CN108114728B - Method for preparing wet catalytic oxidation catalyst by using waste catalytic cracking catalyst - Google Patents
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- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/485—Impregnating or reimpregnating with, or deposition of metal compounds or catalytically active elements
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a method for preparing a wet catalytic oxidation catalyst by using a waste catalytic cracking catalyst. The method comprises the following steps: (1) adding the waste catalytic cracking catalyst into a titanium-containing solution for treatment, and then filtering to obtain a liquid-phase material A and a solid-phase material; (2) adding a manganese source into the liquid-phase material A in the step (1) to obtain a liquid-phase material B; (3) adding the liquid-phase material B obtained in the step (2) and a precipitator into the solid-phase material obtained in the step (1) in a concurrent flow manner, and carrying out aging treatment; (4) and (4) kneading the aged material obtained in the step (3) with activated carbon, kaolin and a binder for molding, drying and roasting to prepare the wet catalytic oxidation catalyst. The method not only can change the waste catalytic cracking catalyst into valuable, but also can ensure that the preparation cost of the wet catalytic oxidation catalyst is low and the performance is good.
Description
Technical Field
The invention relates to the field of wastewater treatment and the field of catalyst preparation, in particular to a method for preparing a wet catalytic oxidation catalyst by using a waste catalytic cracking catalyst.
Background
Catalytic cracking is one of the heavy oil lightening processes commonly adopted by oil refineries, and is also the secondary process with the largest catalyst usage in the oil refining industry. With the heavy and inferior crude oil quality in the world, and under the conditions that the demand for clean oil products is continuously increased and the environmental protection requirement is stricter, the replacement rate of the catalytic cracking catalyst is increased, and the amount of the waste catalytic cracking catalyst is increased day by day due to the deposition of heavy metals, coking and the like. At present, the treatment is usually carried out in an underground burying mode, so that not only are the atmosphere, soil and water resources seriously polluted, but also the resource waste is caused, and the enterprise cost is increased. Therefore, how to effectively treat and utilize the waste catalytic cracking catalyst is a major issue of current interest.
The catalytic cracking catalyst is alumina and silica catalyst, which is natural aluminum silicate, synthetic aluminum silicate and molecular sieve catalyst, and also contains small amount of RE oxide. In the catalytic cracking process, most of heavy metals such as Ni, V, Ca and the like in the raw materials are deposited on the catalyst, and carbon-containing substances generated in the catalytic cracking reaction process are also deposited on the surface of the catalyst to cover the active center of the catalyst or poison the active center, so that the catalyst finally loses activity and cannot meet the use requirement after regeneration, and becomes a waste catalyst.
In the prior art, different methods are adopted to recover the activity of the waste catalytic cracking catalyst, but the effect is poor, for example, CN104801353A, CN104841495A, CN104815704A and the like adopt a method of reacting with silicon tetrachloride and the like to recover the activity of the catalyst, but the heavy metal removal rate is lower, so that the activity recovery of the catalyst is limited.
If the waste catalytic cracking catalyst is used as raw material to produce catalyst with good performance for other purposes, the problem of environmental pollution caused by the waste catalyst can be solved, and a certain economic benefit can be created. Therefore, the preparation of catalysts with other purposes by taking the waste catalytic cracking catalyst as a raw material is one of the important ways of changing waste into valuable.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a method for preparing a wet catalytic oxidation catalyst by using a waste catalytic cracking catalyst. The method not only can change the waste catalytic cracking catalyst into valuable, but also can ensure that the preparation cost of the wet catalytic oxidation catalyst is low and the performance is good.
The invention provides a method for preparing a wet catalytic oxidation catalyst by using a waste catalytic cracking catalyst, which comprises the following steps:
(1) adding the waste catalytic cracking catalyst into a titanium-containing solution for treatment, and then filtering to obtain a liquid-phase material A and a solid-phase material;
(2) adding a manganese source into the liquid-phase material A in the step (1) to obtain a liquid-phase material B;
(3) adding the liquid-phase material B obtained in the step (2) and a precipitator into the solid-phase material obtained in the step (1) in a concurrent flow manner, and carrying out aging treatment;
(4) and (4) kneading the aged material obtained in the step (3) with activated carbon, kaolin and a binder for molding, drying and roasting to prepare the wet catalytic oxidation catalyst.
In the process of the present invention, the spent catalytic cracking catalyst may be pretreated to remove oil and/or carbon deposits from the surface of the catalyst. The oil on the surface of the catalyst can be removed by extraction, washing, or the like. The carbon deposition is removed by a high-temperature roasting method generally, and the roasting conditions are as follows: the roasting temperature is 500-900 ℃, and the roasting time is 1-5 hours.
The waste catalytic cracking catalyst in the step (1) is sourced from a catalytic cracking unit, and the performance of the waste catalytic cracking catalyst does not meet the original reaction requirement. The waste catalytic cracking catalyst is alumina and/or silicon oxide catalyst, which is natural aluminum silicate, synthetic aluminum silicate and molecular sieve catalyst, especially rare earth-containing catalytic cracking catalyst. Since metals such as nickel and vanadium in the raw material are deposited in the catalytic cracking catalyst during the catalytic cracking process, the spent catalytic cracking catalyst generally contains metals such as nickel and vanadium. The waste catalytic cracking catalyst in the step (1) contains nickel oxide and/or vanadium oxide, and the total content of the nickel oxide and/or vanadium oxide accounts for less than 4.0 percent of the weight of the finally obtained wet catalytic oxidation catalyst.
The titanium-containing solution in step (1) is usually prepared by dissolving a titanium-containing compound, wherein the titanium-containing compound is one or more selected from titanium sulfate, titanium chloride and titanium nitrate. The titanium-containing solution contains 0.5-25 g/100mL of titanium element, preferably 1-20 g/100 mL. The conditions for adding the waste catalytic cracking catalyst into the titanium-containing solution for treatment are as follows: the treatment time is 1-5 hours, and the treatment temperature is room temperature-60 ℃.
The manganese source in step (2) can adopt conventional manganese-containing compounds, such as one or more of manganese nitrate, manganese chloride and manganese acetate. And (3) adding the manganese source into the liquid-phase material A in the step (2), adding solvents such as water and the like according to actual requirements to fully dissolve the manganese source, adding the manganese source and the solvents such as water and the like into the liquid-phase material A respectively, or mixing the manganese source and the solvents such as water and the like, and then adding the manganese source and the solvents together into the liquid-phase material A to obtain a liquid-phase material B.
The precipitant in step (3) can be alkaline precipitant, preferably carbonate precipitant, such as one or more of ammonium carbonate, sodium carbonate and potassium carbonate. The reaction conditions of the cocurrent flow reaction control in the step (3) are as follows: the pH value is 6-10, and the temperature is room temperature-80 ℃. The aging conditions in the step (3) are as follows: the pH value is 6.0-10.0, preferably 7.0-9.5, the aging time is 0.5-5 hours, preferably 1-3 hours, and the aging temperature is room temperature-80 ℃.
In the process of the present invention, the material aged in step (3) is preferably washed in a manner known to those skilled in the art to remove the hetero-ions and to bring the pH of the material close to neutral, and then subjected to step (4).
The activated carbon in the step (4) is conventional powdered activated carbon, the granularity is 150-300 meshes, and the specific surface area is 500-3000 m2(ii) in terms of/g. The adhesive is an organic adhesive, preferably one or more of hydroxymethyl cellulose and polyacrylamide.
The using amount of the activated carbon in the step (4) accounts for 20-50% of the weight of the finally obtained wet catalytic oxidation catalyst, and preferably 30-40%. The dosage of the kaolin accounts for 1-15% of the weight of the finally obtained wet catalytic oxidation catalyst. The total dosage of the adhesive accounts for 5-20% of the weight of the finally obtained wet catalytic oxidation catalyst.
And (4) adding a forming aid, such as an extrusion aid and the like, during kneading and forming according to the actual situation.
The drying conditions in the step (4) are as follows: drying for 1-15 hours at 50-150 ℃ can be carried out by adopting a conventional drying method. The molding can be carried out according to the needs, generally in the form of strips, spheres and the like, and the granularity can be determined according to the needs.
In step (4), the calcination is performed under a non-oxygen atmosphere, such as one or more of nitrogen and inert gas. The roasting conditions are as follows: the roasting temperature is 500-750 ℃, and the roasting time is 1-10 hours.
In the method, the addition amount of the waste catalytic cracking catalyst accounts for 20-50% of the weight of the wet catalytic oxidation catalyst, and preferably 30-40%. In the wet catalytic oxidation catalyst in the step (4), based on the weight of the wet catalytic oxidation catalyst, the content of manganese oxide is 3% -15%, the content of rare earth metal calculated by oxide is 1% -10%, and the content of titanium oxide is 1% -15%.
In the method of the present invention, additional rare earth metal, preferably at least one of lanthanum and cerium, may be added during the preparation process according to actual needs by using conventional technical means in the art, for example, after the kneading molding and drying in step (4), the supported rare earth metal is impregnated, and then the drying and roasting treatment are performed to prepare the wet catalytic oxidation catalyst.
The wet oxidation catalyst prepared by the method can be used in the treatment process of organic matter-containing wastewater, and is suitable for treating various industrial organic wastewater containing high Chemical Oxygen Demand (COD) or compounds which can not be degraded by a biochemical method (such as ammonia nitrogen, polycyclic aromatic hydrocarbon and the like) in industries such as coking, dyes, pesticides, printing and dyeing, petrifaction, leather and the like. The organic wastewater treatment can adopt a continuous operation type reactor or a batch operation type reactor. When a continuous operation type reactor is used, a fixed bed reactor may be used, and a fluidized bed reactor may be used.
The wet catalytic oxidation catalyst prepared by the method can be used for reaction under conventional operating conditions, and takes air or oxygen-enriched gas as an oxidation medium as an example, the specific operating conditions are preferably as follows: the reaction temperature is 120-260 ℃, the reaction pressure is 0.3-9.0 MPa, the introduction amount of oxygen is 1-3 times, preferably 1.1-1.8 times of the theoretical requirement amount of the complete oxidation of the wastewater, and the reaction time is 0.5-3.0 h. When a batch operation type reactor is adopted, the dosage of the catalyst is 1-10 g of catalyst per L of wastewater.
The method of the invention has the following advantages:
1. the method can make full use of the waste catalytic cracking catalyst to prepare the wet catalytic oxidation catalyst, realizes the comprehensive utilization of the metal and the carrier on the waste catalytic cracking catalyst, improves the resource utilization rate, saves a large amount of cost, and realizes the waste recycling of the waste catalyst.
2. The wet catalytic oxidation catalyst provided by the invention utilizes an original carrier in the waste catalytic cracking catalyst and later added active carbon and kaolin as carrier components of the wet catalytic oxidation catalyst, and takes later added manganese, titanium and rare earth metals in the waste catalytic cracking catalyst and metals such as nickel and vanadium as active metal components, so that the manganese and the titanium are matched with each other, on one hand, the stability of manganese is increased, the manganese is not easy to run off in the reaction process, on the other hand, the activity of the catalyst is improved, and the removal rate of organic matters is increased.
Detailed Description
The technical solution of the present invention will be described in further detail with reference to examples. The embodiments described herein are only for explaining the present invention and are not intended to limit the scope of the present invention.
The main compositions by weight of the spent catalytic cracking catalysts used in the following examples and comparative examples of the present invention were as follows: 35.8 percent of silicon oxide, 50.9 percent of aluminum oxide, 6.0 percent of rare earth metal calculated by oxide, 1.3 percent of nickel and 0.4 percent of vanadium.
The waste catalytic cracking catalysts used in the examples and comparative examples of the present invention were obtained by oil removal by extraction and carbon removal by high temperature calcination at 700 ℃.
The activated carbon used in the examples and comparative examples of the present invention had a particle size of 200 mesh and a specific surface area of 2100 m2/g。
Example 1
The preparation process of the wet catalytic oxidation catalyst a in this example is as follows:
(1) adding 100g of waste catalytic cracking catalyst into 200mL of titanium sulfate solution (the titanium content is 8g/100 mL), treating for 3.5 hours at 46 ℃, and then filtering to obtain a liquid-phase material A and a solid-phase material;
(2) adding 65g of manganese nitrate and a proper amount of water into the liquid-phase material A in the step (1) and uniformly mixing to obtain a liquid-phase material B;
(3) and (3) adding the liquid-phase material B obtained in the step (2) and an ammonium carbonate solution into the solid-phase material obtained in the step (1) in a concurrent flow manner, controlling the pH of the system to be 9.0, controlling the reaction temperature to be 50 ℃, and aging after the reaction is finished under the aging conditions: the pH value is 9.0, the aging temperature is 65 ℃, and the time is 2.0 hours;
(4) and (4) washing the aged material obtained in the step (3) to be neutral by using deionized water, mixing and kneading the washed material with 85g of active carbon, 13g of kaolin and 16g of hydroxymethyl cellulose, molding, drying at 100 ℃ for 5 hours, roasting at the presence of nitrogen, and roasting at 720 ℃ for 5 hours to obtain the wet catalytic oxidation catalyst A. The obtained wet catalytic oxidation catalyst a mainly had the following composition by weight: the content of manganese oxide is 12%, the content of rare earth metal oxide is 2.3%, the content of titanium oxide is 7%, and the total content of nickel oxide and vanadium oxide is 0.6%.
Example 2
The preparation process of the wet catalytic oxidation catalyst B in this example is as follows:
(1) adding 100g of waste catalytic cracking catalyst into 210mL of titanium nitrate solution (the titanium content is 12g/100 mL), treating for 3.0 hours at 40 ℃, and then filtering to obtain a liquid-phase material A and a solid-phase material;
(2) adding 60g of manganese nitrate and a proper amount of water into the liquid-phase material A obtained in the step (1), and uniformly mixing to obtain a liquid-phase material B;
(3) and (3) adding the liquid-phase material B obtained in the step (2) and a sodium carbonate solution into the solid-phase material obtained in the step (1) in a concurrent flow manner, controlling the pH of the system to be 9.5, controlling the reaction temperature to be 40 ℃, and aging after the reaction is finished under the aging conditions: the pH value is 9.5, the aging temperature is 75 ℃, and the time is 1.5 hours;
(4) and (4) washing the aged material obtained in the step (3) to be neutral by using deionized water, mixing and kneading the washed material with 80g of activated carbon, 15g of kaolin and 19g of hydroxymethyl cellulose, molding, drying at 110 ℃ for 7 hours, roasting at the presence of nitrogen, and roasting at 550 ℃ for 6 hours to obtain the wet catalytic oxidation catalyst B. The obtained wet catalytic oxidation catalyst B mainly had the following composition by weight: the content of manganese oxide is 11%, the content of rare earth metal oxide is 2.6%, the content of titanium oxide is 8%, and the total content of nickel oxide and vanadium oxide is 0.6%.
Example 3
The preparation process of the wet catalytic oxidation catalyst C in this example is as follows:
(1) adding 100g of waste catalytic cracking catalyst into 195mL (the titanium content is 12g/100 mL) of titanium chloride solution, treating for 4.5 hours at 39 ℃, and then filtering to obtain a liquid-phase material A and a solid-phase material;
(2) adding 58g of manganese acetate and a proper amount of water into the liquid-phase material A obtained in the step (1) and uniformly mixing to obtain a liquid-phase material B;
(3) and (3) adding the liquid-phase material B obtained in the step (2) and a potassium carbonate solution into the solid-phase material obtained in the step (1) in a concurrent flow manner, controlling the pH of the system to be 9.0, controlling the reaction temperature to be 62 ℃, and aging after the reaction is finished under the aging conditions: the pH value is 9.0, the reaction temperature is 69 ℃, and the reaction time is 2.5 hours;
(4) and (4) washing the aged material obtained in the step (3) to be neutral by using deionized water, mixing and kneading the washed material with 81g of active carbon, 16g of kaolin and 20g of hydroxymethyl cellulose to form a shape, drying the shape at 80 ℃ for 6 hours, roasting the shape at 600 ℃ for 6.5 hours in the presence of nitrogen, and thus obtaining the wet catalytic oxidation catalyst C. The obtained wet catalytic oxidation catalyst C mainly had the following composition by weight: the content of manganese oxide is 13%, the content of rare earth metal oxide is 3.0%, the content of titanium oxide is 9%, and the total content of nickel oxide and vanadium oxide is 0.7%.
Example 4
The obtained wet catalytic oxidation catalyst A, B, C was used in organic wastewater treatment tests, and 20g of the prepared wet catalytic oxidation catalyst A, B, C was used to degrade 4L of phenol wastewater, the COD of the wastewater was 17750mg/L, the reaction temperature was 167 ℃, the total reaction pressure was 4.5MPa, and after 2.0 hours of reaction, the removal rates of COD in the effluent were 94.2%, 95.0% and 94.1%, respectively, showing good catalytic activity. The catalyst is repeatedly used for 10 times, the removal rate of COD is still more than 93 percent, and the stability of the catalyst is good.
Comparative example 1
The preparation process of the wet catalytic oxidation catalyst DA of this comparative example is as follows:
(1) mixing 100g of waste catalytic cracking catalyst, 85g of active carbon, 13g of kaolin and 25g of hydroxymethyl cellulose, kneading and molding to prepare a carrier;
(2) preparing 65g of manganese nitrate and proper amount of water into a dipping solution A;
(3) the carrier was immersed in the impregnation solution a, dried at 100 ℃ for 5 hours, calcined in the presence of nitrogen, and calcined at 720 ℃ for 5 hours to obtain a wet catalytic oxidation catalyst DA. In the obtained wet catalytic oxidation catalyst DA, its main composition by weight was as follows: the content of manganese oxide is 13%, the content of rare earth metal oxide is 2.5%, and the total content of nickel oxide and vanadium oxide is 0.7%.
Comparative example 2
The obtained wet catalytic oxidation catalyst DA is used for an organic wastewater treatment test, 20g of the prepared wet catalytic oxidation catalyst DA is used for degrading 4L of phenol wastewater, the COD of the wastewater is 17750mg/L, the reaction temperature is 167 ℃, the total reaction pressure is 4.5MPa, and the removal rate of the COD of the effluent is 69.7% after the reaction is carried out for 2.0 hours. The catalyst is repeatedly used for 4 times, the removal rate of COD is obviously reduced by more than 20 percent, and the stability of the catalyst is poor.
Claims (17)
1. A method of preparing a wet catalytic oxidation catalyst from a spent catalytic cracking catalyst, comprising:
(1) adding the waste catalytic cracking catalyst into a titanium-containing solution for treatment, and then filtering to obtain a liquid-phase material A and a solid-phase material;
(2) adding a manganese source into the liquid-phase material A in the step (1) to obtain a liquid-phase material B;
(3) adding the liquid-phase material B obtained in the step (2) and a precipitator into the solid-phase material obtained in the step (1) in a concurrent flow manner, and carrying out aging treatment;
(4) kneading and molding the aged material obtained in the step (3) with activated carbon, kaolin and an adhesive, drying and roasting to prepare a wet catalytic oxidation catalyst;
wherein, the waste catalytic cracking catalyst in the step (1) is a waste catalytic cracking catalyst containing rare earth;
the adding amount of the waste catalytic cracking catalyst in the step (1) accounts for 20-50% of the weight of the finally obtained wet catalytic oxidation catalyst;
the titanium-containing solution in the step (1) is prepared by dissolving a titanium-containing compound, wherein the titanium-containing compound is one or more of titanium sulfate, titanium chloride and titanium nitrate; in the titanium-containing solution, the titanium element is 0.5-25 g/100 mL; the conditions for adding the waste catalytic cracking catalyst into the titanium-containing solution for treatment are as follows: the treatment time is 1-5 hours, and the treatment temperature is room temperature-60 ℃.
2. The method of claim 1, wherein: before the step (1), the waste catalytic cracking catalyst is pretreated to remove oil and/or carbon deposit on the surface of the catalyst; removing oil on the surface of the catalyst by adopting an extraction method or a washing method; removing carbon deposition by adopting a high-temperature roasting method, wherein the roasting conditions are as follows: the roasting temperature is 500-900 ℃, and the roasting time is 1-5 hours.
3. The method of claim 1, wherein: the adding amount of the waste catalytic cracking catalyst in the step (1) accounts for 30-40% of the weight of the finally obtained wet catalytic oxidation catalyst.
4. A method according to claim 3, characterized by: the waste catalytic cracking catalyst in the step (1) contains nickel oxide and/or vanadium oxide, and the total content of the nickel oxide and/or vanadium oxide accounts for less than 4.0 percent of the weight of the finally obtained wet catalytic oxidation catalyst.
5. The method of claim 1, wherein: in the solution containing titanium in the step (1), the amount of titanium is 1-20 g/100 mL.
6. The method of claim 1, wherein: the precipitant in the step (3) is alkaline precipitant; the reaction conditions of the cocurrent flow reaction control in the step (3) are as follows: the pH value is 6-10, and the temperature is room temperature-80 ℃; the aging conditions in the step (3) are as follows: the pH value is 6.0-10.0, the aging time is 0.5-5 hours, and the aging temperature is room temperature-80 ℃.
7. The method of claim 6, wherein: the precipitant in the step (3) is carbonate precipitant, and the aging condition in the step (3) is as follows: the pH value is 7.0-9.5, and the aging time is 1-3 hours.
8. The method of claim 7, wherein: and (3) the precipitator is one or more of ammonium carbonate, sodium carbonate and potassium carbonate.
9. The method of claim 1, wherein: the manganese source in the step (2) is a manganese-containing compound; the activated carbon in the step (4) is powdered activated carbon, the granularity is 150-300 meshes, and the specific surface area is 500-3000 m2(ii)/g; the adhesive is an organic adhesive.
10. The method of claim 9, wherein: the manganese source in the step (2) is one or more of manganese nitrate, manganese chloride and manganese acetate.
11. The method of claim 9, wherein: the adhesive is one or more of hydroxymethyl cellulose or polyacrylamide.
12. The method of claim 1, wherein: the using amount of the activated carbon in the step (4) accounts for 20-50% of the weight of the finally obtained wet catalytic oxidation catalyst; the dosage of the kaolin accounts for 1-15% of the weight of the finally obtained wet catalytic oxidation catalyst; the total dosage of the adhesive accounts for 5-20% of the weight of the finally obtained wet catalytic oxidation catalyst.
13. The method of claim 12, wherein: the using amount of the activated carbon in the step (4) accounts for 30-40% of the weight of the finally obtained wet catalytic oxidation catalyst.
14. The method of claim 1, wherein: the drying conditions in the step (4) are as follows: drying for 1-15 hours at 50-150 ℃; the roasting is carried out under the non-oxygen atmosphere; the roasting conditions are as follows: the roasting temperature is 500-750 ℃, and the roasting time is 1-10 hours.
15. The method of claim 14, wherein: the non-oxygen atmosphere is one or more of inert gases.
16. The method of claim 1, wherein: and (4) after kneading, molding and drying, dipping and loading rare earth metal which is at least one of lanthanum and cerium, and then drying and roasting to prepare the wet catalytic oxidation catalyst.
17. A method according to any of claims 1 to 16, wherein: in the wet catalytic oxidation catalyst in the step (4), based on the weight of the wet catalytic oxidation catalyst, the content of manganese oxide is 3% -15%, the content of rare earth metal calculated by oxide is 1% -10%, and the content of titanium oxide is 1% -15%.
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| CN101185887A (en) * | 2007-12-20 | 2008-05-28 | 上海交通大学 | Catalyst for wet oxidation technique and preparation method thereof |
| CN101844827A (en) * | 2010-05-21 | 2010-09-29 | 华东理工大学 | Method for degrading formaldehyde pollutant with catalyzing wet oxidation process |
| CN105709743A (en) * | 2014-12-01 | 2016-06-29 | 抚顺环科石油化工技术开发有限公司 | Catalytic wet oxidation catalyst and preparation method thereof. |
| CN107442115A (en) * | 2016-05-30 | 2017-12-08 | 中国石化扬子石油化工有限公司 | One kind oil refining waste soda residue wet oxidizing catalyst and preparation method thereof |
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| JPH062227B2 (en) * | 1988-02-29 | 1994-01-12 | 株式会社日本触媒 | Water-resistant carrier, water treatment catalyst containing the carrier, and water treatment method using the catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101185887A (en) * | 2007-12-20 | 2008-05-28 | 上海交通大学 | Catalyst for wet oxidation technique and preparation method thereof |
| CN101844827A (en) * | 2010-05-21 | 2010-09-29 | 华东理工大学 | Method for degrading formaldehyde pollutant with catalyzing wet oxidation process |
| CN105709743A (en) * | 2014-12-01 | 2016-06-29 | 抚顺环科石油化工技术开发有限公司 | Catalytic wet oxidation catalyst and preparation method thereof. |
| CN107442115A (en) * | 2016-05-30 | 2017-12-08 | 中国石化扬子石油化工有限公司 | One kind oil refining waste soda residue wet oxidizing catalyst and preparation method thereof |
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