CN109750156B - Method for recovering vanadium, tungsten/molybdenum and titanium elements from waste SCR denitration catalyst - Google Patents
Method for recovering vanadium, tungsten/molybdenum and titanium elements from waste SCR denitration catalyst Download PDFInfo
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Abstract
The invention belongs to the field of non-ferrous metal recovery, and particularly relates to a method for recovering vanadium, tungsten/molybdenum and titanium elements from a waste SCR denitration catalyst. The method for recovering vanadium, tungsten/molybdenum and titanium elements comprises the steps of pretreatment of the waste catalyst, element separation, element purification and element recovery, and realizes efficient recovery of vanadium, tungsten/molybdenum and titanium elements with high added values in the waste SCR denitration catalyst through a specific recovery process (the chemical properties of tungsten and molybdenum are very close, and the process has the same effect on the tungsten and molybdenum elements). The recovery process has the advantages of high recovery rate, excellent product purity, simplicity, feasibility, low investment cost and the like, and has higher market value in the field of recovery of waste catalyst elements in the flue gas denitration industry.
Description
Technical Field
The invention belongs to the field of non-ferrous metal recovery, and particularly relates to a method for recovering vanadium, tungsten/molybdenum and titanium elements from a waste SCR denitration catalyst.
Background
With the continuous improvement of environmental awareness, except for coal-fired power plants, the emission standards of flue gas pollutants in industries such as steel, cement and waste incineration are sequentially limited by the emission concentration of NOx. At present, as a domestic mainstream smoke denitration technology, an SCR denitration technology is widely applied to NOx emission control of smoke in different industries. The SCR denitration catalyst is the key of the SCR denitration technology, the service life of the SCR denitration catalyst is usually only 2-3 years due to the severe working environment, and the catalyst which is reduced in activity and cannot be recovered through a regeneration technology can finally become a waste SCR denitration catalyst. The waste SCR denitration catalyst is a special solid waste and has the following characteristics:
(1) high toxicity. The waste SCR denitration catalyst contains B-level inorganic highly toxic substances V2O5And heavy metal oxide WO3Or MoO3In the using process, the material can also absorb the highly toxic elements such As As, Hg, Pb and the like in the smoke, which causes the smoke to have high smoke absorption and smoke absorptionThe toxic elements enter the environment and bring great harm.
(2) The yield is high. According to the estimation of relevant data, only the waste SCR denitration catalyst generated by the thermal power plant every year in 2021 can reach 11 ten thousand meters3The above. With the continuous expansion of the application range of the SCR denitration technology, the yield of domestic waste SCR denitration catalysts will be continuously increased, and the reasonable disposal of a large amount of waste SCR denitration catalysts will be a serious challenge in the future.
(3) High added value components. The raw materials used for producing the SCR denitration catalyst are very expensive. The price of ammonium metatungstate is always about 20 ten thousand yuan/ton, the price of ammonium heptamolybdate is over 10 ten thousand yuan/ton, and the highest price of ammonium metavanadate even reaches 50 ten thousand yuan/ton due to insufficient supply. In addition, the price of the titanium dioxide used for producing the SCR denitration catalyst also reaches more than 1.5 ten thousand yuan/ton.
(4) The recovery is difficult, and the high-efficiency recovery technology is short. SCR denitration catalyst contains V2O5、WO3/MoO3And TiO2In addition, SiO is introduced by using a forming aid in the production process2、Al2O3And CaO and other components, and can also absorb sulfur, alkali metals, phosphorus, arsenic, mercury, lead and other elements in the flue gas in the using process, and the complex components undoubtedly increase certain difficulty in recycling high-purity vanadium, tungsten/molybdenum and titanium products; in addition, WO in waste SCR denitration catalyst3Or MoO3The content is often less than 5 wt.%, and V2O5Even below 1 wt%, which is a great challenge for element recovery. At present, no mature technology and relevant units for recovering vanadium, tungsten/molybdenum and titanium elements of the waste vanadium-titanium SCR denitration catalyst exist in China.
Aiming at the characteristics, the development of the technical scheme for efficiently recovering the elements with high added values of vanadium, tungsten/molybdenum and titanium has very important significance in the aspects of environmental protection, resource conservation and the like.
Disclosure of Invention
The invention aims to provide a method for recovering vanadium, tungsten/molybdenum and titanium elements from a waste SCR denitration catalyst. The invention aims at the existence form and chemical characteristics of each component in the waste SCR denitration catalyst, and realizes the high-efficiency separation, purification and recovery of vanadium, tungsten/molybdenum and titanium elements by a specific recovery process.
According to the present invention there is provided a method comprising the steps of:
(1) pretreatment of waste SCR denitration catalyst
① for the flat-plate type waste SCR denitration catalyst, the method comprises blowing off the dust on the surface of the catalyst, separating the catalyst from the metal mesh plate by vibration or knocking and the like, collecting and roasting the fallen catalyst, and fully crushing the catalyst to below 200 meshes.
② for the denitration catalyst of honeycomb SCR is prepared through blowing the loose dust from the blocked part of the channel of catalyst, calcining, blowing dust again to remove the loose dust, and pulverizing to less than 200 meshes.
(2) Separation of titanium from vanadium, tungsten/molybdenum
Mixing the waste catalyst powder obtained in the step (1) with a certain mass of Na2CO3Or NaOH is mixed evenly, then a proper amount of water is added for continuous stirring, and the uniformity and contact of mixed solids are further enhanced; after drying, roasting the mixed solid to obtain a sintered block; pulverizing the sintered cake to below 200 meshes, repeatedly leaching with NaOH solution under heating and stirring to obtain NaVO3、Na2WO4/Na2MoO4、Na2SiO3、NaAlO2And filtering the soluble sodium salt to obtain titanium-rich slag precipitate and solution containing vanadium, tungsten/molybdenum and other elements.
(3) Recovery of titanium
Crushing the titanium-rich slag to below 200 meshes, and dissolving the titanium-rich slag by using a concentrated sulfuric acid solution with the concentration of 80-95% under the conditions of heating at 140-180 ℃ and stirring to obtain titanium-containing slurry; stopping stirring, and keeping heating and curing for 2-5 h; after the ripening is finished, when the temperature is reduced to be below 100 ℃, adding 5% dilute sulfuric acid solution, and then filtering to obtain clear dilute titanium solution; preheating 3-6 times of deionized water and titanium liquid to 90-98 deg.C, and allowing the titanium liquid to stand for 15-30minSlowly and uniformly adding the titanium liquid into deionized water, wherein white precipitates appear when the titanium liquid is just added, and then the titanium liquid gradually becomes a colorless transparent solution; boiling the solution until a large amount of white precipitate appears, stopping heating and stirring, standing for 30min, then restarting stirring, heating and boiling for 2-4h, wherein water needs to be supplemented in the process to keep the volume of the solution relatively stable; finally, TiO is obtained by filtering, washing, drying and roasting recovery2。
(4) Separation and purification of vanadium, tungsten/molybdenum elements
Adjusting the pH value of the solution obtained in the step (2) to 8-11 by using a 5% dilute sulfuric acid solution, heating the solution to 60-90 ℃, stirring for 0.5-3h, and filtering to remove impurity elements such as silicon, aluminum, calcium and the like in hydrolysis precipitation to obtain a clear solution; extracting tungsten/molybdenum elements in the solution by using an extracting agent to obtain a tungsten/molybdenum-containing organic phase; and then back extracting the tungsten/molybdenum element in the organic phase to obtain a tungsten/molybdenum-containing solution.
Adjusting the pH value of the residual solution after extracting tungsten/molybdenum to 0.5-2.0, and extracting vanadium element by using an extracting agent to obtain a vanadium-containing organic phase; and then the vanadium element in the organic phase is back extracted to obtain a vanadium-containing solution.
(5) Recovery of tungsten/molybdenum elements
Evaporating the tungsten/molybdenum-containing solution obtained in the step (4) to dryness, and roasting at 750 ℃ to remove the sulfur element introduced as an impurity by adjusting the pH value in the step (4); under the condition of stirring at room temperature, dissolving the solid obtained by roasting with an ammonia water solution, and then heating and boiling until the residual solution just covers the bottom of the container; fully cooling, filtering to obtain ammonium tungstate/ammonium molybdate which is separated out from the solution, washing with ethanol, drying and roasting to obtain WO3/MoO3And (3) a solid.
(6) Recovery of vanadium
Evaporating the vanadium-containing solution obtained in the step (4) to dryness, and slowly adding a dilute hydrochloric acid solution at room temperature until the solid is completely dissolved to obtain a clear solution; dropwise adding an oxidant solution into the solution to enable the solution to become stable reddish brown; adjusting pH to 1.0-3.0 with dilute hydrochloric acid solution of the same concentration, boiling the solution, and continuing to boil for 1h after red precipitate appears; cooling, filtering, washing, drying and roasting to obtain V2O5And (3) a solid.
Preferably, theIn the step (1), the waste SCR denitration catalyst is a vanadium-titanium catalyst eliminated from industrial flue gas denitration, and the carrier is TiO2The active ingredient is V2O5The catalyst auxiliary is WO3Or MoO3。
Preferably, in the step (1), the roasting temperature is 450-650 ℃, and the roasting time is 2-12 h.
Preferably, in the step (2), Na is used2CO3Or the amount of NaOH is determined by the molar ratio of sodium element to titanium element, wherein the molar ratio of Na to Ti is (1.5-3) to 1.
Preferably, in the step (2), the roasting temperature is 650-.
Preferably, in the step (2), the concentration of the NaOH solution is 1-3 mol/L, the leaching temperature is 60-90 ℃, the leaching times are 2-4 times, the liquid-solid mass ratio of each time is (4-10):1, and the leaching time is 2-6 h.
Preferably, in the step (3), TiO in the titanium-containing slurry2The concentration is 200-300 g/L, and the TiO in the dilute titanium solution is clarified2The concentration is 100-150 g/L.
Preferably, in the step (3), the drying temperature is 60-90 ℃, and the drying time is 2-12 h; the roasting temperature is 450-750 ℃, and the roasting time is 3-6 h.
Preferably, in the step (4), the extractant for extracting the tungsten/molybdenum elements consists of an active ingredient, a phase regulator and a diluent. Wherein the active ingredient is secondary carbon primary amine (N1923) or trioctyl tertiary amine (N235), and the volume accounts for 5-20%; the phase regulator is tributyl phosphate or isooctyl alcohol, and the volume of the phase regulator accounts for 5 to 20 percent; the diluent is sulfonated kerosene, and accounts for 60-90% of the volume; the extraction stages are 2-5 stages, and the volume ratio of the organic phase to the tungsten/molybdenum-containing solution in each stage is 1 (3-5).
Preferably, in the step (4), the stripping agent used for stripping tungsten/molybdenum elements is ammonia water, ethanolamine, ammonium chloride or ammonium bicarbonate solution, the concentration is 1-5 mol/L, the number of stripping stages is 2-5, and the volume ratio of each stage of organic phase to the stripping agent solution is 1 (3-5).
Preferably, in the step (4), the effective component of the extractant for extracting the vanadium element is trioctyl tertiary amine (N235) or di (2-ethylhexyl) phosphate (P204), and the volume of the extractant is 5-20%; the phase regulator is sec-octanol or decanol, and the volume of the phase regulator is 5-20%; the diluent is sulfonated kerosene, and the volume of the sulfonated kerosene accounts for 60-90%; the extraction grade is 2-5 grades, and the volume ratio of each grade of organic phase to vanadium-containing solution is 1 (3-5).
Preferably, in the step (4), the stripping agent for stripping vanadium element is dilute nitric acid or hydrogen peroxide solution, the concentration is 0.5-2.0 mol/L, the number of stripping stages is 2-5, and the volume ratio of each stage of organic phase to the stripping agent solution is 1 (3-5).
Preferably, in the step (5), the concentration of the ammonia water solution is 10-30%, and the liquid-solid mass ratio is (4-8): 1.
Preferably, in the step (5), the drying temperature is 60-90 ℃, and the drying time is 2-12 h; the roasting temperature is 450-600 ℃, and the roasting time is 3-6 h.
Preferably, in the step (6), the diluted hydrochloric acid solution is used at a volume concentration of 2-8%.
Preferably, in the step (6), the oxidant is hydrogen peroxide or dilute nitric acid solution, and the concentration is 0.5-2.5 mol/L.
Preferably, in the step (6), the drying temperature is 60-90 ℃, and the drying time is 2-12 h; the roasting temperature is 450-600 ℃, and the roasting time is 3-6 h.
The invention has the beneficial effects that:
the method aims at high-added-value elements such as vanadium, tungsten/molybdenum and titanium in the waste SCR denitration catalyst, realizes efficient and total recovery of the target elements through a specific recovery process, is simple and feasible in process and low in secondary pollution, the recovery rates of the vanadium, tungsten/molybdenum and titanium elements exceed 90%, and V obtained by recovery2O5And WO3/MoO3Purity over 99.5, TiO2The purity reaches more than 98.5 percent. The method is mainly realized by the following aspects:
(1) in the recovery method provided by the invention, a plurality of chemical reaction processes are involved, and the efficiency of each process is directly related to the recovery rate of the target element. The invention optimizes the experimental conditions according to the existing form and chemical characteristics of the target elements in the waste SCR denitration catalyst,the reaction efficiency of each step is improved, and the loss of the target element in the transfer process is reduced as much as possible. Such as in the mixing of calcined spent catalyst powder and Na2CO3Or when NaOH is used, the mixed solid is stirred by adding water, so that the uniformity and contact of the mixed solid are optimized, and vanadium, tungsten/molybdenum elements are efficiently converted into soluble sodium salts; NaOH solution is used in the leaching step, so that soluble vanadium, tungsten/molybdenum sodium salts can be dissolved, and residual V without sodium salts is treated2O5And WO3/MoO3The dissolution effect is also certain, so that the leaching rate of vanadium, tungsten/molybdenum elements is improved; meanwhile, when vanadium and tungsten/molybdenum elements are purified, the optimal extraction agent, back extraction agent and experimental conditions are determined by exploration, so that the high-efficiency transfer of the vanadium and tungsten/molybdenum elements among solution, an organic phase and the back extraction agent is realized, and the loss rate is lower than 1%; in addition, a hydrolysis method is adopted in the step of recovering titanium and vanadium elements, and a boiling crystallization method is adopted in the step of recovering tungsten/molybdenum elements, so that the method has the advantages of high efficiency, low loss and the like, and extremely accords with the chemical characteristics of target elements.
(2) Besides target elements such as vanadium, tungsten/molybdenum and titanium, a plurality of impurity elements such as silicon, aluminum, calcium, barium, magnesium, sulfur, chlorine, mercury, lead and arsenic exist in the waste SCR denitration catalyst, more impurity elements are introduced in a recovery stage, and the efficient removal of the impurity elements is a guarantee for the purity of recovered products. The recovery method of the invention comprises a very efficient impurity removal step. In the step of purifying vanadium and tungsten/molybdenum elements, the extracting agent and the stripping agent provided by the invention have extremely high selectivity on target elements, and carry few impurity elements in the process of transferring the target elements, thereby realizing the efficient removal of the impurity elements. Through extraction and back extraction, the obtained vanadium, tungsten/molybdenum solution has few impurity types and extremely low content, and is very beneficial to the recovery of subsequent target elements; meanwhile, the element recovery method provided by the invention is also suitable, for example, in the titanium and vanadium recovery by the hydrolysis method, the residual other impurity elements can not be hydrolyzed under the experimental conditions of the method, so that the recovered product has extremely high purity. Before the tungsten/molybdenum element is recovered by a boiling crystallization method, the purpose of high-temperature roasting is to remove the sulfur element, because a large amount of sulfur element is introduced in the previous process, and the sulfur element is not easy to be completely removed by extraction and back extraction, the high-temperature roasting can ensure that the solid separated out by subsequent cooling does not contain sulfur impurities and has higher purity; in addition, soot blowing and roasting in the pretreatment step of the waste catalyst, and hydrolysis for removing silicon and aluminum are beneficial to improving the purity of the recovered product.
(3) The vanadium, tungsten/molybdenum and titanium recovery method provided by the invention is divided into four stages of pretreatment, element separation, element purification and element recovery, the method is clear and simple, the used reagents and processes are easy to realize industrial large-scale application, the cost is low, and the method is the most common V in the field of flue gas denitration2O5-WO3/TiO2And V2O5-MoO3/TiO2The catalyst is very effective.
Detailed Description
The invention provides a method for recovering vanadium, tungsten/molybdenum and titanium elements from a waste SCR denitration catalyst, and the invention is further explained by combining a specific embodiment.
Example 1
Embodiment 1 describes a method for recovering vanadium, tungsten and titanium elements from a waste SCR denitration catalyst, which comprises the following specific steps:
(1) pretreatment of waste SCR denitration catalyst
Taking a waste flat plate type SCR denitration catalyst (V) of a certain power plant2O5-WO3/TiO2) Blowing off surface dust, and separating the catalyst from the metal mesh plate by vibration and knocking; collecting the dropped catalyst, and then roasting at 450 ℃ for 12 h; after calcination, the catalyst is sufficiently crushed to 200 mesh or less to obtain waste catalyst powder.
(2) Separation of titanium from vanadium and tungsten
Mixing the waste catalyst powder with Na2CO3Mixing uniformly, adding appropriate amount of water, stirring, drying, calcining at 650 deg.C for 10 hr to obtain sintered cake, pulverizing to below 200 mesh, heating at 60 deg.C under stirring, and repeatedly leaching with 1 mol/L NaOH solution4 times, wherein the liquid-solid mass ratio of each time is 10:1, and the leaching time is 2 hours; filtering to obtain titanium-rich slag precipitate and solution containing vanadium and tungsten simultaneously.
(3) Recovery of titanium
Pulverizing the titanium-rich slag to below 200 meshes, and dissolving the titanium-rich slag by using a concentrated sulfuric acid solution with the concentration of 80% under the conditions of heating at 180 ℃ and stirring to obtain TiO2Stirring the titanium-containing slurry with the concentration of 200 g/L, keeping heating and curing for 5h, adding 5% dilute sulfuric acid solution when the temperature is reduced to be below 100 ℃ after curing, and filtering to obtain TiO2The method comprises the steps of preparing a clear dilute titanium solution with the concentration of 100 g/L, preheating deionized water and titanium solution which are 3 times the mass of the clear dilute titanium solution to 90 ℃, slowly and uniformly adding the titanium solution into the deionized water within 15min to obtain a colorless transparent solution after the titanium solution is completely added, boiling the solution, stopping heating and stirring when a large amount of white precipitates are generated, standing for 30min, then restarting stirring and heating for boiling for 2h, supplementing water to keep the volume of the solution relatively stable, filtering to obtain a precipitate, fully washing with water, drying at 60 ℃ for 12h, and finally roasting at 450 ℃ to obtain TiO2。
(4) Separation and purification of vanadium and tungsten elements
And (3) adjusting the pH value of the solution obtained in the step (2) to 8.0 by using a 5% dilute sulfuric acid solution, heating the solution to 60 ℃, stirring for 3 hours, and filtering to remove impurity elements such as silicon, aluminum, calcium and the like precipitated by hydrolysis to obtain a clear solution.
Extracting tungsten element with extractant composed of 5% secondary carbon primary amine (N1923), 5% isooctyl alcohol and 90% sulfonated kerosene, wherein the extraction stage number is 5 stages, the volume ratio of organic phase to aqueous phase of each stage is 1:3, and stripping tungsten element from organic phase with 1 mol/L ammonia water solution to obtain tungsten-containing solution, the stripping stage number is 2 stages, and the volume ratio of organic phase to stripping agent of each stage is 1: 5.
Adjusting the pH value of the solution left after tungsten extraction to 0.5, extracting vanadium element by using an extracting agent, wherein the extracting agent consists of 5% of trioctyl tertiary amine (N235), 5% of secondary octanol and 90% of sulfonated kerosene, the extraction grade is 5 grades, the volume ratio of an organic phase to a water phase of each grade is 1:3, and back-extracting the vanadium element from the organic phase by using a hydrogen peroxide solution of 0.5 mol/L to obtain a vanadium-containing solution, the back-extraction grade is 5 grades, and the volume ratio of the organic phase to the back-extracting agent of each grade is 1: 3.
(5) Recovery of tungsten
Evaporating the tungsten-containing solution obtained in the step (4) to dryness, and roasting the residual solid at 750 ℃; under the condition of stirring at room temperature, dissolving a solid obtained by roasting by using an ammonia water solution with the volume concentration of 10%, wherein the liquid-solid mass ratio is 8: 1; then heating and boiling until the residual solution just covers the bottom of the container; fully cooling, filtering to obtain ammonium tungstate precipitated from the solution, washing with ethanol, drying at 60 ℃ for 12h, and roasting at 450 ℃ to obtain WO3And (3) a solid.
(6) Recovery of vanadium
Evaporating the vanadium-containing solution obtained in the step (4) to dryness, slowly adding a dilute hydrochloric acid solution with the volume concentration of 2% at room temperature until the solid is completely dissolved to obtain a clear solution, slowly dropwise adding 0.5 mol/L diluted nitric acid into the solution to enable the solution to become stable reddish brown, adjusting the pH value to 1.0 by using the 2% dilute hydrochloric acid solution, boiling the solution, continuously boiling for 1h after red precipitation occurs, cooling, filtering to obtain a hydrolysis precipitate, fully washing with water, drying at 60 ℃ for 12h, and finally roasting at 450 ℃ to obtain V2O5And (3) a solid.
Through the embodiment 1, the recovery rate of vanadium can reach 92 percent, and V obtained by recovery2O5The purity is 99.65%; the recovery rate of tungsten element can reach 95%, and WO obtained by recovery3The purity is 99.70%; the recovery rate of titanium element can reach 90%, and the recovered TiO2The purity was 98.90%.
Example 2
Embodiment 2 describes a method for recovering vanadium, molybdenum and titanium elements from a waste SCR denitration catalyst, which comprises the following specific steps:
(1) pretreatment of waste SCR denitration catalyst
Taking a waste flat plate type SCR denitration catalyst (V) of a certain power plant2O5-MoO3/TiO2) Blowing off surface dust, and separating the catalyst from the metal mesh plate by vibration and knocking; collecting the dropped catalyst, and then roasting for 2 hours at 650 ℃; after calcination, the catalyst is sufficiently crushed to 200 mesh or less to obtain waste catalyst powder.
(2) Separation of titanium from vanadium and molybdenum
The method comprises the steps of uniformly mixing waste catalyst powder and NaOH solid, adding a proper amount of water, continuously stirring, fully drying, roasting at 800 ℃ for 3 hours to obtain a sintered block, crushing the sintered block to below 200 meshes, repeatedly leaching for 2 times by using NaOH solution with the concentration of 3 mol/L under the conditions of heating at 90 ℃ and stirring, wherein the mass ratio of liquid to solid is 4:1 each time, the leaching time is 2 hours, and filtering to obtain titanium-rich slag precipitate and a solution containing vanadium and molybdenum elements at the same time.
(3) Recovery of titanium
Pulverizing the titanium-rich slag to below 200 meshes, and dissolving the titanium-rich slag by using a concentrated sulfuric acid solution with the concentration of 95% under the conditions of heating at 140 ℃ and stirring to obtain TiO2Stirring the titanium-containing slurry with the concentration of 300 g/L, keeping heating and curing for 2 hours, adding 5 percent dilute sulfuric acid solution when the temperature is reduced to below 60 ℃ after curing, and filtering to obtain TiO2The method comprises the steps of preparing a clear dilute titanium solution with the concentration of 150 g/L, preheating 6 times of deionized water and the titanium solution to 98 ℃, slowly and uniformly adding the titanium solution into the deionized water within 30min to obtain a colorless transparent solution after the titanium solution is completely added, boiling the solution, stopping heating and stirring when a large amount of white precipitates are generated, standing for 30min, then starting stirring again, heating and boiling for 4h, supplementing water to keep the volume of the solution relatively stable, filtering to obtain a precipitate, fully washing with water, drying at 90 ℃ for 2h, and finally roasting at 750 ℃ to obtain TiO2。
(4) Separation and purification of vanadium and molybdenum elements
And (3) adjusting the pH value of the solution obtained in the step (2) to 11 by using a 5% dilute sulfuric acid solution, heating the solution to 90 ℃, stirring for 0.5h, and filtering to remove impurity elements such as silicon, aluminum, calcium and the like precipitated by hydrolysis to obtain a clear solution.
Extracting molybdenum element by using an extracting agent, wherein the extracting agent consists of 20% of trioctyl tertiary amine (N235), 20% of tributyl phosphate and 60% of sulfonated kerosene, the number of extraction stages is 2, the volume ratio of an organic phase to a water phase of each stage is 1:5, and stripping the molybdenum element from the organic phase by using an ammonia water solution of 5 mol/L to obtain a molybdenum-containing solution, the number of stripping stages is 2, and the volume ratio of the organic phase to the stripping agent of each stage is 1: 3.
Adjusting the pH value of the solution left after molybdenum extraction to 2.0, extracting vanadium element by using an extracting agent, wherein the extracting agent consists of 20% of di (2-ethylhexyl) phosphate (P204), 20% of secondary octanol and 60% of sulfonated kerosene, the extraction level is 2 levels, the volume ratio of each level of organic phase to water phase is 1:5, and back-extracting the vanadium element from the organic phase by using 2 mol/L dilute nitric acid solution to obtain the vanadium-containing solution, the back-extraction level is 2 levels, and the volume ratio of each level of organic phase to back-extracting agent is 1: 5.
(5) Recovery of molybdenum
Evaporating the molybdenum-containing solution obtained in the step (4) to dryness, and roasting the residual solid at 750 ℃; under the condition of stirring at room temperature, dissolving a solid obtained by roasting by using an ammonia water solution with the volume concentration of 30%, wherein the liquid-solid mass ratio is 4: 1; then heating and boiling until the residual solution just covers the bottom of the container; fully cooling, filtering to obtain ammonium salt of molybdic acid precipitated from the solution, washing with ethanol, drying at 90 deg.C for 2h, and roasting at 600 deg.C to obtain MoO3And (3) a solid.
(6) Recovery of vanadium
Evaporating the vanadium-containing solution obtained in the step (4) to dryness, slowly adding a dilute hydrochloric acid solution with the volume concentration of 8% at room temperature until the solid is completely dissolved to obtain a clear solution, slowly dropwise adding a 2.5 mol/L dioxygen aqueous solution into the solution to ensure that the solution becomes stable reddish brown, adjusting the pH value to 3.0 by using the 8% dilute hydrochloric acid solution, boiling the solution, continuously boiling for 1h after red precipitation occurs, cooling, filtering to obtain a hydrolysis precipitate, fully washing with water, drying at 90 ℃ for 2h, and finally roasting at 600 ℃ to obtain V2O5And (3) a solid.
By the embodiment 2, the recovery rate of vanadium can reach 93 percent, and V obtained by recovery2O5The purity is 99.85%; the recovery rate of molybdenum element can reach 94%, and the recovered MoO3The purity is 99.80%; the recovery rate of titanium element can reach 91%, and TiO obtained by recovery2The purity was 98.95%.
Example 3
Example 3 describes another method for recovering vanadium, tungsten and titanium from a waste SCR denitration catalyst, which comprises the following specific steps:
(1) pretreatment of waste SCR denitration catalyst
Taking a certain power plant waste honeycomb type SCR denitration catalyst (V)2O5-WO3/TiO2) After soot blowing treatment, roasting the catalyst for 8 hours at the temperature of 600 ℃; blowing ash again, and then fully crushing the catalyst to below 200 meshes to obtain waste catalyst powder.
(2) Separation of titanium from vanadium and tungsten
Mixing the waste catalyst powder with Na2CO3Mixing uniformly, wherein the molar ratio of Na to Ti is 2.5:1, adding a proper amount of water, continuing stirring, fully drying, roasting at 800 ℃ for 6 hours to obtain a sintered block, crushing the sintered block to below 200 meshes, repeatedly leaching for 4 times by using a NaOH solution with the concentration of 1 mol/L under the conditions of heating at 90 ℃ and stirring, wherein the liquid-solid mass ratio of each time is 5:1, and the leaching time is 2 hours, and filtering to obtain a titanium-rich slag precipitate and a solution containing vanadium and tungsten simultaneously.
(3) Recovery of titanium
Pulverizing the titanium-rich slag to below 200 meshes, and dissolving the titanium-rich slag by using a concentrated sulfuric acid solution with the concentration of 95% under the conditions of heating at 150 ℃ and stirring to obtain TiO2Stirring 240 g/L Ti-containing slurry, heating for aging for 4 hr, cooling to below 90 deg.C, adding 5% dilute sulfuric acid solution, and filtering to obtain TiO2The method comprises the steps of preparing clear dilute titanium solution with the concentration of 120 g/L, preheating 4 times of deionized water and titanium solution to 98 ℃, slowly and uniformly adding the titanium solution into the deionized water within 30min to obtain colorless transparent solution after the titanium solution is completely added, boiling the solution, stopping heating and stirring when a large amount of white precipitates are generated, standing for 30min, then starting stirring again, heating and boiling for 3h, supplementing water to keep the volume of the solution relatively stable, filtering to obtain precipitate, fully washing with water, drying at 100 ℃ for 8h, and finally roasting at 600 ℃ to obtain TiO2。
(4) Separation and purification of vanadium and tungsten elements
And (3) adjusting the pH value of the solution obtained in the step (2) to 11 by using a 5% dilute sulfuric acid solution, heating the solution to 70 ℃, stirring for 1h, and filtering to remove impurity elements such as silicon, aluminum, calcium and the like precipitated by hydrolysis to obtain a clear solution.
Extracting tungsten element by using an extracting agent, wherein the extracting agent consists of 20% of secondary carbon primary amine (N1923), 10% of isooctyl alcohol and 70% of sulfonated kerosene, the extraction stage number is 2 stages, the volume ratio of an organic phase to a water phase of each stage is 1:3, and back-extracting the tungsten element from the organic phase by using 2 mol/L of ethanolamine solution to obtain a tungsten-containing solution, the back-extraction stage number is 2 stages, and the volume ratio of the organic phase to the back-extracting agent of each stage is 1: 3.
Adjusting the pH value of the residual solution after tungsten extraction to 1.0, extracting vanadium element by using an extracting agent, wherein the extracting agent consists of 15% of di (2-ethylhexyl) phosphate (P204), 15% of secondary octanol and 70% of sulfonated kerosene, the extraction stage number is 3, the volume ratio of an organic phase to a water phase of each stage is 1:3, and back-extracting the vanadium element from the organic phase by using a dilute nitric acid solution of 1.5 mol/L to obtain a vanadium-containing solution, the back-extraction stage number is 3, and the volume ratio of the organic phase to the back-extracting agent of each stage is 1: 3.
(5) Recovery of tungsten
Evaporating the tungsten-containing solution obtained in the step (4) to dryness, and roasting the residual solid at 750 ℃; under the condition of stirring at room temperature, dissolving a solid obtained by roasting by using an ammonia water solution with the volume concentration of 30%, wherein the liquid-solid mass ratio is 8: 1; then heating and boiling until the residual solution just covers the bottom of the container; fully cooling, filtering to obtain ammonium tungstate precipitated from the solution, washing with ethanol, drying at 60 ℃ for 8h, and finally roasting at 550 ℃ to obtain WO3And (3) a solid.
(6) Recovery of vanadium
Evaporating the vanadium-containing solution obtained in the step (4) to dryness, slowly adding a dilute hydrochloric acid solution with the volume concentration of 3% at room temperature until the solid is completely dissolved to obtain a clear solution, slowly dropwise adding a 1.5 mol/L dioxygen aqueous solution into the solution to ensure that the solution becomes stable reddish brown, adjusting the pH value to 1.5 by using the 3% dilute hydrochloric acid solution, boiling the solution, continuing boiling for 1h after red precipitation occurs, cooling, filtering to obtain a hydrolysis precipitate, fully washing with water, drying at 70 ℃ for 9h, and finally roasting at 550 ℃ to obtain V2O5And (3) a solid.
By the embodiment 3, the recovery rate of vanadium element can reach 95%, and V obtained by recovery2O5The purity is 99.95%; the recovery rate of tungsten element can reach 93%, and WO obtained by recovery3The purity is 99.79%; the recovery rate of titanium element can reach 90%, and the recovered TiO2The purity was 98.83%.
Example 4
Embodiment 4 describes another method for recovering vanadium, molybdenum and titanium from a waste SCR denitration catalyst, which comprises the following specific steps:
(1) pretreatment of waste SCR denitration catalyst
Taking a certain power plant waste honeycomb type SCR denitration catalyst (V)2O5-MoO3/TiO2) After soot blowing treatment, roasting the catalyst at 650 ℃ for 6 hours; blowing ash again, and then fully crushing the catalyst to below 200 meshes to obtain waste catalyst powder.
(2) Separation of titanium from vanadium and molybdenum
The method comprises the steps of uniformly mixing waste catalyst powder and NaOH solid, adding a proper amount of water, continuously stirring, fully drying, roasting at 800 ℃ for 3 hours to obtain a sintered block, crushing the sintered block to below 200 meshes, repeatedly leaching for 2 times by using NaOH solution with the concentration of 2 mol/L under the conditions of heating at 60 ℃ and stirring, wherein the mass ratio of liquid to solid is 6:1 each time, the leaching time is 3 hours, and filtering to obtain titanium-rich slag precipitate and a solution containing vanadium and molybdenum elements at the same time.
(3) Recovery of titanium
Pulverizing the titanium-rich slag to below 200 meshes, and dissolving the titanium-rich slag by using a concentrated sulfuric acid solution with the concentration of 85% under the conditions of heating at 160 ℃ and stirring to obtain TiO2Stirring the titanium-containing slurry with the concentration of 300 g/L, keeping heating and curing for 3h, adding 5% dilute sulfuric acid solution when the temperature is reduced to below 80 ℃ after curing, and filtering to obtain TiO2The method comprises the steps of preparing a clear dilute titanium solution with the concentration of 150 g/L, preheating 6 times of deionized water and the titanium solution to 95 ℃, slowly and uniformly adding the titanium solution into the deionized water within 25min to obtain a colorless transparent solution after the titanium solution is completely added, boiling the solution, stopping heating and stirring when a large amount of white precipitates are generated, standing for 30min, then starting stirring again, heating and boiling for 3h, supplementing water to keep the volume of the solution relatively stable, filtering to obtain a precipitate, fully washing with water, drying at 80 ℃ for 9h, and drying at the maximum temperature for 9hThen roasting at 550 ℃ to obtain TiO2。
(4) Separation and purification of vanadium and molybdenum elements
And (3) adjusting the pH value of the solution obtained in the step (2) to 10 by using a 5% dilute sulfuric acid solution, heating the solution to 80 ℃, stirring for 3 hours, and filtering to remove impurity elements such as silicon, aluminum, calcium and the like precipitated by hydrolysis to obtain a clear solution.
Extracting molybdenum element by using an extracting agent, wherein the extracting agent consists of 20% secondary carbon primary amine (N1923), 10% tributyl phosphate and 70% sulfonated kerosene, the number of extraction stages is 3, the volume ratio of each stage of organic phase to water phase is 1:4, and back-extracting the molybdenum element from the organic phase by using 2 mol/L ammonia water solution to obtain a molybdenum-containing solution, the number of back-extraction stages is 3, and the volume ratio of each stage of organic phase to back-extracting agent is 1: 4.
Adjusting the pH value of the solution left after molybdenum extraction to 1.0, extracting vanadium element by using an extracting agent, wherein the extracting agent consists of 20% of trioctyl tertiary amine (N235), 10% of secondary octanol and 70% of sulfonated kerosene, the extraction grade is 3 grades, the volume ratio of each grade of organic phase to water phase is 1:3, and back-extracting the vanadium element from the organic phase by using 2 mol/L of hydrogen peroxide solution to obtain a vanadium-containing solution, the back-extraction grade is 3 grades, and the volume ratio of each grade of organic phase to back-extracting agent is 1: 3.
(5) Recovery of molybdenum
Evaporating the molybdenum-containing solution obtained in the step (4) to dryness, and roasting the residual solid at 750 ℃; under the condition of stirring at room temperature, dissolving a solid obtained by roasting by using an ammonia water solution with the volume concentration of 30%, wherein the liquid-solid mass ratio is 4: 1; then heating and boiling until the residual solution just covers the bottom of the container; fully cooling, filtering to obtain ammonium salt of molybdic acid precipitated from the solution, washing with ethanol, drying at 80 deg.C for 6h, and roasting at 500 deg.C to obtain MoO3And (3) a solid.
(6) Recovery of vanadium
Evaporating the vanadium-containing solution obtained in the step (4) to dryness, slowly adding a dilute hydrochloric acid solution with the volume concentration of 4% at room temperature until the solid is completely dissolved to obtain a clear solution, slowly dropwise adding a dilute nitric acid solution with the concentration of 1 mol/L into the solution to ensure that the solution becomes stable reddish brown, adjusting the pH value to 1.5 by using the dilute hydrochloric acid solution with the concentration of 4%, boiling the solution, continuing to boil for 1 hour after red precipitation occurs, cooling, and then continuing to boil for 1 hourFiltering to obtain hydrolysis precipitate, washing with water, drying at 70 deg.C for 8 hr, and roasting at 500 deg.C to obtain V2O5And (3) a solid.
By the embodiment 4, the recovery rate of vanadium element can reach 92%, and V obtained by recovery2O5The purity is 99.86%; the recovery rate of molybdenum element can reach 92%, and the recovered MoO3The purity is 99.89%; the recovery rate of titanium element can reach 91%, and TiO obtained by recovery2The purity was 98.93%.
It should be understood that the above-mentioned embodiments are only for illustrating the technical concept and features of the present invention, and are not intended to be exhaustive or to limit the scope of the present invention, for providing those skilled in the art with understanding the present invention and implementing the same. Modifications and equivalents may be made thereto without departing from the spirit and scope of the present invention, which is set forth in the following claims.
Claims (10)
1. A method for recovering vanadium, tungsten/molybdenum and titanium elements from a waste SCR denitration catalyst is characterized by comprising the following steps:
(1) pretreatment of waste SCR denitration catalyst
① aiming at the flat-plate type waste SCR denitration catalyst, blowing off the dust on the surface of the catalyst, separating the catalyst from a metal mesh plate by means of vibration or knocking, collecting and roasting the fallen catalyst, wherein the roasting temperature is 450-650 ℃, the roasting time is 2-12h, and then fully crushing the catalyst to below 200 meshes;
② blowing the part of loose deposition blocked in the pore channel of the catalyst, then roasting the catalyst, wherein the roasting temperature is 450-650 ℃, the roasting time is 2-12h, blowing soot again, removing the residual loose deposition after roasting, and finally fully crushing the catalyst to below 200 meshes;
(2) separation of titanium from vanadium, tungsten/molybdenum
Mixing the waste SCR denitration catalyst powder obtained in the step (1) with a certain mass of Na2CO3Or NaOH mixture isMixing, adding appropriate amount of water, and stirring to further increase contact area and uniformity of mixed solid; after drying, roasting the mixed solid to obtain a sintered block; wherein the roasting temperature is 650-800 ℃, and the roasting time is 3-10 h; crushing the sintered block to below 200 meshes, repeatedly leaching the sintered block by using NaOH solution under the conditions of heating and stirring, and filtering to obtain titanium-rich slag precipitate and a solution containing vanadium, tungsten and molybdenum elements;
(3) recovery of titanium
The titanium-rich slag is precipitated and crushed to be below 200 meshes, and the titanium-rich slag is dissolved by using a concentrated sulfuric acid solution with the concentration of 80-95% under the conditions of heating at 140-180 ℃ and stirring to obtain titanium-containing slurry; stopping stirring, and keeping heating and curing for 2-5 h; after the ripening is finished, when the temperature is reduced to be below 100 ℃, adding 5% dilute sulfuric acid solution, and then filtering to obtain clear dilute titanium solution; preheating 3-6 times of deionized water and titanium liquid to 90-98 ℃, slowly and uniformly adding the titanium liquid into the deionized water within 15-30min, wherein the titanium liquid is white precipitate when being added and then gradually becomes colorless transparent solution; boiling the solution until a large amount of white precipitate appears, stopping heating and stirring, standing for 30min, then restarting stirring, heating and boiling for 2-4h, wherein water needs to be supplemented in the process to keep the volume of the solution relatively stable; finally, TiO is obtained by filtering, washing, drying and roasting recovery2(ii) a Wherein the drying temperature is 60-90 ℃, and the drying time is 2-12 h; the roasting temperature is 450-750 ℃, and the roasting time is 3-6 h;
(4) separation and purification of vanadium, tungsten/molybdenum elements
Adjusting the pH value of the solution obtained in the step (2) to 8-11 by using a 5% dilute sulfuric acid solution, heating the solution to 60-90 ℃, stirring for 0.5-3h, and filtering to remove impurity elements such as silicon, aluminum and calcium in the hydrolysis precipitate to obtain a clear solution; extracting tungsten/molybdenum elements in the solution by using an extracting agent to obtain a tungsten/molybdenum-containing organic phase; then back extracting tungsten/molybdenum elements in the organic phase to obtain a tungsten/molybdenum-containing solution;
adjusting the pH value of the residual solution after extracting tungsten/molybdenum to 0.5-2.0, and extracting vanadium element by using an extracting agent to obtain a vanadium-containing organic phase; then, back extracting vanadium element in the organic phase to obtain vanadium-containing solution;
(5) recovery of tungsten/molybdenum elements
Evaporating the tungsten/molybdenum-containing solution obtained in the step (4) to dryness, and roasting at 750 ℃ to remove the sulfur element introduced as an impurity by adjusting the pH value in the step (4); under the condition of stirring at room temperature, dissolving the solid obtained by roasting with an ammonia water solution, and then heating and boiling until the residual solution just covers the bottom of the container; fully cooling, filtering to obtain ammonium tungstate/ammonium molybdate which is separated out from the solution, washing with ethanol, drying and roasting to obtain WO3/MoO3A solid; wherein the drying temperature is 60-90 ℃, and the drying time is 2-12 h; the roasting temperature is 450-600 ℃, and the roasting time is 3-6 h;
(6) recovery of vanadium
Evaporating the vanadium-containing solution obtained in the step (4) to dryness, and slowly adding a dilute hydrochloric acid solution with the volume concentration of 2-8% at room temperature until the solid is completely dissolved to obtain a clear solution; dropwise adding an oxidant solution into the solution to enable the solution to become stable reddish brown; adjusting pH to 1.0-3.0 with dilute hydrochloric acid solution of the same concentration, boiling the solution, and continuing to boil for 1h after red precipitate appears; cooling, filtering, washing, drying and roasting to obtain V2O5A solid; wherein the drying temperature is 60-90 ℃, and the drying time is 2-12 h; the roasting temperature is 450-600 ℃, and the roasting time is 3-6 h.
2. The method for recovering vanadium, tungsten/molybdenum and titanium elements from the waste SCR denitration catalyst according to claim 1, wherein the waste SCR denitration catalyst in the step (1) is a vanadium-titanium catalyst eliminated in industrial flue gas denitration, and the carrier is TiO2The active ingredient is V2O5The catalyst auxiliary is WO3Or MoO3。
3. The method for recovering vanadium, tungsten/molybdenum and titanium from the waste SCR denitration catalyst according to claim 1, wherein Na used in the step (2)2CO3Or the amount of NaOH is determined by the molar ratio of sodium element to titanium element, wherein the molar ratio of Na to Ti is (1.5-3) to 1.
4. The method for recovering vanadium, tungsten/molybdenum and titanium from the waste SCR denitration catalyst according to claim 1, wherein the concentration of NaOH solution in the step (2) is 1-3 mol/L, the leaching temperature is 60-90 ℃, the leaching times are 2-4 times, the liquid-solid mass ratio is (4-10):1 each time, and the leaching time is 2-6 h.
5. The method for recovering vanadium, tungsten/molybdenum and titanium from the waste SCR denitration catalyst according to claim 1, wherein the TiO in the titanium-containing slurry in the step (3)2The concentration is 200-300 g/L, and the TiO in the dilute titanium solution is clarified2The concentration is 100-150 g/L.
6. The method for recovering vanadium, tungsten/molybdenum and titanium from the waste SCR denitration catalyst according to claim 1, wherein the extractant for extracting the tungsten/molybdenum in the step (4) is composed of an effective component, a phase modifier and a diluent; wherein the active ingredient is secondary carbon primary amine or trioctyl tertiary amine, and the volume of the active ingredient is 5-20%; the phase regulator is tributyl phosphate or isooctyl alcohol, and the volume of the phase regulator accounts for 5 to 20 percent; the diluent is sulfonated kerosene, and accounts for 60-90% of the volume; the extraction stages are 2-5 stages, and the volume ratio of the organic phase to the tungsten/molybdenum-containing solution in each stage is 1 (3-5).
7. The method for recovering vanadium, tungsten/molybdenum and titanium from the waste SCR denitration catalyst according to claim 1, wherein the stripping agent for stripping tungsten/molybdenum in the step (4) is ammonia water, ethanolamine, ammonium chloride or ammonium bicarbonate solution with the concentration of 1-5 mol/L, the number of stripping stages is 2-5, and the volume ratio of each stage of organic phase to the stripping agent solution is 1 (3-5).
8. The method for recovering vanadium, tungsten/molybdenum and titanium from the waste SCR denitration catalyst according to claim 1, wherein the effective component of the extractant for extracting vanadium in the step (4) is trioctyl tertiary amine or di (2-ethylhexyl) phosphate, and the volume of the extractant is 5-20%; the phase regulator is sec-octanol or decanol, and the volume of the phase regulator is 5-20%; the diluent is sulfonated kerosene, and the volume of the sulfonated kerosene accounts for 60-90%; the extraction grade is 2-5 grades, and the volume ratio of each grade of organic phase to vanadium-containing solution is 1 (3-5).
9. The method for recovering vanadium, tungsten/molybdenum and titanium elements from the waste SCR denitration catalyst according to claim 1, wherein a stripping agent for stripping vanadium elements in the step (4) is a dilute nitric acid or hydrogen peroxide solution with a concentration of 0.5-2.0 mol/L, the number of stripping stages is 2-5, and the volume ratio of each stage of organic phase to the stripping agent solution is 1 (3-5).
10. The method for recovering vanadium, tungsten/molybdenum and titanium from the waste SCR denitration catalyst according to claim 1, wherein the concentration of the ammonia water solution used in the step (5) is 10-30%, and the liquid-solid mass ratio is (4-8): 1.
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| CN110468278B (en) * | 2019-09-09 | 2020-07-14 | 中南大学 | Method for treating waste denitration catalyst |
| CN111778398A (en) * | 2019-10-22 | 2020-10-16 | 广东省资源综合利用研究所 | Method for extracting vanadium and tungsten from waste SCR denitration catalyst |
| CN111020193B (en) * | 2019-11-06 | 2022-05-03 | 北京华电光大环境股份有限公司 | Method for recovering vanadium, tungsten and titanium elements from waste SCR denitration catalyst |
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| CN114277263A (en) * | 2021-12-24 | 2022-04-05 | 辽宁东野环保产业开发有限公司 | Method for recovering tungsten from waste catalyst |
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| CN115445604B (en) * | 2022-09-02 | 2023-11-10 | 国能龙源内蒙古环保有限公司 | Recycling recovery method of waste denitration catalyst |
| CN115876751B (en) * | 2023-02-06 | 2023-07-21 | 国能龙源环保有限公司 | Method for determining content of titanium aluminum calcium magnesium iron elements in waste denitration catalyst through fluoride-free digestion |
| CN115869940B (en) * | 2023-03-08 | 2023-05-05 | 国能龙源环保有限公司 | Method for preparing low-temperature denitration catalyst by utilizing titanium-based waste denitration catalyst and low-temperature denitration catalyst |
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