CN110578058A - method for recovering titanium, tungsten, vanadium and silicon in waste catalyst for coal-fired flue gas denitration - Google Patents
method for recovering titanium, tungsten, vanadium and silicon in waste catalyst for coal-fired flue gas denitration Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/122—Lepidoic silicic acid
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
- C22B34/1254—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using basic solutions or liquors
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
- C22B34/225—Obtaining vanadium from spent catalysts
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
- C22B34/365—Obtaining tungsten from spent catalysts
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/009—General processes for recovering metals or metallic compounds from spent catalysts
Abstract
The invention relates to a method for recovering titanium, tungsten, vanadium and silicon in waste denitration catalyst of coal-fired flue gas, which comprises the following steps: 1) pretreating the waste denitration catalyst of the coal-fired flue gas; 2) carrying out alkaline leaching process treatment on the pretreated denitration waste catalyst; 3) solid-liquid separation of the alkali leaching solution to obtain anatase titanium dioxide; 4) separating and purifying silicon in the filtrate to obtain silicic acid; 5) separating and purifying tungsten in the filtrate to obtain tungstic acid; 6) and separating and purifying vanadium in the filtrate to obtain vanadate. Compared with the prior art, the method sequentially separates anatase type titanium dioxide, silicic acid, tungstic acid and vanadate from the waste catalyst for coal-fired flue gas denitration, and further respectively recovers titanium, silicon, tungsten and vanadium.
Description
Technical Field
The invention belongs to the technical field of waste catalyst recovery and resource utilization, and relates to a method for recovering titanium, tungsten, vanadium and silicon in a coal-fired flue gas denitration waste catalyst.
background
at present, the emission control of coal-fired flue gas is more strict, and the emission standard of the latest standard nitrogen oxide is executed to be 100mg/m3. The installed capacity of the thermal power in China reaches 11 hundred million kW by 2018, and the denitration engineering is completely finished. The demand of the power plant for the denitration catalyst still keeps steadily increasing, and is expected to reach 22.31 ten thousand meters by 20203By 2025, it will reach 30.37 ten thousand meters3。
at present, the service life of the denitration catalyst is required to be 2-3 years, which causes the waste amount of the catalyst after use to be greatly increased. According to the actual operation condition of the catalyst, the waste catalyst is continuously and stably produced in China from 2014, the production amount of the waste catalyst is increased year by year, and the waste catalyst is expected to show explosive growth. The Chinese waste denitration catalyst begins to grow explosively in 2017, and the waste amount reaches nearly 25 ten thousand meters by 20253and over 12 million tons. The power plant generates a large amount of waste catalysts, which causes great burden to the power plant. If the materials are randomly stockpiled or disposed improperly, environmental pollution and resource waste are caused.
waste flue gas denitration catalysts (vanadium-titanium series) have been incorporated into hazardous wastes for management. The waste denitration catalyst is composed of precious metals such as titanium dioxide, tungsten trioxide and vanadium oxide, and if the waste denitration catalyst is recycled and recycled, the waste is changed into valuable, the purposes of reducing and recycling hazardous wastes can be realized, and the development of circular economy is promoted.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for recovering titanium, tungsten, vanadium and silicon in waste catalysts for denitration of coal-fired flue gas, which can extract precious metals in the waste catalysts to obtain high-purity products for recycling.
the purpose of the invention can be realized by the following technical scheme:
the method for recovering titanium, tungsten, vanadium and silicon in the waste catalyst for coal-fired flue gas denitration comprises the following steps:
1) pretreating the denitration waste catalyst;
2) Adding an alkali solution, carrying out alkali leaching reaction on the pretreated denitration waste catalyst, and then carrying out first solid-liquid separation to obtain a first solid phase and a first liquid phase;
The reaction equation is:
WO3+2NaOH＝Na2WO4+H2O
V2O5+2NaOH＝2NaVO3+H2O
SiO2+2NaOH＝Na2SiO3+H2O
3) adding an acid solution A into the first liquid phase, standing, and then carrying out second solid-liquid separation to obtain a second solid phase and a second liquid phase;
The reaction equation is:
Na2SiO3+2HCl＝H2SiO3↓+2NaCl
4) Adding an acid solution B into the second solid phase, carrying out an acidification reaction, and then carrying out solid-liquid separation for the third time to obtain a third solid phase and a third liquid phase; adding an oxidant into the second liquid phase for oxidation reaction, then adding an acid solution C for tungsten precipitation reaction, and then carrying out fourth solid-liquid separation to obtain a fourth solid phase and a fourth liquid phase;
The reaction equation is:
Na2WO4+2HCl＝H2WO4↓+2NaCl
5) Adding a calcium salt into the fourth liquid phase, reacting, and performing fifth solid-liquid separation to obtain a fifth solid phase and a fifth liquid phase;
the reaction equation is:
2CaCl2+2NaVO3+H2O＝Ca2V2O7·2H2O↓+4NaCl
the first solid phase is titanium dioxide (anatase titanium dioxide), the third solid phase is silicic acid, the fourth solid phase is tungstic acid, and the fifth solid phase is vanadate.
Further, in step 1), the pretreatment process is as follows: and after the denitration waste catalyst is subjected to ash removal, crushing and grinding the denitration waste catalyst to be less than 200 meshes.
further, the alkali solution is a sodium hydroxide solution or a potassium hydroxide solution, and the acid solution a, the acid solution B and the acid solution C are respectively and independently selected from one of a hydrochloric acid solution or a sulfuric acid solution.
further, the mass concentration of the alkali solution is 30-40 wt%, and the acid solution B is a sulfuric acid solution with the mass concentration of 10-20 wt%.
further, in the step 2), in the alkaline leaching reaction process, the solid-to-liquid ratio is 1 (3-6), the reaction temperature is 120-150 ℃, and the reaction time is 1-4 h. The alkaline leaching solution can be recycled for multiple times by adopting a multiple-cycle alkaline leaching mode, and the consumption of raw materials is reduced by leaching multiple batches of waste catalysts. And (3) carrying out first solid-liquid separation on the alkaline leaching solution after the alkaline leaching reaction is finished.
further, in the step 4), in the acidification reaction process, the solid-to-liquid ratio is 1 (3-6), the reaction temperature is 50-90 ℃, and the reaction time is 0.5-2 h; in the oxidation reaction process, the oxidant is hydrogen peroxide, and the reaction time is 0.5-2 h; in the tungsten precipitation reaction process, the reaction temperature is 70-120 ℃, and the reaction time is 1-3 h.
further, in the step 5), the calcium salt is calcium chloride, and the fourth liquid phase is added with the calcium chloride and then reacts for 1-3h at 90-120 ℃.
Further, the fourth solid phase is roasted at a high temperature to obtain tungsten oxide.
the reaction equation is:
H2WO4＝WO3+2H2O
Furthermore, in the high-temperature roasting process, the roasting temperature is 590-610 ℃, and the roasting time is 1.5-2.5 h.
Compared with the prior art, the invention has the following characteristics:
1) the method has the advantages of simple process, mild and controllable overall reaction conditions, low cost, no secondary pollution, high yield and purity of recovered products and the like, and is suitable for industrial application;
2) in the prior art, a waste catalyst roasting method is mainly adopted, while the wet-process multi-cycle alkaline leaching process is adopted, so that multi-batch alkaline leaching of the catalyst is realized, the reaction temperature is greatly reduced, the consumption of raw materials is reduced, the energy is saved, the environment is protected, and the titanium oxide can not react to generate Na in the alkaline leaching2TiO3；
3) the titanium dioxide obtained by the method is anatase type, and the purity can reach more than 95%;
4) The invention relates to a recovery and refining process of silicon, and the purity of silicic acid reaches more than 90%. However, the conventional techniques for recovering a spent catalyst rarely involve purification of silicon. In the waste denitration catalyst, the content of silicon accounts for 7%, and the silicon is recycled to obtain a high-purity silicic acid product, so that the economic benefit can be increased;
5) the invention develops a process route of firstly precipitating tungsten and then precipitating vanadium, efficiently separates tungsten and vanadium from a tungsten and vanadium mixed solution, solves the problems of low purity of products containing vanadium and tungsten in tungsten, and the like, and has the tungsten precipitation rate of more than 90 percent, the purity of tungsten oxide products of more than 95 percent and the recovery rate of vanadium of more than 90 percent.
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
example 1:
1) Removing ash from the denitration waste catalyst, crushing and grinding the denitration waste catalyst into powder of less than 200 meshes;
2) Adding sodium hydroxide solution into the waste catalyst powder in the step 1) to perform multi-cycle alkaline leaching reaction, wherein the concentration of sodium hydroxide is 30 wt%, the solid-liquid mass ratio of the alkaline leaching reaction is 1:4, the reaction temperature is 130 ℃, and the reaction time is 2 hours. Recycling the alkaline leaching solution for many times, leaching 3 batches of waste catalysts in the alkaline leaching solution, and performing solid-liquid separation on the alkaline leaching solution after the alkaline leaching reaction is finished to obtain a solid phase titanium dioxide;
3) Adding hydrochloric acid into the liquid phase part subjected to solid-liquid separation in the step 2), standing, and performing solid-liquid separation;
4) Adding a sulfuric acid solution into the solid phase part subjected to solid-liquid separation in the step 3) to perform an acidification reaction, wherein the concentration of the sulfuric acid solution is 10 wt%, the solid-liquid ratio of the acidification reaction is 1:4, the reaction temperature is 60 ℃, and the reaction time is 1 hour. After the reaction is finished, the solid phase obtained by solid-liquid separation is silicic acid;
5) adding a hydrogen peroxide oxidant into the liquid phase part subjected to solid-liquid separation in the step 3) for oxidation, standing, adding hydrochloric acid into the new solution for tungsten precipitation reaction, wherein the reaction time is 1 hour, the reaction temperature is 80 ℃, after the reaction is finished, the solid phase obtained by solid-liquid separation is tungstic acid, and then performing high-temperature roasting to obtain tungsten oxide, and the liquid phase is vanadium-containing liquid;
6) adding solid calcium chloride into the vanadium-containing liquid obtained in the step 5) for reaction, wherein the reaction time is 1 hour, the reaction temperature is 90 ℃, and after the reaction is finished, the solid phase obtained by solid-liquid separation is a vanadate product.
example 2:
1) Removing ash from the denitration waste catalyst, crushing and grinding the denitration waste catalyst into powder of less than 200 meshes;
2) Adding sodium hydroxide solution into the waste catalyst powder obtained in the step 1) to perform multi-cycle alkaline leaching reaction, wherein the concentration of sodium hydroxide is 35 wt%, the solid-to-liquid ratio of the alkaline leaching reaction is 1:4, the reaction temperature is 140 ℃, and the reaction time is 2 hours. Recycling the alkaline leaching solution for multiple times, leaching 4 batches of waste catalysts with alkali, and performing solid-liquid separation on the alkaline leaching solution after the alkaline leaching reaction is finished to obtain a solid phase titanium dioxide;
3) adding hydrochloric acid into the liquid phase part subjected to solid-liquid separation in the step 2), standing, and performing solid-liquid separation;
4) adding a sulfuric acid solution into the solid phase part subjected to solid-liquid separation in the step 3) for carrying out an acidification reaction, wherein the concentration of the sulfuric acid solution is 15 wt%, the solid-liquid ratio of the acidification reaction is 1:5, the reaction temperature is 70 ℃, and the reaction time is 0.5 hour. After the reaction is finished, the solid phase obtained by solid-liquid separation is silicic acid;
5) adding a hydrogen peroxide oxidant into the liquid phase part subjected to solid-liquid separation in the step 3) for oxidation, standing, adding hydrochloric acid into a new solution for tungsten precipitation reaction, wherein the reaction time is 1 hour, the reaction temperature is 100 ℃, after the reaction is finished, the solid phase obtained by solid-liquid separation is tungstic acid, and then performing high-temperature roasting to obtain tungsten oxide, and the liquid phase is vanadium-containing liquid;
6) adding solid calcium chloride into the vanadium-containing liquid obtained in the step 5) for reaction, wherein the reaction time is 2 hours, the reaction temperature is 100 ℃, and after the reaction is finished, the solid phase obtained by solid-liquid separation is a vanadate product.
example 3:
1) removing ash from the denitration waste catalyst, crushing and grinding the denitration waste catalyst into powder of less than 200 meshes;
2) adding sodium hydroxide solution into the waste catalyst powder obtained in the step 1) to perform multi-cycle alkaline leaching reaction, wherein the concentration of sodium hydroxide is 40 wt%, the solid-to-liquid ratio of the alkaline leaching reaction is 1:6, the reaction temperature is 150 ℃, and the reaction time is 3 hours. Recycling the alkaline leaching solution for multiple times, leaching 5 batches of waste catalysts with alkali, and performing solid-liquid separation on the alkaline leaching solution after the alkaline leaching reaction is finished to obtain a solid phase titanium dioxide;
3) adding hydrochloric acid into the liquid phase part subjected to solid-liquid separation in the step 2), standing, and performing solid-liquid separation;
4) adding a sulfuric acid solution into the solid phase part subjected to solid-liquid separation in the step 3) to perform an acidification reaction, wherein the concentration of the sulfuric acid solution is 13 wt%, the solid-liquid ratio of the acidification reaction is 1:4, the reaction temperature is 70 ℃, and the reaction time is 1 hour. After the reaction is finished, the solid phase obtained by solid-liquid separation is silicic acid;
5) Adding a hydrogen peroxide oxidant into the liquid phase part subjected to solid-liquid separation in the step 3) for oxidation, standing, adding hydrochloric acid into the new solution for tungsten precipitation reaction, wherein the reaction time is 1 hour, the reaction temperature is 90 ℃, after the reaction is finished, the solid phase obtained by solid-liquid separation is tungstic acid, and then performing high-temperature roasting to obtain tungsten oxide, and the liquid phase is vanadium-containing liquid;
6) Adding solid calcium chloride into the vanadium-containing liquid obtained in the step 5) for reaction, wherein the reaction time is 3 hours, the reaction temperature is 90 ℃, and after the reaction is finished, the solid phase obtained by solid-liquid separation is a vanadate product.
Example 4:
the method for recovering titanium, tungsten, vanadium and silicon in the waste catalyst for coal-fired flue gas denitration comprises the following steps:
1) After the denitration waste catalyst is subjected to ash removal, crushing and grinding the denitration waste catalyst to be less than 200 meshes;
2) And adding a sodium hydroxide solution with the mass concentration of 30 wt% to perform an alkaline leaching reaction on the pretreated denitration waste catalyst, wherein the solid-liquid ratio is 1:6, the reaction temperature is 120 ℃, and the reaction time is 4 hours. Then carrying out first solid-liquid separation to obtain first solid-phase titanium dioxide and a first liquid phase;
3) adding a hydrochloric acid solution into the first liquid phase, standing for 5 hours, and performing second solid-liquid separation to obtain a second solid phase and a second liquid phase;
4) and adding a sulfuric acid solution with the mass concentration of 10 wt% into the second solid phase to carry out acidification reaction, wherein the solid-liquid ratio is 1:6, the reaction temperature is 50 ℃, and the reaction time is 2 hours. Then carrying out solid-liquid separation for the third time to obtain a third solid-phase silicic acid and a third liquid phase; and adding an oxidant into the second liquid phase for oxidation reaction, wherein the oxidant is hydrogen peroxide, and the reaction time is 0.5 h. And then adding hydrochloric acid solution to carry out tungsten precipitation reaction, wherein the reaction temperature is 70 ℃, and the reaction time is 3 hours. And then carrying out solid-liquid separation for the fourth time to obtain a fourth solid phase tungstic acid and a fourth liquid phase, and roasting the tungstic acid at high temperature to obtain tungsten oxide. In the high-temperature roasting process, the roasting temperature is 590 ℃, and the roasting time is 2.5 hours;
5) adding calcium chloride into the fourth liquid phase, reacting at 90 ℃ for 3h, and performing fifth solid-liquid separation to obtain fifth solid-phase vanadate and a fifth liquid phase.
Example 5:
The method for recovering titanium, tungsten, vanadium and silicon in the waste catalyst for coal-fired flue gas denitration comprises the following steps:
1) after the denitration waste catalyst is subjected to ash removal, crushing and grinding the denitration waste catalyst to be less than 200 meshes;
2) Adding a potassium hydroxide solution with the mass concentration of 40 wt%, and carrying out alkaline leaching reaction on the pretreated denitration waste catalyst, wherein the solid-liquid ratio is 1:3, the reaction temperature is 150 ℃, and the reaction time is 1 h. Then carrying out first solid-liquid separation to obtain first solid-phase titanium dioxide and a first liquid phase;
3) adding a sulfuric acid solution into the first liquid phase, standing for 3 hours, and performing second solid-liquid separation to obtain a second solid phase and a second liquid phase;
4) and adding a sulfuric acid solution with the mass concentration of 20 wt% into the second solid phase to carry out acidification reaction, wherein the solid-liquid ratio is 1:3, the reaction temperature is 90 ℃, and the reaction time is 0.5 h. Then carrying out solid-liquid separation for the third time to obtain a third solid-phase silicic acid and a third liquid phase; and adding an oxidant into the second liquid phase for oxidation reaction, wherein the oxidant is hydrogen peroxide, and the reaction time is 1 h. And then adding a sulfuric acid solution to carry out tungsten precipitation reaction, wherein the reaction temperature is 120 ℃, and the reaction time is 1 h. And then carrying out solid-liquid separation for the fourth time to obtain a fourth solid phase tungstic acid and a fourth liquid phase, and roasting the tungstic acid at high temperature to obtain tungsten oxide. In the high-temperature roasting process, the roasting temperature is 610 ℃, and the roasting time is 1.5 h;
5) Adding calcium chloride into the fourth liquid phase, reacting at 120 ℃ for 1h, and performing fifth solid-liquid separation to obtain fifth solid-phase vanadate and a fifth liquid phase.
example 6:
the method for recovering titanium, tungsten, vanadium and silicon in the waste catalyst for coal-fired flue gas denitration comprises the following steps:
1) after the denitration waste catalyst is subjected to ash removal, crushing and grinding the denitration waste catalyst to be less than 200 meshes;
2) And adding 35 wt% of sodium hydroxide solution to perform alkaline leaching reaction on the pretreated denitration waste catalyst, wherein the solid-liquid ratio is 1:4, the reaction temperature is 130 ℃, and the reaction time is 3 hours. Then carrying out first solid-liquid separation to obtain first solid-phase titanium dioxide and a first liquid phase;
3) adding a hydrochloric acid solution into the first liquid phase, standing for 4 hours, and performing second solid-liquid separation to obtain a second solid phase and a second liquid phase;
4) Adding a sulfuric acid solution with the mass concentration of 15 wt% into the second solid phase, and carrying out an acidification reaction, wherein the solid-liquid ratio is 1:5, the reaction temperature is 70 ℃, and the reaction time is 1 h. Then carrying out solid-liquid separation for the third time to obtain a third solid-phase silicic acid and a third liquid phase; and adding an oxidant into the second liquid phase for oxidation reaction, wherein the oxidant is hydrogen peroxide, and the reaction time is 2 hours. And then adding a sulfuric acid solution to carry out tungsten precipitation reaction, wherein the reaction temperature is 90 ℃, and the reaction time is 2 hours. And then carrying out solid-liquid separation for the fourth time to obtain a fourth solid phase tungstic acid and a fourth liquid phase, and roasting the tungstic acid at high temperature to obtain tungsten oxide. In the high-temperature roasting process, the roasting temperature is 600 ℃, and the roasting time is 2 hours;
5) Adding calcium chloride into the fourth liquid phase, reacting at 110 ℃ for 2h, and performing fifth solid-liquid separation to obtain fifth solid-phase vanadate and a fifth liquid phase.
the embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (9)
1. the method for recovering titanium, tungsten, vanadium and silicon in the waste catalyst for coal-fired flue gas denitration is characterized by comprising the following steps of:
1) pretreating the denitration waste catalyst;
2) Adding an alkali solution, carrying out alkali leaching reaction on the pretreated denitration waste catalyst, and then carrying out first solid-liquid separation to obtain a first solid phase and a first liquid phase;
3) Adding an acid solution A into the first liquid phase, standing, and then carrying out second solid-liquid separation to obtain a second solid phase and a second liquid phase;
4) Adding an acid solution B into the second solid phase, carrying out an acidification reaction, and then carrying out solid-liquid separation for the third time to obtain a third solid phase and a third liquid phase; adding an oxidant into the second liquid phase for oxidation reaction, then adding an acid solution C for tungsten precipitation reaction, and then carrying out fourth solid-liquid separation to obtain a fourth solid phase and a fourth liquid phase;
5) Adding a calcium salt into the fourth liquid phase, reacting, and performing fifth solid-liquid separation to obtain a fifth solid phase and a fifth liquid phase;
the first solid phase is titanium dioxide, the third solid phase is silicic acid, the fourth solid phase is tungstic acid, and the fifth solid phase is vanadate.
2. the method for recovering titanium, tungsten, vanadium and silicon in the waste catalyst for coal-fired flue gas denitration according to claim 1, wherein in the step 1), the pretreatment process is as follows: and after the denitration waste catalyst is subjected to ash removal, crushing and grinding the denitration waste catalyst to be less than 200 meshes.
3. The method for recovering titanium, tungsten, vanadium and silicon in the waste catalyst for denitration of coal-fired flue gas according to claim 1, wherein the alkali solution is a sodium hydroxide solution or a potassium hydroxide solution, and the acid solution A, the acid solution B and the acid solution C are respectively and independently selected from one of a hydrochloric acid solution and a sulfuric acid solution.
4. the method for recovering titanium, tungsten, vanadium and silicon in the waste catalyst for coal-fired flue gas denitration according to claim 3, wherein the mass concentration of the alkali solution is 30-40 wt%, and the acid solution B is a sulfuric acid solution with the mass concentration of 10-20 wt%.
5. the method for recovering titanium, tungsten, vanadium and silicon in the waste catalyst for denitration of coal-fired flue gas as claimed in claim 1, wherein in the step 2), the solid-to-liquid ratio in the alkaline leaching reaction process is 1 (3-6), the reaction temperature is 120 ℃ and 150 ℃, and the reaction time is 1-4 h.
6. the method for recovering titanium, tungsten, vanadium and silicon in the waste catalyst for denitration of the coal-fired flue gas according to claim 1, wherein in the step 4), in the acidification reaction process, the solid-to-liquid ratio is 1 (3-6), the reaction temperature is 50-90 ℃, and the reaction time is 0.5-2 h; in the oxidation reaction process, the oxidant is hydrogen peroxide, and the reaction time is 0.5-2 h; in the tungsten precipitation reaction process, the reaction temperature is 70-120 ℃, and the reaction time is 1-3 h.
7. the method for recovering titanium, tungsten, vanadium and silicon in the waste catalyst for coal-fired flue gas denitration according to claim 1, wherein in the step 5), the calcium salt is calcium chloride, and the calcium chloride is added into the fourth liquid phase and then reacts for 1-3 hours at 90-120 ℃.
8. The method for recovering titanium, tungsten, vanadium and silicon in the waste catalyst for denitration of coal-fired flue gas according to claim 1, wherein the fourth solid phase is calcined at a high temperature to obtain tungsten oxide.
9. The method for recovering titanium, tungsten, vanadium and silicon in the waste catalyst for denitration of coal-fired flue gas as claimed in claim 8, wherein in the high-temperature roasting process, the roasting temperature is 590-610 ℃, and the roasting time is 1.5-2.5 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111302397A (en) * | 2020-03-13 | 2020-06-19 | 中国科学院城市环境研究所 | Method and device for recovering waste denitration catalyst |
| CN111646498A (en) * | 2020-06-11 | 2020-09-11 | 华北电力大学 | Method for recovering mixed ammonium salt and lead titanate from waste SCR denitration catalyst |
| CN111676372A (en) * | 2020-06-17 | 2020-09-18 | 中国电建集团装备研究院有限公司 | Method for refining titanium dioxide in waste catalyst for coal-fired flue gas denitration |
| CN113528834A (en) * | 2021-07-14 | 2021-10-22 | 中国石油大学(北京) | Method for recovering vanadium, tungsten and titanium from waste vanadium-titanium-based SCR catalyst |
| CN114477288A (en) * | 2021-12-16 | 2022-05-13 | 中南大学 | Comprehensive utilization and treatment method for wolframite resources |
| CN114984972A (en) * | 2021-03-01 | 2022-09-02 | 国家能源投资集团有限责任公司 | Method for recovering vanadium, tungsten and titanium powder from waste denitration catalyst, vanadium, tungsten and titanium powder, denitration catalyst and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111302397A (en) * | 2020-03-13 | 2020-06-19 | 中国科学院城市环境研究所 | Method and device for recovering waste denitration catalyst |
| CN111302397B (en) * | 2020-03-13 | 2022-06-24 | 中国科学院城市环境研究所 | Method and device for recovering waste denitration catalyst |
| CN111646498A (en) * | 2020-06-11 | 2020-09-11 | 华北电力大学 | Method for recovering mixed ammonium salt and lead titanate from waste SCR denitration catalyst |
| CN111676372A (en) * | 2020-06-17 | 2020-09-18 | 中国电建集团装备研究院有限公司 | Method for refining titanium dioxide in waste catalyst for coal-fired flue gas denitration |
| CN114984972A (en) * | 2021-03-01 | 2022-09-02 | 国家能源投资集团有限责任公司 | Method for recovering vanadium, tungsten and titanium powder from waste denitration catalyst, vanadium, tungsten and titanium powder, denitration catalyst and preparation method thereof |
| CN114984972B (en) * | 2021-03-01 | 2023-08-29 | 国家能源投资集团有限责任公司 | Method for recycling vanadium-tungsten-titanium powder from waste denitration catalyst, vanadium-tungsten-titanium powder, denitration catalyst and preparation method of denitration catalyst |
| CN113528834A (en) * | 2021-07-14 | 2021-10-22 | 中国石油大学(北京) | Method for recovering vanadium, tungsten and titanium from waste vanadium-titanium-based SCR catalyst |
| CN114477288A (en) * | 2021-12-16 | 2022-05-13 | 中南大学 | Comprehensive utilization and treatment method for wolframite resources |
| CN114477288B (en) * | 2021-12-16 | 2024-01-09 | 中南大学 | Comprehensive utilization processing method for wolframite resources |
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