CN110218859B - Method for extracting valuable elements of waste denitration catalyst through medium-temperature tunnel type solid-state activation - Google Patents
Method for extracting valuable elements of waste denitration catalyst through medium-temperature tunnel type solid-state activation Download PDFInfo
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Abstract
The invention discloses a method for extracting valuable elements of a waste denitration catalyst by medium-temperature tunnel type solid activation. Washing and drying the leached residues to obtain a titanium dioxide product. Adding double salt into the filtrate to remove impurities of silicon and aluminum, adding a precipitator into the filtrate after impurity removal to precipitate vanadium and tungsten, carrying out liquid-solid separation on the precipitate after washing, filtering and selectively leaching vanadium, washing and drying the obtained slag phase to obtain a calcium tungstate product, adding ammonia water into the vanadium-containing filtrate to precipitate vanadium, and finally recovering vanadium element in the form of ammonium metavanadate. The method provided by the invention realizes fine separation of valuable elements in the waste catalyst, has the advantages of high recovery rate, low energy consumption, cyclic utilization of production waste liquid and no secondary pollution.
Description
Technical Field
The invention belongs to the field of SCR denitration waste catalyst recovery, and particularly relates to a recovery process of an SCR waste catalyst containing tungsten, vanadium and titanium.
Background
With the increasing demand of people on life and production, the demand of electricity is also increasing, but the combustion of a large amount of fossil fuel in the thermal power generation process can generate a large amount of SO2、CO2、NOxThe harm to the ecological environment is also more and more serious when the waste gas is used, and the haze is aggravated by smoke particles formed by incomplete combustion of fossil energy, so that the life health of human beings is seriously influenced; NOxWill combine with water in the air to produce nitric acid and nitrate, aggravate the formation of acid rain; under certain conditions, the nitrogen oxide is combined with other atmospheric pollutants to generate photochemical smog pollution; in addition, NOxMay also be made of3Decompose and cause ozone holes. Therefore, the NO of the thermal power plant is strictly controlledxEmissions are becoming more and more stringent. Currently, catalytic reduction is used to remove NOxIs controlling NOxOne of the main methods of emissions (i.e., denitration) is the design and preparation of the catalyst at the heart of the process. China is about to meet a denitration peak period, and the low cost of catalyst manufacture also becomes the requirement of social development. The metal substances of titanium, tungsten, vanadium and the like are key raw materials for producing the vanadium-tungsten-titanium system catalyst, account for 80-90% of the total weight of the catalyst and account for more than 80% of the total cost of the catalyst, but no method for effectively reducing the consumption of the metal of titanium, tungsten and the like exists at present, so that the cost of the denitration catalyst is high, in addition, heavy metal substances harmful to organisms and environment such as vanadium and the like are contained in the waste denitration catalyst (namely unqualified denitration catalyst products, intermediate products or ineffective catalysts generated in the production process), and the large amount of waste materials are indirectly damaged to the public environment, for example, valuable metals in the waste materials can be recycled, so that the ecological environment can be protected, and valuable resources are fully utilized.
The recovery method of valuable metals in the waste catalyst mainly comprises dry recovery, wet recovery and dry-wet combined recovery.
The dry recovery comprises sublimation, oxidation roasting, chloride volatilization and the like, and is commonly used for Cu-Ni, Ni-Mo/Al2O3The recovery of metals in the catalyst is equal, but the dry recovery has high energy consumption, and SO may be released in the melting and calcining processesxAnd organic matters, causing air pollution, and requiring an additional exhaust gas treatment device.
The wet recovery method mainly comprises the steps of dissolving valuable metal compounds in the waste catalyst by using acid liquor, alkali liquor or other solvents, filtering, removing impurities and drying to obtain corresponding oxide or salt compounds. In addition, the electrolytic recovery of valuable metals is also referred to as wet recovery.
Because the components contained in the existing catalyst are often two or more, the useful components are difficult to be well separated and recovered by adopting a dry method or a wet method, and therefore, the purpose is achieved by adopting a dry-wet combined method in many cases. The dry-wet method combination has low energy consumption, does not cause secondary pollution, and can finely separate valuable components in the waste catalyst.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a method for extracting valuable elements of a waste denitration catalyst through medium-temperature tunnel type solid-state activation, and provides an efficient and clean recovery process technology for the SCR denitration waste catalyst.
The method specifically comprises the following steps:
(1) performing medium-temperature tunnel type solid-state activation reaction, namely crushing and grinding the SCR denitration waste catalyst and 10-20% alkali salt (Na) by mass2CO3) Mixing with 1-3% of activating agent (sodium-based double salt), and extruding into brick. The extrusion molding material is conveyed to a tunnel type activation reactor through the trailer plate surface for activation, the material enters the tunnel type activation reactor and passes through a preheating zone, an activation reaction zone and a cooling zone, activation is finished after cooling, the whole activation process is 2-3 hours, the temperature of the preheating zone is 200 ℃, the temperature of the activation reaction zone is 400-750 ℃, and the temperature of the cooling zone is 80-100 ℃.
(2) Water leaching, namely delivering the activated material to a high-speed disperser for water quenching and scattering, wherein the water addition amount of the water quenching is 2 times of the mass of the material, delivering the ore pulp scattered by the high-speed disperser to an efficient leaching tank through an ore pulp pump, adding water to ensure that the solid-to-liquid ratio of the ore pulp in the efficient leaching machine is 3:1, leaching, wherein the leaching temperature is 40-90 ℃, the leaching time is 1-2 hours, pumping the ore pulp after leaching into a filter press for filtering to obtain solid-phase slag and filtrate, wherein the solid-phase slag is titanium oxide slag which is not leached, and the filtrate is a solution containing vanadium, tungsten and a small amount of silicon and aluminum impurities. And washing and filtering the obtained leaching slag, and then sending the leached slag to a drying furnace for drying for 2 hours at the temperature of 600-800 ℃ to obtain a titanium oxide product with the purity of more than 95 percent.
(3) Removing impurities from silicon and aluminum in the leaching filtrate, sending the leaching filtrate to a purification tank, and adding a composite precipitator (MgCl) according to the molar ratio of the leaching filtrate to silicon and aluminum ions of 1:12Or MgSO 24) And the operation temperature is 80 ℃, the pH of the reaction end point is controlled to be 9.0-9.5, the mixture is stirred for 30min, the mixture is stood for 1h and filtered, and impurities of silicon and aluminum in the solution are precipitated in a slag phase.
(4) And precipitating vanadium and tungsten, sending filtrate obtained by filtering the silicon-aluminum precipitate to a precipitation operation tank, adding hydrochloric acid to adjust the pH of the solution to 8.0-10, adding calcium chloride according to the molar ratio of 2:1 to vanadium and tungsten ions, stirring for 30min, standing for 1h, filtering, and precipitating the vanadium and tungsten ions in the solution in a slag phase.
(5) And (2) carrying out selective leaching at normal temperature, washing and filtering the obtained precipitate, adding 10-20% formic acid into the filtered slag to carry out selective leaching of vanadium, wherein the process pH is 6.5, the temperature is normal temperature, the leaching time is 30min, and the vanadium leaching rate reaches 98%. Tungsten is in the solid phase in the form of calcium tungstate. And washing the solid-phase slag obtained by filtering with clear water with a liquid-solid ratio of 3:1, filtering, and drying at 200 ℃ to obtain a calcium tungstate product.
(6) Precipitating vanadium, filtering to obtain filtrate, adding 5% ammonia water/m3Precipitating vanadium, and finally recovering vanadium element in the form of ammonium metavanadate.
Advantageous effects
The invention provides a method for extracting valuable elements of a waste denitration catalyst by medium-temperature tunnel type solid-state activation, which has the following beneficial effects: through the combined treatment of the medium-temperature tunnel type solid activation reaction dry method and the wet method, the high-efficiency leaching rate recovery of valuable elements vanadium and tungsten in the waste denitration catalyst is realized. The process is more environment-friendly, has low energy consumption and no secondary pollution, and can carry out a finer separation and recovery process on valuable components in the waste catalyst.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
The raw material comes from the waste SCR denitration catalyst of a certain power plant in Guizhou, wherein the content of titanium oxide is 86.2%, the content of vanadium pentoxide is 0.47%, and the content of tungstic acid is 3.72%. The catalyst is crushed to 80 meshes of more than 98 percent, is uniformly mixed with 20 percent of sodium carbonate and 3 percent of sodium-based double salt, is extruded and molded, is sent to a tunnel type activation reactor to be activated for 2 hours, and passes through a preheating zone of 200 ℃, an activation reaction zone of 650 ℃ and a cooling zone of 90 ℃. Sending the activated material into a high-speed disperser with water for water quenching, then dispersing and scattering the material at high speed, pumping the material to an efficient leaching tank under the condition of uniform stirring, stirring and reacting for 2 hours at the temperature of 70 ℃ according to the liquid-solid ratio of 3:1, after the reaction and leaching are finished, obtaining leaching slag, and washing and drying the leaching slag to obtain a titanium oxide product with the purity of 95.5%; adjusting the pH of the obtained leaching filtrate to 11, heating to 80 ℃, adding composite precipitator aluminum sulfate and magnesium sulfate, adding the composite precipitator according to the molar ratio of the aluminum sulfate to silicon-aluminum ions of 1:1, controlling the reaction end point to be pH10, stirring for 30min, standing for 1h, filtering, and precipitating impurities of silicon and aluminum in the solution in a slag phase. And (3) after impurity removal, adjusting the pH of the solution to 9 by using hydrochloric acid, adding calcium chloride according to the molar ratio of the solution to vanadium and tungsten ions of 2:1, stirring for 30min, standing for 1h, filtering, and precipitating vanadium and tungsten ions in the solution. Washing the precipitate with water, filtering, adding formic acid into the filtered residue, and selectively leaching at normal temperature for 30min to obtain vanadium extract with pH of 6.5 and vanadium leaching rate of 98.6%. Tungsten exists in a solid phase in the form of calcium tungstate, and a calcium tungstate product is obtained after washing and drying at 200 ℃. And adding ammonia water into the normal-temperature selective leaching solution to precipitate vanadium, and finally recovering the vanadium element in the form of ammonium metavanadate.
Example two
The raw material is from a waste SCR denitration catalyst of a certain power plant in Guizhou, wherein the content of titanium oxide is 85.2%, the content of vanadium pentoxide is 0.57%, and the content of tungstic acid is 3.92%. The catalyst is crushed to 80 meshes of more than 98 percent, is uniformly mixed with 15 percent of sodium carbonate and 1.5 percent of sodium-based double salt, is extruded and molded, is sent to a tunnel type activation reactor to be activated for 2 hours, and passes through a preheating zone at 200 ℃, an activation reaction zone at 700 ℃ and a cooling zone at 90 ℃. Sending the activated material into a high-speed disperser with water for water quenching, then dispersing and scattering the material at high speed, pumping the material to an efficient leaching tank under the condition of uniform stirring, stirring and reacting for 2 hours at the temperature of 80 ℃ according to the liquid-solid ratio of 3:1, after the reaction leaching is finished, obtaining leaching slag, and washing and drying the leaching slag to obtain a titanium oxide product with the purity of 95.1%; adjusting the pH of the obtained leaching filtrate to 11, heating to 80 ℃, adding composite precipitator aluminum sulfate and magnesium sulfate, adding the composite precipitator according to the molar ratio of the aluminum sulfate to silicon-aluminum ions of 1:1, controlling the reaction end point to be 10.5, stirring for 30min, standing for 1h, filtering, and precipitating impurities of silicon and aluminum in the solution in a slag phase. And (3) after impurity removal, adjusting the pH of the solution to 10 by using hydrochloric acid, adding calcium chloride according to the molar ratio of the solution to vanadium and tungsten ions of 2:1, stirring for 30min, standing for 1h, filtering, and precipitating vanadium and tungsten ions in the solution. Washing the precipitate with water, filtering, adding formic acid into the filtered residue, and selectively leaching at normal temperature for 30min with pH of 6.5 to obtain vanadium leaching rate of 98.4%. Tungsten exists in a solid phase in the form of calcium tungstate, and a calcium tungstate product is obtained after washing and drying at 200 ℃. And adding ammonia water into the normal-temperature selective leaching solution to precipitate vanadium, and finally recovering the vanadium element in the form of ammonium metavanadate.
EXAMPLE III
The raw material is from a waste SCR denitration catalyst of a certain power plant in Guizhou, wherein the content of titanium oxide is 87.2 percent, the content of vanadium pentoxide is 0.61 percent, and the content of tungstic acid is 3.82 percent. The catalyst is crushed to 80 meshes of more than 98 percent, is uniformly mixed with 10 percent of sodium carbonate and 2 percent of sodium-based double salt, is extruded and molded, is sent to a tunnel type activation reactor to be activated for 2 hours, and passes through a preheating zone at 200 ℃, an activation reaction zone at 750 ℃ and a cooling zone at 90 ℃. Sending the activated material into a high-speed disperser with water for water quenching, then dispersing and scattering the material at high speed, pumping the material to an efficient leaching tank under the condition of uniform stirring, stirring and reacting for 2 hours at the temperature of 90 ℃ according to the liquid-solid ratio of 3:1, after the reaction and leaching are finished, obtaining leaching slag, and washing and drying the leaching slag to obtain a titanium oxide product with the purity of 95.5%; adjusting the pH of the obtained leaching filtrate to 11, heating to 80 ℃, adding composite precipitator aluminum sulfate and magnesium sulfate, adding the composite precipitator according to the molar ratio of the aluminum sulfate to silicon-aluminum ions of 1:1, controlling the reaction end point to be pH8.5, stirring for 30min, standing for 1h, filtering, and precipitating impurities of silicon and aluminum in the solution in a slag phase. And (3) after impurity removal, adjusting the pH of the solution to 8.0 by using hydrochloric acid, adding calcium chloride according to the molar ratio of the solution to vanadium and tungsten ions of 2:1, stirring for 30min, standing for 1h, filtering, and precipitating vanadium and tungsten ions in the solution. Washing the precipitate with water, filtering, adding formic acid into the filtered residue, and selectively leaching at normal temperature for 30min with pH of 6.5 to obtain vanadium leaching rate of 98.3%. Tungsten exists in a solid phase in the form of calcium tungstate, and a calcium tungstate product is obtained after washing and drying at 200 ℃. And adding ammonia water into the normal-temperature selective leaching solution to precipitate vanadium, and finally recovering the vanadium element in the form of ammonium metavanadate.
Example four
The raw material is from a waste SCR denitration catalyst of a certain power plant in Guizhou, wherein the content of titanium oxide is 87.2 percent, the content of vanadium pentoxide is 0.31 percent, and the content of tungstic acid is 3.42 percent. The catalyst is crushed to 80 meshes of more than 98 percent, is uniformly mixed with 10 percent of sodium carbonate and 1 percent of sodium-based double salt, is extruded and molded, is sent to a tunnel type activation reactor to be activated for 2 hours, and passes through a preheating zone at 200 ℃, an activation reaction zone at 750 ℃ and a cooling zone at 90 ℃. Sending the activated material into a high-speed disperser with water for water quenching, then dispersing and scattering the material at high speed, pumping the material to an efficient leaching tank under the condition of uniform stirring, stirring and reacting for 2 hours at the temperature of 90 ℃ according to the liquid-solid ratio of 3:1, after the reaction and leaching are finished, obtaining leaching slag, and washing and drying the leaching slag to obtain a titanium oxide product with the purity of 95.0%; adjusting the pH of the obtained leaching filtrate to 11, heating to 80 ℃, adding composite precipitator aluminum sulfate and magnesium sulfate, adding the composite precipitator according to the molar ratio of the aluminum sulfate to silicon-aluminum ions of 1:1, controlling the reaction end point to be 10.5, stirring for 30min, standing for 1h, filtering, and precipitating impurities of silicon and aluminum in the solution in a slag phase. And (3) after impurity removal, adjusting the pH of the solution to 10 by using hydrochloric acid, adding calcium chloride according to the molar ratio of the solution to vanadium and tungsten ions of 2:1, stirring for 30min, standing for 1h, filtering, and precipitating vanadium and tungsten ions in the solution. Washing the precipitate with water, filtering, adding formic acid into the filtered residue, and selectively leaching at normal temperature for 30min with pH of 6.5 to obtain vanadium leaching rate of 98.1%. Tungsten exists in a solid phase in the form of calcium tungstate, and a calcium tungstate product is obtained after washing and drying at 200 ℃. And adding ammonia water into the normal-temperature selective leaching solution to precipitate vanadium, and finally recovering the vanadium element in the form of ammonium metavanadate.
In conclusion, the method for extracting valuable elements of the waste denitration catalyst through medium-temperature tunnel type solid-state activation realizes efficient leaching of vanadium and tungsten from the denitration waste catalyst; and enriching vanadium and tungsten by combining with calcium chloride precipitation, selectively leaching vanadium at normal temperature to realize selective separation of tungsten and vanadium, precipitating vanadium by using vanadium-containing solution ammonia water, and recycling valuable metals in the SCR denitration waste catalyst by using products of titanium dioxide, calcium tungstate and ammonium metatungstate.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (4)
1. The method for extracting valuable elements of the waste denitration catalyst by medium-temperature tunnel type solid-state activation is characterized by comprising the following steps of:
(1) the method comprises the steps of (1) carrying out medium-temperature tunnel type solid-state activation reaction, uniformly mixing SCR denitration waste catalyst material which is crushed to reach the fineness requirement that 80-mesh material accounts for more than or equal to 98%, 10-20% of sodium carbonate and 1-3% of sodium-based complex salt, carrying out extrusion forming, putting the mixture into a tunnel type activation reactor, carrying out the whole activation reaction for 2-3 hours through a preheating zone at 200 ℃, an activation reaction zone at 400-750 ℃ and a cooling zone at 80-100 ℃, and feeding the activated material to a high-speed dispersion machine for water quenching and scattering;
(2) water leaching, namely pumping the scattered ore pulp into a high-efficiency leaching tank, adding water according to the liquid-solid ratio of 3:1, stirring for 1-2 hours at the operation temperature of 40-90 ℃ under the action of ultrasonic waves, performing liquid-solid separation after leaching to obtain leaching liquid and leaching residues, and washing and drying the leaching residues to obtain a product titanium dioxide;
(3) removing impurities from silicon and aluminum in the leaching filtrate, adjusting p H to 11, adding aluminum sulfate and magnesium sulfate as composite precipitator, adding the aluminum sulfate and the magnesium sulfate according to the quantity ratio of silicon-aluminum ionic substances of 1:1, precipitating impurities of silicon and aluminum in the solution in a slag phase, and filtering to obtain silicon-aluminum slag and an impurity-removed liquid;
(4) precipitating vanadium and tungsten, adjusting the solution p H to 8.0-10% by hydrochloric acid after impurity removal, adding calcium chloride, stirring, standing and filtering after stirring, precipitating vanadium and tungsten ions in the solution, performing liquid-solid separation to obtain vanadium and tungsten precipitates and a precipitated solution, and mixing the precipitated solution and the impurity removed solution;
(5) selectively leaching at normal temperature, washing and filtering tungsten and vanadium precipitates, adding 10-20% formic acid for selective leaching, controlling the selective leaching process p H to be 6.5, leaching most vanadium into a solution, allowing tungsten to exist in a solid phase in the form of calcium tungstate, washing and drying to obtain a calcium tungstate product;
(6) precipitating vanadium, adding 5% ammonia water into the normal temperature leaching solution to precipitate vanadium, and finally recovering vanadium element in the form of ammonium metavanadate.
2. The method for extracting valuable elements from waste denitration catalysts through medium-temperature tunnel type solid activation according to claim 1, characterized in that in the step (1), a water quenching and high-speed dispersion machine breaks up the valuable elements with a liquid-solid ratio of 2: 1.
3. The method for extracting valuable elements from a waste denitration catalyst through medium-temperature tunnel type solid-state activation according to claim 1, wherein in the step (2), agitation leaching is performed under ultrasonic operation.
4. The method for extracting valuable elements from a waste denitration catalyst through medium-temperature tunnel type solid-state activation according to claim 1, wherein in the step (4), the calcium chloride is added according to the amount ratio of vanadium-tungsten ionic substances of 2: 1.
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| CN110643808B (en) * | 2019-11-07 | 2021-06-22 | 赣州有色冶金研究所有限公司 | Method for extracting tungsten from low-grade wolframite |
| CN111996379B (en) * | 2020-08-27 | 2022-01-25 | 江西理工大学 | Method for recovering valuable metal from waste SCR denitration catalyst |
| CN115770565B (en) * | 2021-09-06 | 2024-06-28 | 中国石油天然气股份有限公司 | Flue gas denitration catalyst and preparation method thereof |
| CN115924926B (en) * | 2022-11-22 | 2024-05-14 | 辽宁智优环保科技有限公司 | Method for efficiently recycling valuable components in waste SCR catalyst |
| CN115717201A (en) * | 2022-11-25 | 2023-02-28 | 辽宁智优环保科技有限公司 | Method for recovering metal oxide from waste SCR denitration catalyst |
| CN118086679A (en) * | 2024-03-29 | 2024-05-28 | 广东省科学院资源利用与稀土开发研究所 | Method for recovering vanadium from waste nickel aluminum powder for catalyst |
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