CN115194163A - Method for preparing titanium-tungsten powder by recovering waste SCR denitration catalyst - Google Patents
Method for preparing titanium-tungsten powder by recovering waste SCR denitration catalyst Download PDFInfo
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Abstract
The invention relates to a method for preparing titanium-tungsten powder by recovering a waste denitration catalyst, and belongs to the field of recovery of waste denitration catalysts. The method comprises the steps of pretreating a waste denitration catalyst by deashing, crushing and grinding to obtain waste denitration catalyst powder, further removing impurities and purifying by a flat-throwing layering process to obtain powder with high tungsten content, uniformly mixing the powder and a calcium compound in a ratio of 1: 0.2-0.8, adding ultrapure water in a liquid-solid ratio of 1: 5-10, and then inputting the mixture into a ball mill for grinding reaction to obtain slurry. Calcining the slurry in a rotary kiln to obtain a mixture of the waste denitration catalyst and a calcium compound after reaction, pickling and dissolving calcium vanadate in the mixture, and filtering; washing and drying the filter residue, grinding the filter residue into powder to obtain titanium tungsten powder, adjusting the pH of the filtrate to precipitate calcium vanadate, and filtering and drying the calcium vanadate. And obtaining the titanium-tungsten powder to be finely ground. According to the invention, vanadium in the waste denitration catalyst is extracted by calcining at high temperature to form a calcification so as to obtain the titanium-tungsten powder material, so that the calcining cost is reduced.
Description
Technical Field
The invention belongs to the field of waste denitration catalyst recovery, and particularly relates to a method for producing titanium-tungsten powder by using a waste denitration catalyst based on a high-temperature calcination method.
Background
The selective catalytic reduction denitration technology takes a denitration catalyst as the core of the process to remove nitrogen oxides in flue gas, the process is a flue gas denitration technology with the widest application range in the coal industry due to the efficient and stable characteristics, but the service life of the denitration catalyst is 2-3 years, and various catalysts are inactivated due to the action of flue gas with complex components during use and are discarded. In recent years, the service life of the catalyst is prolonged along with the increase of the amount of the waste denitration catalyst.
The waste denitration catalyst is used as the hazardous waste specified in the national hazardous waste book, and the main components of the waste denitration catalyst, such as vanadium, tungsten, titanium and other metal elements, are national strategic metal resources, so that the waste denitration catalyst has extremely high recovery value. In recent years, the nation encourages safe disposal of waste denitration catalyst resources, realizes multiple utilization of strategic metal resources, and not only obtains economic benefits but also reduces environmental pollution.
Patent CN112408470A (reference 1) discloses a method for producing titanium dioxide by using a waste denitration catalyst based on a high-temperature calcination method, which comprises the steps of ash removal, impurity removal, crushing, alkali liquor mixing, calcination, grinding, filtration washing, drying, fine grinding and the like to obtain titanium dioxide and vanadium tungsten products, but the alkali liquor is added twice for reaction, and a large amount of washing is adopted to reduce the pH value of filtrate, so that the alkali consumption is increased, a large amount of waste liquor is produced and is difficult to treat, and the production cost is higher.
Chinese patent CN101921916A (comparison document 2) discloses a method for recovering metal oxide from waste flue gas denitration catalyst, which comprises the steps of primary roasting, crushing, grinding, mixed alkali, secondary roasting, hot water soaking, precipitation filtering, acid washing, water washing and roasting to obtain titanium dioxide, and the filtrate is subjected to subsequent treatment to obtain V 2 O 5 、MoO 3 And WO 3 A product; however, this process uses two high temperature roasts, and requires mixing in sodium carbonate and grinding to fine<200 mu m, the operation is more complicated, and the patent is mainly used for preparing V 2 O 5 、MoO 3 And WO 3 The product discussion is more detailed, mainly aiming at recovering V 2 O 5 、MoO 3 And WO 3 These three products. Chinese patent CN106337133B (reference 3) discloses a method for recovering titanium, vanadium and tungsten from a waste denitration catalyst: mixing the waste denitration catalyst, the iron-containing raw material, the carbon-containing raw material, the adhesive and the calcium-containing raw material, granulating into a spherical material, and calcining at 1500-1650 ℃ to obtain the vanadium-tungsten-containing pig iron and titanium slag. The calcination temperature of the process is relatively high, resulting in TiO 2 The crystal form of the titanium dioxide is changed, the energy consumption is high, and the titanium dioxide is not suitable for the preparation or production of the titanium dioxide. CN202011187934.2 (comparison document 4) discloses a treatment process of a vanadium-titanium denitration waste catalyst, which comprises the following steps: crushing and pulverizing: crushing the vanadium-titanium denitration waste catalyst into powder with the particle size of less than 100 mu m; sodium treatment roasting: adding the crushed vanadium-titanium denitration waste catalyst into soda ash and water according to a certain proportion, mixing, and adding into a rotary kiln for sodium modification roasting transformation; leaching: adding water into the mixture, ball-milling, sieving and leaching to obtain filtrate and filter residue; recovering vanadium: adding excessive ammonium chloride into the filtrate, mechanically stirring for 0.5-1h, standing for precipitation, and filtering to obtain filtrate and ammonium metavanadate; recovering molybdic acid and tungstic acid: heating the filtrate to 60-70 ℃ by steam, adjusting the pH value of sulfuric acid to 2, and filtering to obtain molybdic acid, tungstic acid and filtrate; adjusting the pH value and washing: the filter residue and water are filled into a reactor according to the mass ratio of 1The reaction product is subjected to solid-liquid separation, and then the solid is washed by water to prepare titanic acid precipitate; and (3) calcining: calcining titanic acid precipitate to obtain TiO 2 。
Disclosure of Invention
The invention provides a method for producing titanium-tungsten powder by using a waste denitration catalyst based on a high-temperature calcination method, which comprises the steps of crushing and grinding the waste denitration catalyst, retaining heavy powder with higher tungsten content in a front layer by a flat-throwing layering process, removing light impurities such as alkali metal and the like, wet-grinding the powder with higher tungsten content to form slurry, calcining the slurry to improve the reaction rate of waste denitration catalytic metal oxide and calcium compound, and separating different metal elements by acid washing. Drying the filter residue to obtain titanium-tungsten powder, and then recycling vanadium in the filtrate through precipitation. The invention mainly aims to solve the following technical problems in the related art: firstly, the recycling rate of the waste denitration catalyst is improved, and the environmental pollution is reduced; and the process flow and the recovery cost of the titanium-tungsten powder are simplified.
The invention is realized by the following technical scheme:
a method for preparing titanium tungsten powder by recovering a waste SCR denitration catalyst is characterized by comprising the following steps:
(1) Carrying out pretreatment of ash removal, crushing and grinding on a waste denitration catalyst to obtain waste denitration catalyst powder, further removing impurities and purifying by a flat-throwing layering process to obtain powder with higher tungsten content, uniformly mixing the powder and a calcium compound in a ratio of 1: 0.2-0.8, adding ultrapure water in a liquid-solid ratio of 1: 5-10, and then inputting the mixture into a ball mill for grinding reaction to obtain slurry;
(2) And calcining the slurry to obtain a mixture of the waste denitration catalyst and the calcium compound after reaction, pickling and dissolving calcium vanadate in the mixture, and filtering. And recycling the acidic filtrate for multiple times, washing and drying the filter residue, and grinding the filter residue into powder to obtain the titanium-tungsten powder. Further, the filtrate which is recycled for many times is filtered and dried after the pH value of the filtrate is adjusted to precipitate calcium vanadate.
Further, in the step (1), the ash removal is to remove floating ash on the surface and dust in the holes through air circulation, and the airflow pressure is set to be 0.2-2MPa; crushing is to mechanically crush the deashed waste denitration catalyst to 5-10mm: grinding is carried out to grind the waste denitration catalyst pieces to an average particle size of 50-120 mu m, so as to obtain waste denitration catalyst powder, and facilitate the reaction among reactants. Further, the materials in the screen mesh of the flat-throwing layering process in the step (1) freely fall by gravity, the powder materials are layered under the action of vertical air flow with the speed of 2-4m/s, and the first 60-90% of the layered materials are collected for use. In the horizontal throwing layering process, powder falling from a vertical airflow enables powder with high tungsten and titanium metal oxide content and heavy weight to be retained in the front layer under the action of airflow at a certain speed, impurities such as alkali metal and silicon with light weight are brought to the rear layer by the airflow, so that metals with different weights are layered, then heavy powder with low impurity content in the front layer is collected for subsequent treatment process, and impurity components in the waste denitration catalyst powder are further reduced.
Further, the calcium compound in the step (1) is CaO, ca (OH) 2 、CaCO 3 One or more of them.
Further, the ball mill in the step (1) grinds for 2-8h to 50-80 μm, the solid content of the slurry is 10-20%, and the temperature of the slurry is 60-80 ℃. The ball milling can not only further reduce the particle size of the powder, but also ensure that the powder is mixed more uniformly in the process and the mixed powder is kept in an alkaline environment, thereby further promoting the reaction in the calcining process.
Further, the calcining temperature in the step (2) is 450-780 ℃, and the calcining time is 1-3h. And maintaining an alkaline environment for the slurry after wet grinding by adding ultrapure water, so as to promote further activation of valuable metal oxides in the waste denitration catalyst. The direct calcination of the aqueous slurry promotes the retention of the alkaline environment of the reactants in the heating process, the heating promotes the reaction between the calcium compound in the slurry and the waste denitration catalyst to further occur, and the calcination temperature generated by the reaction is effectively reduced. Meanwhile, due to the boiling effect in the process of evaporating the water to dryness, holes are formed among powder materials, and the reaction between the compound and the waste denitration catalyst at high temperature is facilitated.
The main reactions that may occur during calcination are as follows:
WO 3 +CaO/Ca(OH) 2 /CaCO 3 ＝CaWO 4 +H 2 O/CO 2 (1)
V 2 O 5 +CaO/Ca(OH) 2 /CaCO 3 ＝CaV 2 O 6 +H 2 O/CO 2 (2)
CaV 2 O 6 +CaO＝Ca 2 V 2 O 7 (3)
further, the acid in the step (2) is HCl and HNO 3 、H 2 SO 4 One or more than one of the components with the concentration of 1-4mol/L and the solid-liquid ratio of 1: 2-5.
Further, the temperature of the acid washing in the step (2) is 40-90 ℃, and the reaction time is 0.5-1.5h. Acid washing makes calcium vanadate, calcium pyrovanadate and the like generated by calcination generate vanadate and dissolve in the solution, and calcium tungstate is converted into tungstic acid and remains in the precipitate together with titanium dioxide. The vanadium content of the waste denitration catalyst powder is low, so that the acid solution needs to be recycled for multiple times to improve the vanadium concentration. By adjusting the pH value of the acid liquor, calcium ions can react with vanadate to generate calcium vanadate precipitate, and a calcium vanadate product with higher purity can be obtained after filtration and drying, so that the recovery of vanadium is facilitated.
Further, the drying temperature in the step (2) is 110-180 ℃, and the drying time is 0.5-2h. The drying process not only removes acid liquor and water contained in the filter residue, but also converts tungstic acid in the filter residue into tungsten trioxide through pyrolysis, thereby obtaining regenerated titanium-tungsten powder for recycling. After filtering and drying, a calcium vanadate product with higher purity can be obtained, and the recovery of vanadium is convenient to realize.
Further, the average particle size of the pulverized powder in the step (2) is 10-30 μm. The titanium tungsten powder product meets the standard of industrial production and use by secondary grinding, and the circulation of the waste denitration catalyst is realized.
The technical innovation points of the invention are as follows:
(1) Compared with all comparison documents, the method adds a flat-throwing layering process and a mixed grinding process, wherein powder falling from a vertical airflow in the flat-throwing layering process enables powder with higher contents of tungsten and titanium metal oxides and heavier weight to be retained in a front layer under the action of airflow at a certain speed, impurities such as alkali metal and silicon with lighter weight are brought to a rear layer by the airflow, so that metals with different weights are layered, then heavy powder with lower impurity content in the front layer is collected, ultrapure water is added for wet grinding, and mixed grinding treatment is carried out, so that not only is impurity components in the waste denitration catalyst powder reduced, but also the slurry after wet grinding is kept in an alkaline environment, and valuable metal oxides in the waste denitration catalyst are further activated. The direct calcination of the aqueous slurry promotes the alkaline environment of reactants to be preserved in the temperature rise process, the temperature rise promotes the reaction between the calcium compound in the slurry and the waste denitration catalyst to further occur, and the calcination temperature generated by the reaction is effectively reduced. And then calcium compound is matched as sintering aid, so that the roasting temperature of the product is directly reduced from over 1000 ℃ to 450-780 ℃.
(2) Compared with the document 1, the invention adds a step of acid washing after the calcination, instead of the step of grinding with alkaline water, in addition to adding a step of mixed grinding before the flat polishing and layering process and adding a step of matching calcium compound as a sintering aid, so that the acid washing can dissolve calcium vanadate generated by the calcination, calcium pyrovanadate and the like in the solution while reducing the discharge of the alkaline water, and the calcium tungstate is converted into tungstic acid and remains in the precipitate together with titanium dioxide. Not only can obtain a calcium vanadate product with higher purity, but also improves the purity of the titanium-tungsten powder.
(3) The comparison document 2 adopts a secondary roasting process, and the production process is complex and high in cost.
(4) The comparison document 3 is that the baking temperature is high.
(5) Reference 4 discloses a processing technology of vanadium titanium system denitration spent catalyst, adopts sodium salt roasting, actually produces ammonium metavanadate, ammonium molybdate and ammonium tungstate through a water immersion method after roasting, realizes the recovery of vanadium through ammonium metavanadate, and does not relate to the production problem of titanium tungsten powder.
The invention is characterized in that the TiO is reserved 2 And WO 3 The components are prepared into a titanium-tungsten powder carrier, so that the process steps are shortened, the alkali consumption in the reaction process and the wastewater output are reduced, and the existing method for completely separating and recovering titanium dioxide causes the titanium dioxide recovery process to be complex, the alkali consumption to be large and the wastewater to be largeLarge output and the like.
The beneficial technical effects of the invention are as follows:
(1) The titanium tungsten powder is prepared from the waste denitration catalyst, so that the waste denitration catalyst recovery process is simplified, the output of waste liquid is reduced, the cost is reduced, and the risk of environmental pollution is reduced.
(2) By controlling the ball milling temperature, the calcining temperature and the calcining time, the V is improved 2 O 5 Reaction with calcium compound while inhibiting calcium compound and TiO 2 The reaction between the titanium and the tungsten powder reduces energy and recovers the titanium and the tungsten powder in a relatively energy-saving mode.
(3) Vanadium components are separated by alkali neutralization and precipitation, so that an evaporation crystallization process with high energy consumption is avoided, and the obtained calcium vanadate and other products have the same economic value as vanadium oxide.
Drawings
FIG. 1 is a flow chart of a method for preparing titanium tungsten powder by recovering a waste SCR denitration catalyst.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail with reference to specific embodiments. It should be understood that the description herein of specific embodiments is for purposes of illustration only and is not intended to limit the invention to the particular embodiments, but it will be understood by those skilled in the art that the invention will be, in any case, fully understood without such details. The invention is intended to cover alternatives, modifications, equivalents and alternatives which may be included within the spirit and scope of the invention as defined by the appended claims.
Example 1
Referring to fig. 1, a method for recovering and preparing titanium-tungsten powder from a waste SCR denitration catalyst comprises the steps of pretreatment, flat polishing and layering, material mixing, ball milling, calcining, acid washing and filtering to obtain filter residue and filtrate, further reusing the filtrate for multiple times to improve the vanadium content, adjusting the pH value to precipitate vanadium, drying to obtain a calcium vanadate product, and washing and drying the filter residue to obtain the titanium-tungsten powder.
The pretreatment comprises the steps of ash removal, crushing and grinding. The ash removal is to remove floating ash on the surface of the denitration catalyst and dust in holes through air circulation, set the airflow pressure to be 0.8MPa, mechanically crush the deashed waste denitration catalyst to 5-10mm, and then grind to obtain waste denitration catalyst powder with the average particle size of 80-150 mu m. After the catalyst powder is subjected to horizontal casting and layering at the vertical wind speed of 2m/s, the first 80% of the layered powder is collected, and further impurity removal is completed. Uniformly mixing the collected heavy powder of the front layer with CaO of which the mass is 0.8 times that of the heavy powder, and then mixing the powder with ultrapure water according to a liquid-solid ratio of 10:1, jointly inputting the materials into a ball mill for ball milling, setting the ball milling temperature to be 50 ℃ and the ball milling time to be 2h: calcining the ball-milled slurry at the calcining temperature of 750 ℃, preserving heat for 1.5h, and then cooling in air.
Further, mixing the roasted powder with 2mol/L HCl in a liquid-solid ratio of 5:1 proportion is added into a stirring reactor, and the reaction temperature is set to be 60 ℃ for reaction for 0.5h. Then filtering to obtain filtrate and filter residue. And (3) recycling the filtrate again after keeping the acid concentration of the filtrate at 2mol/L, and regulating the pH of the filtrate after repeated recycling to be more than or equal to 7 by using alkali liquor to precipitate, filter and dry calcium vanadate so as to obtain a calcium vanadate product. Drying the acid-washed filter residue at 150 ℃ for 1h to obtain titanium tungsten powder, and grinding the titanium tungsten powder for the second time until the particle size of the powder is 10-30 mu m.
Example 2
A method for recycling and preparing titanium tungsten powder from a waste SCR denitration catalyst comprises the steps of pretreatment, flat polishing and layering, mixing, ball milling, calcining, acid washing and filtering to obtain filter residues and filter liquor, further reusing the filter liquor for multiple times to improve the vanadium content, adjusting the PH to precipitate vanadium, drying to obtain a calcium vanadate product, and washing and drying the filter residues to obtain the titanium tungsten powder.
The pretreatment comprises the steps of ash removal, crushing and grinding. The ash removal is to remove floating ash on the surface of the denitration catalyst and dust in holes through air circulation, set the airflow pressure to be 0.6MPa, mechanically crush the deashed denitration catalyst to 5-8mm, and then grind the deashed denitration catalyst to obtain the denitration catalyst powder with the average particle size of 80-120 mu m. Further, after the catalyst powder is horizontally thrown and layered at the vertical wind speed of 2.5m/s, the first 70% of the layered powder is collected, and further impurity removal is completed. The front layer of heavier powder and 0.8 times the mass of CaCO are collected 3 After uniform mixing, mixing the powder and ultrapure water according to a liquid-solid ratio of 10:1, inputting the mixture into a ball mill for ball milling, and setting the ball milling time to be 2h: calcining the ball-milled slurry at the calcining temperature of 700 ℃, and preserving heat for 2 hoursAnd air cooling.
Further, mixing the roasted powder with 2mol/L HCl in a liquid-solid ratio of 4:1 proportion is added into a stirring reactor, and the reaction temperature is set to 40 ℃ for reaction for 1 hour. Then filtering to obtain filtrate and filter residue. And (3) recycling the filtrate again after keeping the acid concentration of the filtrate at 2mol/L, and regulating the pH of the filtrate after repeated recycling to be more than or equal to 7 by using alkali liquor to precipitate, filter and dry calcium vanadate so as to obtain a calcium vanadate product. And drying the acid-washed filter residue at 120 ℃ for 0.5 to obtain titanium-tungsten powder, and grinding the titanium-tungsten powder for the second time until the particle size of the powder is 10-30 mu m.
Embodiment 3
A method for recycling and preparing titanium-tungsten powder from a waste SCR denitration catalyst comprises the steps of pretreatment, flat polishing and layering, material mixing, ball milling, calcining, acid washing and filtering to obtain filter residues and filtrate, further reusing the filtrate for multiple times to improve the vanadium content, adjusting the pH value to precipitate vanadium, drying to obtain a calcium vanadate product, and drying the filter residues to obtain the titanium-tungsten powder.
The pretreatment comprises the steps of ash removal, crushing and grinding. The ash removal is to remove floating ash on the surface of the denitration catalyst and dust in holes through air circulation, set the airflow pressure to be 0.5MPa, mechanically crush the deashed denitration catalyst to 7-10mm, and then grind the deashed denitration catalyst to obtain the denitration catalyst powder with the average particle size of 80-100 microns. Further, after the catalyst powder is subjected to flat-casting layering at the vertical wind speed of 3m/s, the first 80% of the layered powder is collected, and further impurity removal is completed. The front layer of heavier powder and 1.0 times the mass of Ca (OH) are collected 2 After uniform mixing, mixing the powder with ultrapure water according to a liquid-solid ratio of 8:1, inputting the mixture into a ball mill for ball milling, and setting the ball milling time to be 4h: calcining the ball-milled slurry at the calcining temperature of 730 ℃, preserving heat for 2 hours and then cooling in air.
Further, the roasted powder is mixed with 3mol/L HNO 3 And (2) according to the liquid-solid ratio of 5:1 proportion is added into a stirring reactor, and the reaction temperature is set to be 50 ℃ for reaction for 1 hour. Then filtering to obtain filtrate and filter residue. And (3) recycling the filtrate again after keeping the acid concentration of the filtrate at 3mol/L, and regulating the pH of the filtrate after repeated recycling to be more than or equal to 10 by ammonia water to precipitate, filter and dry calcium vanadate to obtain a calcium vanadate product. Washing the acid-washed filter residue with water, drying at 120 deg.C for 1 hr to obtain titanium-tungsten powder, grinding for the second time until the average particle diameter of the powder is 15 μmThe preparation is used.
Example 4
A method for recycling and preparing titanium-tungsten powder from a waste SCR denitration catalyst comprises the steps of pretreatment, flat polishing and layering, material mixing, ball milling, calcining, acid washing and filtering to obtain filter residues and filtrate, further reusing the filtrate for multiple times to improve the vanadium content, adjusting the pH value to precipitate vanadium, drying to obtain a calcium vanadate product, and drying the filter residues to obtain the titanium-tungsten powder.
The pretreatment comprises the steps of ash removal, crushing and grinding. The ash removal is to remove floating ash on the surface of the denitration catalyst and dust in holes through air circulation, set the airflow pressure to be 1.5MPa, mechanically crush the deashed denitration catalyst to 7-10mm, and then grind the deashed denitration catalyst to obtain the denitration catalyst powder with the average particle size of 80-100 microns. And after the catalyst powder is subjected to flat-casting layering at the vertical wind speed of 3m/s, collecting the first 80% of the layered powder, and finishing further impurity removal. Collecting heavy powder in the front layer and CaO with the mass of 1.0 time of that of the heavy powder, uniformly mixing the heavy powder with deionized water according to the liquid-solid ratio of 6:1, inputting the materials into a ball mill together for ball milling, and setting the ball milling time to be 1.5h: calcining the ball-milled slurry at the calcination temperature of 727 ℃, preserving the heat for 2.5 hours and then cooling in air.
Further, mixing the calcined powder with 1.5mol/L HCl in a liquid-solid ratio of 5:1 proportion is added into a stirring reactor, and the reaction temperature is set to 85 ℃ for reaction for 0.5h. Then filtering to obtain filtrate and filter residue. And (3) recycling the filtrate after keeping the acid concentration of the filtrate at 1.5mol/L, adjusting the pH of the filtrate after repeated recycling to be more than or equal to 7 by ammonia water, precipitating, filtering and drying the calcium vanadate to obtain a calcium vanadate product. And drying the acid-washed filter residue for 2 hours at 120 ℃, and grinding for the second time until the particle size of the powder is less than 20 mu m to obtain the titanium-tungsten powder product.
Example 5
A method for recycling and preparing titanium-tungsten powder from a waste SCR denitration catalyst comprises the steps of pretreatment, flat polishing and layering, material mixing, ball milling, calcining, acid washing and filtering to obtain filter residues and filtrate, further reusing the filtrate for multiple times to improve the vanadium content, adjusting the pH value to precipitate vanadium, drying to obtain a calcium vanadate product, and drying the filter residues to obtain the titanium-tungsten powder.
The pretreatment comprises the steps of deashing, crushing and grinding. The ash removal is to remove denitration catalyst through air circulationSetting the airflow pressure of the floating ash on the surface of the agent and the dust in the holes to be 2MPa, mechanically crushing the deashed waste denitration catalyst to 6-10mm, and grinding to obtain waste denitration catalyst powder with the average particle size of 100-150 mu m. After the catalyst powder is subjected to horizontal casting and layering at the vertical wind speed of 3m/s, the first 85% of the layered powder is collected, and further impurity removal is completed. The powder with the heavier front layer and CaCO with the mass of 0.6 times of that of the powder are collected 3 After uniform mixing, mixing the powder with deionized water according to a liquid-solid ratio of 10:1, inputting the mixture into a ball mill for ball milling, and setting the ball milling time to be 4h: calcining the ball-milled slurry at the calcining temperature of 650 ℃, preserving heat for 1.5h, and then cooling in air.
Further, mixing the calcined powder with 1.5mol/L HCl in a liquid-solid ratio of 5:1 proportion is added into a stirring reactor, and the reaction temperature is set to 85 ℃ for reaction for 0.5h. Then filtering to obtain filtrate and filter residue. And (3) recycling the filtrate again after keeping the acid concentration of the filtrate at 1.5mol/L, and regulating the pH of the filtrate after repeated recycling to be more than or equal to 7 by using sodium hydroxide to precipitate, filter and dry calcium vanadate so as to obtain a calcium vanadate product. Drying the acid-washed filter residue for 2h at 150 ℃, and grinding for the second time until the particle size of the powder is 10-20 μm to obtain the titanium-tungsten powder product.
Example 6
A method for recycling and preparing titanium-tungsten powder from a waste SCR denitration catalyst comprises the steps of pretreatment, flat polishing and layering, material mixing, ball milling, calcining, acid washing and filtering to obtain filter residues and filtrate, further reusing the filtrate for multiple times to improve the vanadium content, adjusting the pH value to precipitate vanadium, drying to obtain a calcium vanadate product, and drying the filter residues to obtain the titanium-tungsten powder.
The pretreatment comprises the steps of ash removal, crushing and grinding. The ash removal is to remove floating ash on the surface of the denitration catalyst and dust in holes through air circulation, set the airflow pressure to be 0.8MPa, mechanically crush the deashed denitration catalyst to 6-10mm, and then grind the deashed denitration catalyst to obtain the denitration catalyst powder with the average particle size of 100-150 mu m. After the catalyst powder is subjected to horizontal casting and layering at the vertical wind speed of 2.5m/s, the first 80% of the layered powder is collected, and further impurity removal is completed. Collecting the front layer heavier powder and Ca (OH) with the mass 0.8 times of that of the powder 2 After uniform mixing, mixing the powder with deionized water according to a liquid-solid ratio of 10:1, jointly inputting the raw materials into a ball mill for ball milling, and setting the ball milling time as4h: calcining the ball-milled slurry at the calcining temperature of 650 ℃, preserving heat for 1h and then cooling in air.
Further, mixing the roasted powder with 2mol/L HCl in a liquid-solid ratio of 4:1 proportion is added into a stirring reactor, and the reaction temperature is set to 40 ℃ for reaction for 1 hour. Then filtering to obtain filtrate and filter residue. And (3) recycling the filtrate again after keeping the acid concentration of the filtrate at 2mol/L, and regulating the pH of the filtrate after repeated recycling to be more than or equal to 7 by using alkali liquor to precipitate, filter and dry calcium vanadate so as to obtain a calcium vanadate product. Drying the acid-washed filter residue at 160 ℃ for 0.5h to obtain titanium-tungsten powder, and grinding the titanium-tungsten powder for the second time until the particle size of the powder is 10-20 mu m.
Example 7
A method for recycling and preparing titanium tungsten powder from a waste SCR denitration catalyst comprises the steps of pretreatment, flat polishing and layering, mixing, ball milling, calcining, acid washing and filtering to obtain filter residues and filter liquor, further reusing the filter liquor for multiple times to improve the vanadium content, adjusting PH to precipitate vanadium, drying to obtain a calcium vanadate product, and drying the filter residues to obtain the titanium tungsten powder.
The pretreatment comprises the steps of ash removal, crushing and grinding. The ash removal is to remove floating ash on the surface of the denitration catalyst and dust in holes through air circulation, set the airflow pressure to be 0.7MPa, mechanically crush the deashed denitration catalyst to 5-8mm, and then grind the deashed denitration catalyst to obtain the denitration catalyst powder with the average particle size of 120-150 mu m. After the catalyst powder is subjected to horizontal casting and layering at the vertical wind speed of 2m/s, the first 65% of the layered powder is collected, and further impurity removal is completed. Collecting the powder with the heavier front layer and mixed calcium compound (30% CaCO) 0.8 times its mass 3 70% cao), and then mixing the powder with deionized water in a liquid-solid ratio of 8:1, inputting the mixture into a ball mill for ball milling, and setting the ball milling time to be 4h: calcining the ball-milled slurry at the calcining temperature of 630 ℃, preserving heat for 2 hours and then cooling the slurry along with the furnace.
Further, mixing the roasted powder with 2mol/L HCl in a liquid-solid ratio of 4:1 proportion is added into a stirring reactor, and the reaction temperature is set to 40 ℃ for reaction for 1 hour. Then filtering to obtain filtrate and filter residue. And (3) recycling the filtrate after keeping the acid concentration of the filtrate at 2mol/L, and regulating the pH of the filtrate after repeated recycling to be more than or equal to 7 by using calcium oxide to precipitate, filter and dry the calcium vanadate so as to obtain a calcium vanadate product. Drying the acid-washed filter residue at 130 ℃ for 1h to obtain titanium tungsten powder, and grinding the titanium tungsten powder for the second time until the particle size of the powder is 10-30 mu m.
Example 8
A method for recycling and preparing titanium tungsten powder from a waste SCR denitration catalyst comprises the steps of pretreatment, flat polishing and layering, mixing, ball milling, calcining, acid washing and filtering to obtain filter residues and filter liquor, further reusing the filter liquor for multiple times to improve the vanadium content, adjusting PH to precipitate vanadium, drying to obtain a calcium vanadate product, and drying the filter residues to obtain the titanium tungsten powder.
The pretreatment comprises the steps of deashing, crushing and grinding. The ash removal is to remove floating ash on the surface of the denitration catalyst and dust in holes through air circulation, set the airflow pressure to be 0.5MPa, mechanically crush the deashed denitration catalyst to 7-10mm, and then grind the deashed denitration catalyst to obtain the denitration catalyst powder with the average particle size of 80-130 mu m. After the catalyst powder is horizontally thrown and layered at the vertical wind speed of 4m/s, the first 90 percent of the layered powder is collected to complete further impurity removal. The powder with the heavier front layer and 0.8 times its mass (50% CaCO) 3 50% of CaO), and then mixing the powder with deionized water according to a liquid-solid ratio of 6:1, jointly inputting the materials into a ball mill for ball milling, and setting the ball milling time to be 4h: calcining the ball-milled slurry at the calcining temperature of 730 ℃, preserving heat for 1h, and cooling along with the furnace.
Further, mixing the roasted powder with 4mol/L HCl according to a liquid-solid ratio of 2:1 proportion, adding into a stirring reactor, and setting the reaction temperature at 80 ℃ for reaction for 0.5h. Then filtering to obtain filtrate and filter residue, keeping the acid concentration of the filtrate at 4mol/L for reuse, adjusting the pH of the filtrate after repeated reuse to be more than or equal to 7 by calcium oxide, precipitating calcium vanadate, filtering and drying to obtain a calcium vanadate product. Drying the acid-washed filter residue at 150 ℃ for 0.5h to obtain titanium-tungsten powder, and grinding the titanium-tungsten powder for the second time until the particle size of the powder is 10-30 mu m.
Example 9
A method for recycling and preparing titanium tungsten powder from a waste SCR denitration catalyst comprises the steps of pretreatment, flat polishing and layering, mixing, ball milling, calcining, acid washing and filtering to obtain filter residues and filter liquor, further reusing the filter liquor for multiple times to improve the vanadium content, adjusting PH to precipitate vanadium, drying to obtain a calcium vanadate product, and drying the filter residues to obtain the titanium tungsten powder.
The pretreatment comprises the steps of ash removal, crushing and grinding. The ash removal is to remove floating ash on the surface of the denitration catalyst and dust in holes through air circulation, set the airflow pressure to be 1.5MPa, mechanically crush the deashed denitration catalyst to 7-10mm, and then grind the deashed denitration catalyst to obtain the denitration catalyst powder with the average particle size of 80-130 mu m. After the catalyst powder is subjected to horizontal casting and layering at the vertical wind speed of 2.5m/s, the first 75% of the layered powder is collected, and further impurity removal is completed. Uniformly mixing the collected heavier powder on the front layer with CaO which is 0.8 times of the weight of the powder, and then mixing the powder with deionized water according to a liquid-solid ratio of 6:1, inputting the mixture into a ball mill for ball milling, and setting the ball milling time to be 4h: calcining the ball-milled slurry at the calcining temperature of 780 ℃, preserving heat for 0.5h and then cooling.
Further, mixing the roasted powder with 3mol/L HCl according to a liquid-solid ratio of 3:1 proportion is added into a stirring reactor, and the reaction temperature is set to be 80 ℃ for reaction for 0.5h. Then filtering to obtain filtrate and filter residue, keeping the acid concentration of the filtrate at 3mol/L, recycling again, adjusting the pH of the filtrate after repeated recycling to be more than or equal to 7 by potassium hydroxide, precipitating calcium vanadate, filtering and drying to obtain a calcium vanadate product. Drying the acid-washed filter residue at 180 ℃ for 0.5h to obtain titanium-tungsten powder, and grinding the titanium-tungsten powder for the second time until the average particle size of the powder is 10 mu m.
Embodiment 10
A method for recycling and preparing titanium tungsten powder from a waste SCR denitration catalyst comprises the steps of pretreatment, flat polishing and layering, mixing, ball milling, calcining, acid washing and filtering to obtain filter residues and filter liquor, further reusing the filter liquor for multiple times to improve the vanadium content, adjusting PH to precipitate vanadium, drying to obtain a calcium vanadate product, and drying the filter residues to obtain the titanium tungsten powder.
The pretreatment comprises the steps of ash removal, crushing and grinding. The ash removal is to remove floating ash on the surface of the denitration catalyst and dust in holes through air circulation, set the airflow pressure to be 1.6MPa, mechanically crush the deashed denitration catalyst to 6-8mm, and then grind the deashed denitration catalyst to obtain the denitration catalyst powder with the average particle size of 100-150 mu m. After the catalyst powder is horizontally thrown and layered at the vertical wind speed of 3m/s, the first 80 percent of the impurity layered powder is collected to complete further impurity removal. The front layer of heavier powder and 2 mass times of CaCO are collected 3 After uniform mixing, mixing the powder with deionized water according to a liquid-solid ratio of 5:1, jointly inputting the materials into a ball mill for ball milling, and setting the ball milling time to be 4h: calcining the ball-milled slurry at the calcining temperature of 660 ℃, preserving heat for 2h and cooling.
Further, the roasted powder is mixed with 3mol/L HNO 3 And (2) according to the liquid-solid ratio of 5:1 proportion, adding into a stirring reactor, and setting the reaction temperature at 90 ℃ for reaction for 0.5h. Then filtering to obtain filtrate and filter residue, keeping the acid concentration of the filtrate at 3mol/L, recycling again, adjusting the pH of the filtrate after repeated recycling to be more than or equal to 7 by calcium hydroxide, precipitating calcium vanadate, filtering and drying to obtain a calcium vanadate product. Washing the acid-washed filter residue with water, drying at 180 ℃ for 0.5h to obtain titanium-tungsten powder, and grinding for the second time until the average particle size of the powder is 15 mu m.
Claims (10)
1. A method for preparing titanium tungsten powder by recovering a waste SCR denitration catalyst is characterized by comprising the following steps:
(1) Carrying out ash removal, crushing and grinding pretreatment on a waste denitration catalyst to obtain waste denitration catalyst powder, further removing impurities and purifying by a flat-throwing layering process to obtain powder with higher tungsten content, uniformly mixing the powder with a calcium compound in a ratio of 1: 0.2-0.8, adding ultrapure water in a liquid-solid ratio of 1: 5-10, and then inputting the mixture into a ball mill for grinding reaction to obtain slurry;
(2) Calcining the slurry to obtain a mixture obtained after the reaction of the waste denitration catalyst and a calcium compound, pickling and dissolving calcium vanadate in the mixture, filtering, recycling the acidic filtrate for multiple times, washing and drying filter residues, and grinding the filter residues to obtain titanium-tungsten powder; further, the filtrate which is recycled for many times is filtered and dried after the calcium vanadate is precipitated by adjusting the pH value.
2. The method for preparing titanium-tungsten powder by recovering the waste SCR denitration catalyst according to claim 1, wherein the ash removal in the step (1) is to remove floating ash on the surface and dust in holes through air circulation, and the airflow pressure is set to be 0.2-2MPa; crushing is to mechanically crush the deashed waste denitration catalyst to 5-10mm: grinding the waste denitration catalyst to an average particle size of 50-120 mu m to obtain waste denitration catalyst powder.
3. The method for preparing titanium-tungsten powder by recovering the waste SCR denitration catalyst according to claim 1, wherein the materials in the screen mesh of the horizontal throwing layering process in the step (1) freely fall by gravity, the powder is layered under the action of vertical air flow with the speed of 2-4m/s, and the first 60-90% of the layered materials are collected for use.
4. The method for preparing TiW powder by recovering the waste SCR denitration catalyst according to claim 1, wherein the calcium compound in the step (1) is CaO, ca (OH) 2 、CaCO 3 One or more of them.
5. The method for preparing titanium-tungsten powder by recycling the waste SCR denitration catalyst according to claim 1, wherein the ball mill in the step (1) grinds for 2-8h to 50-80 μm, the solid content of the slurry is 10-20%, and the temperature of the slurry is 60-80 ℃.
6. The method for preparing titanium-tungsten powder by recycling the waste SCR denitration catalyst according to claim 1, wherein the calcination temperature in the step (2) is 450-780 ℃ and the calcination time is 1-3h.
7. The method for preparing titanium-tungsten powder by recycling waste SCR denitration catalyst according to claim 1, wherein the acid in the step (2) is HCl or HNO 3 、H 2 SO 4 One or more than one of the components with the concentration of 1-4mol/L and the solid-liquid ratio of 1: 2-5.
8. The method for preparing titanium-tungsten powder by recycling the waste SCR denitration catalyst according to claim 1, wherein the acid washing temperature in the step (2) is 40-90 ℃, and the reaction time is 0.5-1.5h.
9. The method for preparing titanium-tungsten powder by recovering the waste SCR denitration catalyst according to claim 1, wherein the drying temperature in the step (2) is 110-180 ℃, and the drying time is 0.5-2h.
10. The method for preparing titanium-tungsten powder by recovering waste SCR denitration catalyst according to claim 1, wherein the average particle size of the pulverized powder in the step (2) is 10-30 μm.
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