colorless. The activated carbon obtained by drying is a catalyst that adsorbs and fixes a certain amount of metal ions, which is stored for later use. The obtained catalyst is used for the degradation of organic matter in wastewater. The reaction temperature is 40℃, the oxygen pressure is 0.8MPa, and the reaction is carried out in a high-pressure reactor for 4h, and the organic matter degradation rate is 68%.

[0028] Comparative Example 6 Weigh a certain amount of coconut shell activated carbon particles, add them to a 2mol / L hypochlorous acid solution, heat and reflux for 4h, filter out the activated carbon after cooling, wash with a certain amount of deionized water and dry. Prepare a 50 g / L cobalt acetate aqueous solution, add the treated activated carbon, and soak for 60h. Filter the activated carbon from the cobalt acetate aqueous solution, wash the activated carbon with water until the washed liquid is colorless. The activated carbon obtained by drying is a catalyst that adsorbs and fixes a certain amount of metal ions, which is stored for later use. The obtained catalyst is used for the degradation of organic matter in wastewater. The reaction temperature is 30℃, the oxygen pressure is 0.5MPa, and the reaction is carried out in a high-pressure reactor for 8h, and the organic matter degradation rate is 35%.

[0029] Comparative Example 7 Weigh a certain amount of powdered coconut shell activated carbon, add it to a 0.05mol / L nitrous acid solution, heat and reflux for 4h, filter out the activated carbon after cooling, wash with a certain amount of deionized water and dry. Prepare an aqueous solution containing 30g / L nickel acetate, add the treated activated carbon, and soak for 100h. Filter the activated carbon from the nickel acetate aqueous solution, wash the activated carbon with water until the washed liquid is colorless. The activated carbon obtained by drying is a catalyst that adsorbs and fixes a certain amount of metal ions, which is stored for use. The obtained catalyst is used for the degradation of organic matter in wastewater. At a reaction temperature of 55°C, an oxygen pressure of 0.4MPa, and a high-pressure reactor for 3h, the organic matter degradation rate is 67%.

[0030] Comparative Example 8 Weigh a certain amount of columnar coconut shell activated carbon, add it to 0.03mol / L potassium chlorate solution, heat and reflux for 1h, filter out the activated carbon after cooling, wash with a certain amount of deionized water and dry. Prepare a 9g / L copper acetate aqueous solution, add the treated activated carbon, and soak for 150h. Filter the activated carbon from the copper acetate aqueous solution, wash the activated carbon with water until the washed liquid is colorless. The activated carbon obtained by drying is a catalyst that adsorbs and fixes a certain amount of metal ions, which is stored for later use. The obtained catalyst is used for the degradation of organic matter in wastewater. The reaction temperature is 65℃, the oxygen pressure is 0.7MPa, and the reaction is carried out in a high-pressure reactor for 4h, and the organic matter degradation rate is 67%.

[0031] Comparative Example 9 Weigh a certain amount of silver-loaded activated carbon and add it to 1 mol / L KMnO 4The solution was heated to reflux for 4 hours, and the activated carbon was filtered out after cooling, and then washed and dried with a certain amount of deionized water. Prepare an aqueous solution of cobalt acetate containing 120g / L, add the treated activated carbon, and soak for 240 hours. Filter the activated carbon from the aqueous solution of cobalt acetate, and wash the activated carbon with water until the washed liquid is colorless. The activated carbon obtained by drying is a catalyst that adsorbs and fixes a certain amount of metal ions, which is stored for later use. The obtained catalyst is used for the degradation of organic matter in wastewater. The reaction temperature is 60°C, the oxygen pressure is 1MPa, and the reaction is carried out in a high-pressure reactor for 2.5 hours, and the organic matter degradation rate is 58%.

[0032] Comparative Example 10 Weigh a certain amount of powdered wood activated carbon, add it to a 0.03mol / L sulfuric acid solution, heat and reflux for 1h, filter out the activated carbon after cooling, wash with a certain amount of deionized water, and dry it. Prepare an aqueous solution of 170g / L ferric acetate, add the treated activated carbon, and soak it for 500h. Filter the activated carbon from the ferric acetate aqueous solution, wash the activated carbon with water until the washed liquid is colorless. The activated carbon obtained by drying is a catalyst that adsorbs and fixes a certain amount of metal ions, which is stored for later use. The obtained catalyst is used for the degradation of organic matter in wastewater. The reaction temperature is 40℃, the oxygen pressure is 0.8MPa, and the reaction is carried out in a high-pressure reactor for 5h, and the organic matter degradation rate is 43%.

[0033] Comparative Example 11 Weigh a certain amount of powdered wood activated carbon and add it to 2 mol / L KMnO 4 The solution was heated to reflux for 6 hours, and the activated carbon was filtered out after cooling, and then washed and dried with a certain amount of deionized water. A methanol solution containing 240g / L of cobalt acetate was prepared, and the treated activated carbon was added and soaked for 50 hours. The activated carbon was filtered out from the cobalt acetate methanol solution and washed with methanol until the washed liquid was colorless. The activated carbon obtained by drying is a catalyst that adsorbs and fixes a certain amount of metal ions, and is stored for later use. The obtained catalyst was used for the degradation of organic matter in wastewater. The reaction temperature was 50°C, the oxygen pressure was 1MPa, and the reaction was carried out in a high-pressure reactor for 0.5h, and the organic matter degradation rate was 30%.

[0034] Comparative Example 12 Weigh a certain amount of powdered wood activated carbon and add it to 0.1 mol / L KMnO 4The solution was heated to reflux for 2 hours, and the activated carbon was filtered out after cooling, and then washed and dried with a certain amount of deionized water. Prepared an ethanol solution containing 8g / L of manganese acetate, added the treated activated carbon, and soaked for 12 hours. Filter the activated carbon from the ethanol solution of manganese acetate, and wash the activated carbon with water until the washed liquid is colorless. The activated carbon obtained by drying is a catalyst that adsorbs and fixes a certain amount of metal ions, which is stored for later use. The obtained catalyst is used for the degradation of organic matter in wastewater. The reaction temperature is 60°C, the oxygen pressure is 0.25MPa, and the reaction is carried out in a high-pressure reactor for 2 hours, and the organic matter degradation rate is 86%. Example 1

[0035] Weigh a certain amount of powdered wood activated carbon and add it to 0.03 mol / L KMnO 4 Solution, heat to reflux for 0.5h, filter out activated carbon after cooling, wash with a certain amount of deionized water and dry. Prepare an aqueous solution of cobalt acetate containing 10g / L, add the treated activated carbon, and soak for 5h. Filter the activated carbon from the aqueous solution of cobalt acetate, wash the activated carbon with water until the washed liquid is colorless. Add a certain amount of 28w% ammonia water that can completely immerse the activated carbon, soak for 2h, filter the activated carbon from the ammonia solution, wash the activated carbon with water until it is neutral and then dry. Then add it to a 1g / L aqueous solution of cobalt acetate and soak for 12h. Filter the activated carbon from the aqueous solution of cobalt acetate, wash the activated carbon with water until the washed liquid is colorless. Dry the resulting catalyst and store it for use.

[0036] 1 g of the obtained catalyst was used to degrade organic matter in 1 kg of wastewater at a reaction temperature of 60°C and an oxygen pressure of 0.25 MPa in a high-pressure reactor for 2 hours, and the degradation rate of the organic matter was 92%. Example 2

[0037] Weigh a certain amount of powdered coconut shell activated carbon and add it to 0.1 mol / L KMnO 4 The solution was heated to reflux for 1 hour, and the activated carbon was filtered out after cooling, and then washed and dried with a certain amount of deionized water. Prepare an aqueous solution of cobalt acetate containing 1g / L, add the treated activated carbon, and soak for 12 hours. Filter the activated carbon from the aqueous solution of cobalt acetate, wash the activated carbon with water until the washed liquid is colorless. Add a certain amount of 15w% ammonia water that can completely immerse the activated carbon, soak for 4 hours, filter the activated carbon from the ammonia solution, wash the activated carbon with water until it is neutral, and then dry it. Then add it to a 20g / L aqueous solution of cobalt acetate and soak for 24 hours. Filter the activated carbon from the aqueous solution of cobalt acetate, wash the activated carbon with water until the washed liquid is colorless. The catalyst obtained by drying is stored for use.

[0038] 1 g of the obtained catalyst was used to degrade organic matter in 500 g of wastewater. The reaction was carried out in a high-pressure reactor at a reaction temperature of 60° C. and an oxygen pressure of 0.25 MPa for 2 h, and the degradation rate of the organic matter was 91%. Example 3

[0039] Weigh a certain amount of powdered bone activated carbon and add it to 1 mol / L KMnO 4 The solution was heated to reflux for 2 hours, and the activated carbon was filtered out after cooling, and then washed and dried with a certain amount of deionized water. Prepare an aqueous solution of cobalt acetate containing 18g / L, add the treated activated carbon, and soak for 20 hours. Filter the activated carbon from the aqueous solution of cobalt acetate, wash the activated carbon with water until the washed liquid is colorless. Add a certain amount of 1w% ammonia water that can completely immerse the activated carbon, soak for 4 hours, filter the activated carbon from the ammonia solution, wash the activated carbon with water until it is neutral, and then dry it. Then add it to a 10g / L aqueous solution of cobalt acetate and soak for 6 hours. Filter the activated carbon from the aqueous solution of cobalt acetate, wash the activated carbon with water until the washed liquid is colorless. The dried catalyst is stored for use.

[0040] 1 g of the obtained catalyst was used to degrade organic matter in 100 g of wastewater at a reaction temperature of 60°C and an oxygen pressure of 0.25 MPa in a high-pressure reactor for 6 hours, and the degradation rate of the organic matter was 94%. Example 4

[0041] Weigh a certain amount of powdered coal-based activated carbon and add it to 1.5 mol / L KMnO 4 The solution was heated to reflux for 1.5 hours, and the activated carbon was filtered out after cooling, and washed and dried with a certain amount of deionized water. Prepare an aqueous solution of cobalt acetate containing 8g / L, add the treated activated carbon, and soak for 6 hours. Filter the activated carbon from the aqueous solution of cobalt acetate, wash the activated carbon with water until the washed liquid is colorless. Add a certain amount of 10w% ammonia water that can completely immerse the activated carbon, soak for 2.5 hours, filter the activated carbon from the ammonia solution, wash the activated carbon with water until it is neutral, and then dry it. Then add it to a 12g / L aqueous solution of cobalt acetate and soak for 12 hours. Filter the activated carbon from the aqueous solution of cobalt acetate, wash the activated carbon with water until the washed liquid is colorless. The catalyst obtained by drying is stored for use.

[0042] 1 g of the obtained catalyst was used to degrade organic matter in 20 g of wastewater at a reaction temperature of 70°C and an oxygen pressure of 2 MPa in a high-pressure reactor for 8 hours, and the degradation rate of the organic matter was 97%. Example 5

[0043] Weigh a certain amount of powdered fruit shell activated carbon, add it to a 0.5mol / L potassium dichromate solution, heat and reflux for 1h, filter out the activated carbon after cooling, wash with a certain amount of deionized water and dry. Prepare a 10g / L cobalt acetate aqueous solution, add the treated activated carbon, and soak for 12h. Filter the activated carbon from the cobalt acetate aqueous solution, wash the activated carbon with water until the washed liquid is colorless. Add a certain amount of 25w% ammonia water that can completely immerse the activated carbon, soak for 2h, filter the activated carbon from the ammonia solution, wash the activated carbon with water until it is neutral and then dry. Then add it to an 8g / L cobalt acetate aqueous solution and soak for 12h. Filter the activated carbon from the cobalt acetate aqueous solution, wash the activated carbon with water until the washed liquid is colorless. Dry the resulting catalyst and store it for use.

[0044] 1 g of the obtained catalyst was used to degrade organic matter in 100 g of wastewater at a reaction temperature of 60°C and an oxygen pressure of 0.25 MPa in a high-pressure reactor for 2.5 hours, and the degradation rate of the organic matter was 94%. Example 6

[0045] Weigh a certain amount of powdered silver-loaded activated carbon, add it to a 0.05mol / L hydrogen peroxide solution, heat and reflux for 0.5h, filter out the activated carbon after cooling, wash with a certain amount of deionized water, and dry. Prepare a 15g / L cobalt acetate aqueous solution, add the treated activated carbon, and soak for 12h. Filter the activated carbon from the cobalt acetate aqueous solution, wash the activated carbon with water until the washed liquid is colorless. Add a certain amount of 25w% ammonia water that can completely immerse the activated carbon, soak for 2h, filter the activated carbon from the ammonia solution, wash the activated carbon with water until it is neutral, and then dry it. Then add it to a 10g / L cobalt acetate aqueous solution and soak for 6h. Filter the activated carbon from the cobalt acetate aqueous solution, wash the activated carbon with water until the washed liquid is colorless. Dry the resulting catalyst and store it for use.

[0046] 1 g of the obtained catalyst was used to degrade organic matter in 50 g of wastewater at a reaction temperature of 60°C and an oxygen pressure of 0.25 MPa in a high-pressure reactor for 3.5 hours, and the degradation rate of the organic matter was 95%. Example 7

[0047] Weigh a certain amount of powdered wood activated carbon and add it to 0.03 mol / L KMnO 4Solution, heat to reflux for 1h, filter out activated carbon after cooling, wash with a certain amount of deionized water and dry. Prepare an aqueous solution of cobalt acetate containing 10g / L, add the treated activated carbon, and soak for 6h. Filter the activated carbon from the aqueous solution of cobalt acetate, wash the activated carbon with water until the washed liquid is colorless. Add a certain amount of 28w% ammonia water that can completely immerse the activated carbon, soak for 1h, filter the activated carbon from the ammonia solution, wash the activated carbon with water until it is neutral and then dry. Then add it to a 10g / L aqueous solution of cobalt acetate and soak for 12h. Filter the activated carbon from the aqueous solution of cobalt acetate, wash the activated carbon with water until the washed liquid is colorless. Dry the resulting catalyst and store it for use.

[0048] 1 g of the obtained catalyst was used to degrade organic matter in 100 g of wastewater at a reaction temperature of 60°C and an oxygen pressure of 0.25 MPa in a high-pressure reactor for 2 hours, and the degradation rate of the organic matter was 100%. Example 8

[0049] Weigh a certain amount of powdered wood activated carbon, add it to a 0.03mol / L hypochlorous acid solution, heat and reflux for 1h, filter out the activated carbon after cooling, wash with a certain amount of deionized water and dry. Prepare an aqueous solution of cobalt acetate containing 8g / L, add the treated activated carbon, and soak for 6h. Filter the activated carbon from the cobalt acetate aqueous solution, wash the activated carbon with water until the washed liquid is colorless. Add a certain amount of 20w% ammonia water that can completely immerse the activated carbon, soak for 1.5h, filter the activated carbon from the ammonia solution, wash the activated carbon with water until it is neutral and then dry. Then add it to an 8g / L cobalt acetate aqueous solution and soak for 12h. Filter the activated carbon from the cobalt acetate aqueous solution, wash the activated carbon with water until the washed liquid is colorless. Dry the resulting catalyst and store it for use.

[0050] 1 g of the obtained catalyst was used to degrade organic matter in 200 g of wastewater at a reaction temperature of 60° C. and an oxygen pressure of 1.8 MPa in a high-pressure reactor for 2 h, and the degradation rate of the organic matter was 95%. Example 9

[0051] Weigh a certain amount of powdered wood activated carbon, add it to a 0.05mol / L nitric acid solution, heat and reflux for 0.5h, filter out the activated carbon after cooling, wash with a certain amount of deionized water and dry. Prepare a 6g / L cobalt acetate aqueous solution, add the treated activated carbon, and soak for 5h. Filter the activated carbon from the cobalt acetate aqueous solution, wash the activated carbon with water until the washed liquid is colorless. Add a certain amount of 15w% ammonia water that can completely immerse the activated carbon, soak for 3h, filter the activated carbon from the ammonia solution, wash the activated carbon with water until it is neutral and then dry. Then add it to a 15g / L cobalt acetate aqueous solution and soak for 12h. Filter the activated carbon from the cobalt acetate aqueous solution, wash the activated carbon with water until the washed liquid is colorless. Dry the resulting catalyst and store it for use.

[0052] 1 g of the obtained catalyst was used to degrade organic matter in 500 g of wastewater at a reaction temperature of 50° C. and an oxygen pressure of 1.6 MPa in a high-pressure reactor for 3 hours, and the degradation rate of the organic matter was 92%. Example 10

[0053] Weigh a certain amount of powdered wood activated carbon, add it to a 0.03mol / L nitrous acid solution, heat and reflux for 6h, filter out the activated carbon after cooling, wash with a certain amount of deionized water and dry. Prepare an aqueous solution of cobalt acetate containing 18g / L, add the treated activated carbon, and soak for 8h. Filter the activated carbon from the aqueous solution of cobalt acetate, wash the activated carbon with water until the washed liquid is colorless. Add a certain amount of 14w% ammonia water that can completely immerse the activated carbon, soak for 2h, filter the activated carbon from the ammonia solution, wash the activated carbon with water until it is neutral and then dry. Then add it to a 2g / L manganese acetate aqueous solution and soak for 24h. Filter the activated carbon from the manganese acetate aqueous solution, wash the activated carbon with water until the washed liquid is colorless. Dry the resulting catalyst and store it for use.

[0054] 1 g of the obtained catalyst was used to degrade organic matter in 100 g of wastewater at a reaction temperature of 60°C and an oxygen pressure of 1.5 MPa in a high-pressure reactor for 7 hours, and the degradation rate of the organic matter was 82%. Embodiment 11

[0055] Weigh a certain amount of powdered wood activated carbon, add it to a 0.2mol / L sulfuric acid solution, heat and reflux for 0.5h, filter out the activated carbon after cooling, wash with a certain amount of deionized water and dry. Prepare a 10g / L cobalt acetate aqueous solution, add the treated activated carbon, and soak for 6h. Filter the activated carbon from the cobalt acetate aqueous solution, wash the activated carbon with water until the washed liquid is colorless. Add a certain amount of 10w% ammonia water that can completely immerse the activated carbon, soak for 4h, filter the activated carbon from the ammonia solution, wash the activated carbon with water until it is neutral and then dry. Then add it to a 20g / L cobalt acetate aqueous solution and soak for 12h. Filter the activated carbon from the cobalt acetate aqueous solution, wash the activated carbon with water until the washed liquid is colorless. Dry the resulting catalyst and store it for use.

[0056] 1 g of the obtained catalyst was used to degrade organic matter in 100 g of wastewater at a reaction temperature of 20°C, an oxygen pressure of 0.1 MPa, and a reaction time of 0.5 h in a high-pressure reactor, and the degradation rate of the organic matter was 87%. Example 12

[0057] Weigh a certain amount of powdered wood activated carbon, add it to a 0.005mol / L potassium chlorate solution, heat and reflux for 1.5h, filter out the activated carbon after cooling, wash with a certain amount of deionized water and dry. Prepare an aqueous solution of manganese acetate containing 12g / L, add the treated activated carbon, and soak for 6h. Filter the activated carbon from the manganese acetate aqueous solution, wash the activated carbon with water until the washed liquid is colorless. Add a certain amount of 20w% ammonia water that can completely immerse the activated carbon, soak for 1h, filter the activated carbon from the ammonia solution, wash the activated carbon with water until it is neutral and then dry. Then add it to an 8g / L manganese acetate aqueous solution and soak for 12h. Filter the activated carbon from the manganese acetate aqueous solution, wash the activated carbon with water until the washed liquid is colorless. Dry the resulting catalyst and store it for use.

[0058] 1 g of the obtained catalyst was used to degrade organic matter in 100 g of wastewater at a reaction temperature of 30°C and an oxygen pressure of 0.2 MPa in a high-pressure reactor for 2.5 hours, and the degradation rate of the organic matter was 85%. Embodiment 13

[0059] Weigh a certain amount of powdered wood activated carbon and add it to 0.1 mol / L KMnO 4The solution was heated to reflux for 1 hour, and the activated carbon was filtered out after cooling, and then washed and dried with a certain amount of deionized water. Prepare an aqueous solution of nickel acetate containing 10g / L, add the treated activated carbon, and soak for 12 hours. Filter the activated carbon from the aqueous solution of nickel acetate, wash the activated carbon with water until the washed liquid is colorless. Add a certain amount of 28w% ammonia water that can completely immerse the activated carbon, soak for 2 hours, filter the activated carbon from the ammonia solution, wash the activated carbon with water until it is neutral, and then dry it. Then add it to an 18g / L nickel acetate aqueous solution and soak for 12 hours. Filter the activated carbon from the cobalt acetate and manganese acetate aqueous solutions, wash the activated carbon with water until the washed liquid is colorless. The dried catalyst is stored for use.

[0060] 1 g of the obtained catalyst was used to degrade organic matter in 100 g of wastewater at a reaction temperature of 70°C and an oxygen pressure of 0.85 MPa in a high-pressure reactor for 4 hours, and the degradation rate of the organic matter was 81%. Embodiment 14

[0061] Weigh a certain amount of powdered wood activated carbon and add it to 0.03 mol / L KMnO 4 Solution, heat to reflux for 0.5h, filter out activated carbon after cooling, wash with a certain amount of deionized water and dry. Prepare a 12g / L copper acetate aqueous solution, add the treated activated carbon, and soak for 5h. Filter the activated carbon from the copper acetate aqueous solution, wash the activated carbon with water until the washed liquid is colorless. Add a certain amount of 20w% ammonia water that can completely immerse the activated carbon, soak for 2h, filter the activated carbon from the ammonia solution, wash the activated carbon with water until it is neutral and then dry. Then add it to a 5g / L manganese acetate aqueous solution and soak for 24h. Filter the activated carbon from the manganese acetate aqueous solution, wash the activated carbon with water until the washed liquid is colorless. Dry the resulting catalyst and store it for use.

[0062] 1 g of the obtained catalyst was used to degrade organic matter in 100 g of wastewater at a reaction temperature of 65°C and an oxygen pressure of 0.55 MPa in a high-pressure reactor for 6 hours, and the degradation rate of the organic matter was 83%. Embodiment 15

[0063] Weigh a certain amount of powdered wood activated carbon and add it to 0.05 mol / L KMnO 4The solution was heated to reflux for 3 hours, and the activated carbon was filtered out after cooling, and then washed and dried with a certain amount of deionized water. Prepare an aqueous solution of chromium acetate containing 9g / L, add the treated activated carbon, and soak for 5 hours. Filter the activated carbon from the aqueous solution of chromium acetate, wash the activated carbon with water until the washed liquid is colorless. Add a certain amount of 12w% ammonia water that can completely immerse the activated carbon, soak for 2 hours, filter the activated carbon from the ammonia solution, wash the activated carbon with water until it is neutral, and then dry it. Then add it to a 15g / L aqueous solution of ferric acetate and soak for 10 hours. Filter the activated carbon from the aqueous solution of ferric acetate, wash the activated carbon with water until the washed liquid is colorless. The catalyst obtained by drying is stored for standby use.

[0064] 1 g of the obtained catalyst was used to degrade organic matter in 100 g of wastewater at a reaction temperature of 60°C and an oxygen pressure of 0.35 MPa in a high-pressure reactor for 8 hours, and the degradation rate of the organic matter was 84%. Example 16

[0065] Weigh a certain amount of powdered wood activated carbon and add it to 0.03 mol / L KMnO 4 The solution was heated to reflux for 1h, and the activated carbon was filtered out after cooling, and then washed and dried with a certain amount of deionized water. Prepare an aqueous solution containing 10g / L of cobalt acetate and 5g / L of manganese acetate, add the treated activated carbon, and soak for 12h. Filter the activated carbon from the aqueous solution of cobalt acetate and manganese acetate, and wash the activated carbon with water until the washed liquid is colorless. Add a certain amount of 18w% ammonia water that can completely immerse the activated carbon, soak for 2h, filter the activated carbon from the ammonia solution, wash the activated carbon with water until it is neutral, and then dry it. Then add it to an aqueous solution containing 10g / L of cobalt acetate and 5g / L of manganese acetate, and soak for 12h. Filter the activated carbon from the aqueous solution of cobalt acetate and manganese acetate, and wash the activated carbon with water until the washed liquid is colorless. The dried catalyst is stored for use.

[0066] 1 g of the obtained catalyst was used to degrade organic matter in 100 g of wastewater at a reaction temperature of 55°C and an oxygen pressure of 0.45 MPa in a high-pressure reactor for 4.5 hours, and the degradation rate of the organic matter was 80%. Embodiment 17

[0067] Weigh a certain amount of powdered wood activated carbon and add it to 0.03 mol / L KMnO 4The solution was heated to reflux for 1.5 hours, and the activated carbon was filtered out after cooling, and then washed and dried with a certain amount of deionized water. First, 8g / L of ferric acetate aqueous solution was added to the treated activated carbon and soaked for 8 hours. After filtering the activated carbon from the ferric acetate aqueous solution, the activated carbon was washed with water until the washed liquid was colorless. A certain amount of 18w% ammonia water that can completely immerse the activated carbon was added, soaked for 1 hour, the activated carbon was filtered out from the ammonia aqueous solution, and the activated carbon was washed with water until it was neutral and then dried. Then it was added to a 6g / L chromium acetate aqueous solution and soaked for 12 hours. The activated carbon was filtered out from the chromium acetate aqueous solution and washed with water until the washed liquid was colorless. The catalyst obtained by drying was stored for standby use.

[0068] 1 g of the obtained catalyst was used to degrade organic matter in 100 g of wastewater at a reaction temperature of 30°C and an oxygen pressure of 0.65 MPa in a high-pressure reactor for 8 hours, and the degradation rate of the organic matter was 67%. Embodiment 18

[0069] Weigh a certain amount of powdered wood activated carbon and add it to 0.03 mol / L KMnO 4 Solution, heat to reflux for 1.5h, filter out activated carbon after cooling, wash with a certain amount of deionized water and dry. Prepare an aqueous solution containing 8g / L manganese acetate and 2g / L chromium acetate, add the treated activated carbon, and soak for 8h. Filter the activated carbon from the aqueous solution of manganese acetate and chromium acetate, wash the activated carbon with water until the washed liquid is colorless. Add a certain amount of 18w% ammonia water that can completely immerse the activated carbon, soak for 1h, filter the activated carbon from the ammonia solution, wash the activated carbon with water until it is neutral and then dry. Then add it to an aqueous solution containing 6g / L manganese acetate and 10g / L chromium acetate, and soak for 12h. Filter the activated carbon from the aqueous solution of cobalt acetate and manganese acetate, wash the activated carbon with water until the washed liquid is colorless. Dry the resulting catalyst and store it for use.

[0070] 1 g of the obtained catalyst was used to degrade organic matter in 500 g of wastewater at a reaction temperature of 20°C and an oxygen pressure of 1.2 MPa in a high-pressure reactor for 7.5 hours, and the degradation rate of the organic matter was 46%. Embodiment 19

[0071] Weigh a certain amount of powdered wood activated carbon and add it to 0.03 mol / L KMnO 4Solution, heat to reflux for 1.5h, filter out activated carbon after cooling, wash with a certain amount of deionized water and dry. Prepare an aqueous solution containing 8g / L manganese acetate and 2g / L chromium acetate, add the treated activated carbon, and soak for 8h. Filter the activated carbon from the aqueous solution of manganese acetate and chromium acetate, wash the activated carbon with water until the washed liquid is colorless. Add a certain amount of 18w% ammonia water that can completely immerse the activated carbon, soak for 1h, filter the activated carbon from the ammonia solution, wash the activated carbon with water until it is neutral and then dry. Then add it to an aqueous solution containing 6g / L copper acetate and 10g / L chromium acetate and soak for 12h. Filter the activated carbon from the aqueous solution of chromium acetate and manganese acetate, wash the activated carbon with water until the washed liquid is colorless. Dry the resulting catalyst and store it for use.

[0072] 1 g of the obtained catalyst was used to degrade organic matter in 200 g of wastewater at a reaction temperature of 45°C and an oxygen pressure of 0.95 MPa in a high-pressure reactor for 6.5 hours, and the degradation rate of the organic matter was 57%. Embodiment 20

[0073] Weigh a certain amount of powdered wood activated carbon and add it to 0.03 mol / L KMnO 4 The solution was heated to reflux for 1.5 hours. After cooling, the activated carbon was filtered out, washed with deionized water until colorless, and then dried. Next, an aqueous solution containing 8g / L manganese acetate was prepared, and the treated activated carbon was added thereto and soaked for 8 hours. After filtering, it was washed again with water until colorless and dried. After that, the activated carbon was immersed in a sufficient amount of 18% ammonia solution for 1 hour, filtered again, washed until neutral and dried. Finally, the activated carbon was added to a mixed solution containing 6g / L manganese acetate and 10g / L cobalt acetate and soaked for 12 hours. After filtering, washing and drying, the obtained catalyst was stored for standby use.

[0074] 1 g of the obtained catalyst was used to degrade organic matter in 1 kg of wastewater. The organic matter in the wastewater was degraded for 2 h in a high-pressure reactor at 60°C and 1.0 MPa oxygen pressure, and the degradation rate of the organic matter was measured to be 95%.

Claims

1. A method for preparing an oxidation catalyst for degrading organic matter, characterized in that: The steps include: (1) placing activated carbon in an oxidant solution, heating and refluxing, modifying the surface of the activated carbon, and then washing and drying to obtain a carrier; (2) immersing the carrier in a solution of a first metal salt so that the first metal salt is adsorbed on the surface of the carrier, and then washing to remove excess first metal salt on the surface of the carrier; (3) immersing the carrier treated in step (2) in an aqueous ammonia solution, and washing to remove excess ammonia on the surface of the carrier after the reaction; (4) Immersing the carrier treated in step (3) in a solution of a second metal salt so that the second metal salt is adsorbed on the surface of the carrier, and then washing to remove excess second metal salt on the surface of the carrier to obtain the catalyst.

2. The preparation method according to claim 1, characterized in that: The first metal salt or the second metal salt is one or a mixture of more than one of cobalt salt, manganese salt, iron salt, chromium salt, nickel salt or copper salt; preferably, the first metal salt or the second metal salt is a cobalt salt or a manganese salt; more preferably, the first metal salt and the second metal salt are both cobalt salts.

3. The preparation method according to claim 1, characterized in that: The concentration of the oxidant solution in step (1) is less than 2 mol / L.

4. The preparation method according to claim 1, characterized in that: The oxidant in step (1) is a mixture of one or more of potassium permanganate, potassium chlorate, potassium dichromate, hydrogen peroxide, hypochlorous acid, nitric acid, nitrous acid or sulfuric acid.

5. The preparation method according to claim 1, characterized in that: The activated carbon described in step (1) is a mixture of one or more of wood activated carbon, coconut shell activated carbon, coal activated carbon, fruit shell activated carbon, bone activated carbon or silver-loaded activated carbon.

6. The preparation method according to claim 1, characterized in that: The heating reflux time in step (1) is less than 6 hours.

7. The preparation method according to claim 1, characterized in that: The concentration of the first metal salt solution in step (2) or the second metal salt solution in step (4) is less than 240 g / L.

8. The preparation method according to claim 1, characterized in that: The concentration of the ammonia water described in step (3) is below 28wt%.

9. The catalyst prepared by the preparation method according to any one of claims 1 to 8.

10. Use of the catalyst prepared by the preparation method according to any one of claims 1 to 8 in the degradation of organic matter in wastewater, characterized in that: The applications include: The catalyst, oxygen and wastewater are placed in a reactor for reaction, the reaction temperature is 20-70° C., the oxygen reaction pressure is 0.1-2 MPa, the catalyst dosage is 0.1%-5wt%, and the reaction time is 0.5-8 h.