CN112960697B - Efficient waste SCR denitration catalyst recovery method - Google Patents
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Abstract
The invention relates to a method for efficiently recovering a waste SCR denitration catalyst, and belongs to the field of non-ferrous metal recovery. The invention provides a process for recovering tungsten from a waste SCR denitration catalyst, which greatly improves the comprehensive benefit of titanium recovery and mainly comprises the steps of raw material pretreatment, tungsten element extraction, coarse titanium slag recovery, tungsten element purification, zirconium tungstate recovery and the like. The process has the advantages of high product value, low loss of target recovery elements, low cost investment and the like, and can realize efficient treatment of the waste SCR denitration catalyst.
Description
Technical Field
The invention belongs to the technical field of non-ferrous metal recovery, and particularly relates to a method for efficiently recovering a waste SCR denitration catalyst, in particular to a method for preparing nano zirconium tungstate and recovering coarse titanium slag by taking the waste SCR denitration catalyst as a raw material.
Background
With the gradual promotion of environmental awareness and requirements, in addition to electric power plants, various industries such as steel, waste incineration, cement, glass and the like begin to be forcibly required to remove nitrogen oxides in flue gas, and the development of novel SCR denitration catalysts aiming at flue gas conditions of different industries is always a technical hotspot and a difficult point in the denitration field. Meanwhile, along with the development and application of the novel SCR denitration catalyst suitable for various flue gases, the yield of the waste SCR denitration catalyst is greatly increased, and the simple stacking and landfill can not meet the requirements of relevant regulations and specifications and is not suitable any more. Therefore, a technology for efficiently disposing of the waste SCR denitration catalyst has been a research hotspot in the field of denitration.
The content of tungsten element in the waste SCR denitration catalyst is relatively low, the efficiency of each reaction in the recovery process has great influence on the recovery rate of final elements, the deposition rate is often low when the tungsten element is deposited in the prior art, so that a great amount of precious elements are wasted, meanwhile, a great amount of impurity elements are deposited together with the tungsten element, the purity of the final product is not ideal, and the product value is generally low. The recovery process of titanium element has similar defects with tungsten element, and the feasibility of the process is directly limited by the complex process, low element recovery rate and poor product purity. Therefore, there is a need to develop a high-efficiency process for disposing the waste SCR denitration catalyst.
The total content of titanium dioxide and tungsten trioxide in the waste SCR denitration catalyst can reach over 75 percent, and the method for efficiently recovering tungsten and titanium elements in the form of nano zirconium tungstate and coarse titanium slag is a novel waste SCR denitration catalyst recovery mode.
Disclosure of Invention
The invention aims to solve the technical problem of providing an efficient recovery method of a waste SCR denitration catalyst, and high-quality nano zirconium tungstate and coarse titanium slag are recovered and obtained through a specific recovery process according to the existence form and chemical characteristics of titanium and tungsten elements in the waste SCR denitration catalyst.
In order to solve the technical problems, the invention adopts a technical scheme that: the method for recovering the high-efficiency waste SCR denitration catalyst comprises the following steps:
(1) pretreatment of raw materials: roasting the waste SCR denitration catalyst raw material, further cleaning the waste catalyst by using a cleaning solution consisting of 10-20% of rosin polyoxyethylene ester (RPGC), 5-15% of tartaric acid and 65-85% of triethanolamine after soot blowing, and crushing to obtain waste catalyst powder;
(2) extracting tungsten element: preparing a saturated sodium chloride solution, slowly adding the waste catalyst powder obtained in the step (1) into the saturated sodium chloride solution, stirring the mixture to be pasty, and roasting the mixture at the temperature of 750 ℃ and 850 ℃ for 3-6 hours to obtain a sintered block; crushing the sintered cake to 150 meshes, repeatedly leaching the roasted sodium tungstate by using an ethanolamine solution with the volume concentration of 10-20%, and filtering to obtain a sodium tungstate solution and a titanium precipitate;
(3) and (3) recovering coarse titanium slag: washing the titanium precipitate obtained in the step (2) with clear water, removing impurity elements attached to the surface, drying and recovering to obtain coarse titanium slag;
(4) tungsten element purification: preparing an extracting agent to extract tungsten element from the solution obtained in the step (2), wherein the extracting agent consists of an effective component, a phase regulator and a diluent, the effective component is trioctyl tertiary amine, the phase regulator is sec-octanol, the diluent is sulfonated kerosene, the number of extraction stages is 1-3, and the volume ratio of an organic phase to a water phase at each stage is 1: 3-5; using ammonium chloride, ammonium bicarbonate or ammonium carbonate solution as a stripping agent to strip tungsten elements from the extractant to obtain stripping solution, wherein the stripping stage number is 1-3, and the volume ratio of an organic phase to a water phase of each stage is 1: 3-5;
(5) And (3) recovering zirconium tungstate: preparing a mixed aqueous solution of zirconium chloride, ethylene diamine tetraacetic acid and hexadecyl trimethyl ammonium bromide as a precipitant, adding the precipitant into a stripping solution, heating the solution to 80-95 ℃, continuously stirring for 2-4h, and then cooling and standing the solution at room temperature for 6-12 h; filtering to obtain zirconium tungstate precipitate, washing the precipitate with ethanol, and finally drying and recovering to obtain the nano zirconium tungstate.
Further, the waste SCR denitration catalyst in the step (1) is eliminated V for industrial flue gas denitration2O5-WO3/TiO2Catalyst of the type comprising WO3、TiO2、V2O5、Al2O3、SiO2And CaO.
Further, the roasting temperature in the step (1) is 550-750 ℃, and the roasting time is 3-6 h.
Further, the volume fractions of the effective components, the phase regulator and the diluent in the extracting agent in the step (4) are respectively 5-15%, 10-20% and 65-85%.
Further, the concentration of the stripping agent solution in the step (4) is 1-2.5 mol/L.
Further, the concentration of each component of the precipitating agent in the step (5) is as follows: zirconium chloride is 1-2mol/L, ethylene diamine tetraacetic acid is 0.25-0.75mol/L, and hexadecyl trimethyl ammonium bromide is 0.1-0.3 mol/L.
Further, the molar ratio of zirconium chloride in the precipitating agent to tungsten element in the solution in the step (5) is 1-1.2: 1.
Further, the particle size of the waste catalyst powder in the step (1) is 300 meshes or less.
The method provided by the invention can be used for efficiently recovering titanium and tungsten elements in the waste SCR denitration catalyst, so that high-quality nano zirconium tungstate and coarse titanium slag are obtained. Wherein the purity of the zirconium tungstate is more than 99 percent, the content of titanium dioxide in the coarse titanium slag can reach more than 87 percent, and the recovery rates of tungsten and titanium elements respectively reach more than 95 percent and 97 percent.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be embodied in other specific forms than those described herein, and it will be apparent to those skilled in the art that the present invention may be practiced without departing from the spirit and scope of the present invention.
Example 1: with V2O5-WO3/TiO2The method for preparing nano zirconium tungstate and recovering coarse titanium slag by using the waste SCR denitration catalyst as a raw material comprises the following specific steps:
(1) pretreatment of raw materials
Roasting the waste catalyst for 6 hours at 550 ℃, further cleaning the waste catalyst by using a cleaning solution consisting of 10 percent of rosin polyoxyethylene ester (RPGC), 5 percent of tartaric acid and 85 percent of triethanolamine after soot blowing treatment, and crushing the waste catalyst to be less than 300 meshes to obtain waste catalyst powder;
(2) Extraction of tungsten element
Preparing a saturated sodium chloride solution, slowly adding the waste catalyst powder obtained in the step (1) into the saturated sodium chloride solution, stirring the mixture to be pasty, and roasting the mixture for 6 hours at 750 ℃ to obtain a sintered block; crushing the sintered cake to 150 meshes, repeatedly leaching sodium tungstate generated after roasting by using ethanolamine solution with the volume concentration of 10%, and filtering to obtain sodium tungstate solution and titanium precipitate;
(3) coarse titanium slag recovery
Washing and drying the precipitate obtained in the step (2) to obtain coarse titanium slag, and completing the recovery of titanium element;
(4) purification of tungsten element
Preparing an extracting agent consisting of 5% of trioctyl tertiary amine, 10% of octanol, 5% of decanol and 85% of sulfonated kerosene according to volume fraction, and performing 3-stage extraction on tungsten elements in a sodium tungstate solution, wherein the volume ratio of an organic phase to a water phase of each stage is 1: 3; preparing an ammonium chloride solution with the concentration of 1mol/L, and performing 3-stage back extraction on tungsten element entering an organic phase, wherein the volume ratio of each stage of organic phase to a water phase is 1: 3;
(5) zirconium tungstate recovery
Preparing a precipitator, wherein the concentrations of zirconium chloride, ethylene diamine tetraacetic acid and hexadecyl trimethyl ammonium bromide in the precipitator are 1mol/L, 0.25mol/L and 0.1mol/L respectively; adding a precipitant into the stripping solution according to a molar ratio of zirconium chloride/tungsten element of 1, heating the solution to 80 ℃, continuously stirring for 2 hours, and then placing the solution in a room temperature environment for cooling and standing for 6 hours; filtering to obtain zirconium tungstate precipitate, washing with ethanol, drying, and recovering to obtain nanometer zirconium tungstate to recover tungsten element;
By the embodiment 1, the recovery rate of the tungsten element is 95.37 percent, and the recovery rate of the titanium element is 97.81 percent; the purity of the recovered nano zirconium tungstate is 99.20%, and the content of titanium dioxide in the recovered coarse titanium slag is 87.56%.
Example 2: with V2O5-WO3/TiO2The method for preparing nano zirconium tungstate and recovering coarse titanium slag by using the waste SCR denitration catalyst as a raw material comprises the following specific steps:
(1) pretreatment of raw materials
Roasting the waste catalyst for 4 hours at 650 ℃, further cleaning the waste catalyst by using a cleaning solution consisting of 20 percent of rosin polyoxyethylene ester (RPGC), 15 percent of tartaric acid and 65 percent of triethanolamine after soot blowing treatment, and crushing the waste catalyst to be less than 300 meshes to obtain waste catalyst powder;
(2) extraction of tungsten element
Preparing a saturated sodium chloride solution, slowly adding the waste catalyst powder obtained in the step (1) into the saturated sodium chloride solution, stirring the mixture to be pasty, and roasting the mixture for 3 hours at 850 ℃ to obtain a sintered block; crushing the sintered cake to 150 meshes, repeatedly leaching sodium tungstate generated after roasting by using an ethanolamine solution with the volume concentration of 20%, and filtering to obtain a sodium tungstate solution and a titanium precipitate;
(3) coarse titanium slag recovery
Washing and drying the precipitate obtained in the step (2) to obtain coarse titanium slag, and completing the recovery of titanium element;
(4) Purification of tungsten element
Preparing an extracting agent consisting of 10% of trioctyl tertiary amine, 10% of octanol and 80% of sulfonated kerosene according to volume fraction, and performing 2-stage extraction on tungsten element in a sodium tungstate solution, wherein the volume ratio of each stage of organic phase to water phase is 1: 4; preparing an ammonium bicarbonate solution with the concentration of 2mol/L, and performing 3-stage back extraction on tungsten element entering an organic phase, wherein the volume ratio of each stage of organic phase to a water phase is 1: 4;
(5) zirconium tungstate recovery
Preparing a precipitator, wherein the concentrations of zirconium chloride, ethylene diamine tetraacetic acid and hexadecyl trimethyl ammonium bromide in the precipitator are 1.5mol/L, 0.55mol/L and 0.15mol/L respectively; adding a precipitant into the stripping solution according to a molar ratio of zirconium chloride to tungsten element of 1.1, heating the solution to 90 ℃, continuously stirring for 2.5h, and then placing the solution in a room temperature environment for cooling and standing for 8 h; filtering to obtain zirconium tungstate precipitate, washing with ethanol, drying, and recovering to obtain nanometer zirconium tungstate to recover tungsten element.
By the embodiment 2, the recovery rate of the tungsten element is 95.93 percent, and the recovery rate of the titanium element is 97.98 percent; the purity of the recovered nano zirconium tungstate is 99.34%, and the content of titanium dioxide in the recovered crude titanium slag is 87.89%.
Example 3: with V2O5-WO3/TiO2The method for preparing nano zirconium tungstate and recovering coarse titanium slag by using the waste SCR denitration catalyst as a raw material comprises the following specific steps:
(1) Pretreatment of raw materials
Roasting the waste catalyst for 3 hours at 750 ℃, further cleaning the waste catalyst by using a cleaning solution consisting of 15 percent of rosin polyoxyethylene ester (RPGC), 10 percent of tartaric acid and 75 percent of triethanolamine after soot blowing treatment, and crushing the waste catalyst to be less than 300 meshes to obtain waste catalyst powder;
(2) extraction of tungsten element
Preparing a saturated sodium chloride solution, slowly adding the waste catalyst powder obtained in the step (1) into the saturated sodium chloride solution, stirring the mixture to be pasty, and roasting the mixture at 800 ℃ for 4 hours to obtain a sintered block; crushing the sintered cake to 150 meshes, repeatedly leaching sodium tungstate generated after roasting by using an ethanolamine solution with the volume concentration of 15%, and filtering to obtain a sodium tungstate solution and a titanium precipitate;
(3) coarse titanium slag recovery
Washing and drying the precipitate obtained in the step (2) to obtain coarse titanium slag, and completing the recovery of titanium element;
(4) purification of tungsten element
Preparing an extracting agent consisting of 10% of trioctyl tertiary amine, 15% of isooctanol and 75% of sulfonated kerosene according to volume fraction, and performing 1-stage extraction on tungsten element in a sodium tungstate solution, wherein the volume ratio of an organic phase to a water phase is 1: 5; preparing an ammonium carbonate solution with the concentration of 2.5mol/L, and performing 1-stage back extraction on the tungsten element entering an organic phase, wherein the volume ratio of the organic phase to a water phase is 1: 5;
(5) Zirconium tungstate recovery
Preparing a precipitator, wherein the concentrations of zirconium chloride, ethylene diamine tetraacetic acid and hexadecyl trimethyl ammonium bromide in the precipitator are 2mol/L, 0.75mol/L and 0.3mol/L respectively; adding a precipitant into the stripping solution according to a molar ratio of zirconium chloride/tungsten element of 1.2, heating the solution to 95 ℃, continuously stirring for 4 hours, and then placing the solution in a room temperature environment for cooling and standing for 12 hours; filtering to obtain zirconium tungstate precipitate, washing with ethanol, drying, and recovering to obtain nanometer zirconium tungstate to recover tungsten element.
By the embodiment 3, the recovery rate of the tungsten element is 96.77 percent, and the recovery rate of the titanium element is 98.05 percent; the purity of the recovered nano zirconium tungstate is 99.78%, and the content of titanium dioxide in the recovered coarse titanium slag is 87.98%.
Example 4: with V2O5-WO3/TiO2The method for preparing nano zirconium tungstate and recovering coarse titanium slag by using the waste SCR denitration catalyst as a raw material comprises the following specific steps:
(1) pretreatment of raw materials
Roasting the waste catalyst for 3.5h at 670 ℃, further cleaning the waste catalyst by using a cleaning solution consisting of 10 percent of rosin polyoxyethylene ester (RPGC), 15 percent of tartaric acid and 75 percent of triethanolamine after soot blowing treatment, and crushing the waste catalyst to be less than 300 meshes to obtain waste catalyst powder;
(2) extraction of tungsten element
Preparing a saturated sodium chloride solution, slowly adding the waste catalyst powder obtained in the step (1) into the saturated sodium chloride solution, stirring the mixture to be pasty, and roasting the mixture at 750 ℃ for 5 hours to obtain a sintered block; crushing the sintered cake to 150 meshes, repeatedly leaching sodium tungstate generated after roasting by using an ethanolamine solution with the volume concentration of 15%, and filtering to obtain a sodium tungstate solution and a titanium precipitate;
(3) coarse titanium slag recovery
Washing and drying the precipitate obtained in the step (2) to obtain coarse titanium slag, and completing the recovery of titanium element;
(4) purification of tungsten element
Preparing an extracting agent consisting of 14% of trioctyl tertiary amine, 15% of octanol and 72% of sulfonated kerosene according to volume fraction, and performing 2-stage extraction on tungsten element in a sodium tungstate solution, wherein the volume ratio of each stage of organic phase to water phase is 1: 4; preparing an ammonium chloride solution with the concentration of 1.5mol/L, and performing 1-stage back extraction on tungsten element entering an organic phase, wherein the volume ratio of each stage of organic phase to a water phase is 1: 4;
(5) zirconium tungstate recovery
Preparing a precipitator, wherein the concentrations of zirconium chloride, ethylene diamine tetraacetic acid and hexadecyl trimethyl ammonium bromide in the precipitator are 1.6mol/L, 0.65mol/L and 0.25mol/L respectively; adding a precipitant into a stripping solution according to a molar ratio of zirconium chloride to tungsten element of 1.05, heating the solution to 85 ℃, continuously stirring for 3.5 hours, and then placing the solution in a room temperature environment for cooling and standing for 10 hours; filtering to obtain zirconium tungstate precipitate, washing with ethanol, drying, and recovering to obtain nanometer zirconium tungstate to recover tungsten element.
Through example 4, the recovery rate of the tungsten element is 96.21%, and the recovery rate of the titanium element is 98.93%; the purity of the recovered nanometer zirconium tungstate is 99.41%, and the content of titanium dioxide in the recovered crude titanium slag is 87.67%.
The method provided by the invention can be used for efficiently recovering titanium and tungsten elements in the waste SCR denitration catalyst, so that high-quality nano zirconium tungstate and coarse titanium slag are obtained. Wherein the purity of the zirconium tungstate is more than 99 percent, the content of titanium dioxide in the coarse titanium slag can reach more than 87 percent, and the recovery rates of tungsten and titanium elements respectively reach more than 95 percent and 97 percent.
The above detailed description is provided for a method for recovering an efficient waste SCR denitration catalyst provided by the present application, and a specific example is applied in the present application to explain the principle and the implementation manner of the present application, and the description of the above example is only used to help understanding the method and the core idea of the present application; meanwhile, for a person skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.
Claims (8)
1. A method for recovering an efficient waste SCR denitration catalyst is characterized by comprising the following steps:
(1) Pretreatment of raw materials: roasting the waste SCR denitration catalyst raw material, further cleaning the waste catalyst by using a cleaning solution consisting of 10-20% of rosin polyoxyethylene ester (RPGC), 5-15% of tartaric acid and 65-85% of triethanolamine after soot blowing, and crushing to obtain waste catalyst powder;
(2) extracting tungsten element: preparing a saturated sodium chloride solution, slowly adding the waste catalyst powder obtained in the step (1) into the saturated sodium chloride solution, stirring the mixture to be pasty, and roasting the mixture for 3 to 6 hours at the temperature of 750-; crushing the sintered cake to 150 meshes, repeatedly leaching the roasted sodium tungstate by using an ethanolamine solution with the volume concentration of 10-20%, and filtering to obtain a sodium tungstate solution and a titanium precipitate;
(3) and (3) recovering the coarse titanium slag: washing the titanium precipitate obtained in the step (2) with clear water, removing impurity elements attached to the surface, drying and recovering to obtain coarse titanium slag;
(4) tungsten element purification: preparing an extracting agent to extract tungsten element from the solution obtained in the step (2), wherein the extracting agent consists of an effective component, a phase regulator and a diluent, the effective component is trioctyl tertiary amine, the phase regulator is sec-octanol, the diluent is sulfonated kerosene, the number of extraction stages is 1-3, and the volume ratio of an organic phase to a water phase at each stage is 1: 3-5; using ammonium chloride, ammonium bicarbonate or ammonium carbonate solution as a stripping agent to strip tungsten elements from the extractant to obtain stripping solution, wherein the stripping stage number is 1-3, and the volume ratio of an organic phase to a water phase of each stage is 1: 3-5;
(5) Recovering zirconium tungstate: preparing a mixed aqueous solution of zirconium chloride, ethylene diamine tetraacetic acid and hexadecyl trimethyl ammonium bromide as a precipitant, adding the precipitant into a stripping solution, heating the solution to 80-95 ℃, continuously stirring for 2-4h, and then cooling and standing the solution at room temperature for 6-12 h; filtering to obtain zirconium tungstate precipitate, cleaning the precipitate by using ethanol, and finally drying and recovering to obtain the nano zirconium tungstate.
2. The method for recovering the high-efficiency waste SCR denitration catalyst according to claim 1, wherein the method comprises the following steps: the waste SCR denitration catalyst in the step (1) is eliminated V for industrial flue gas denitration2O5-WO3/TiO2Catalyst of the type comprising WO3、TiO2、V2O5、Al2O3、SiO2And CaO.
3. The method for recovering the high-efficiency waste SCR denitration catalyst according to claim 1, wherein the method comprises the following steps: the roasting temperature in the step (1) is 550-750 ℃, and the roasting time is 3-6 h.
4. The method for recovering the high-efficiency waste SCR denitration catalyst according to claim 1, wherein the method comprises the following steps: in the step (4), the volume fractions of the effective components, the phase regulator and the diluent in the extractant are respectively 5-15%, 10-20% and 65-85%.
5. The method for recovering the high-efficiency waste SCR denitration catalyst according to claim 1, wherein the method comprises the following steps: the concentration of the stripping agent solution in the step (4) is 1-2.5 mol/L.
6. The method for recovering the high-efficiency waste SCR denitration catalyst according to claim 1, wherein the method comprises the following steps: the concentration of each component of the precipitator in the step (5) is as follows: zirconium chloride is 1-2mol/L, ethylene diamine tetraacetic acid is 0.25-0.75mol/L, and hexadecyl trimethyl ammonium bromide is 0.1-0.3 mol/L.
7. The method for recovering the high-efficiency waste SCR denitration catalyst according to claim 1, wherein the method comprises the following steps: in the step (5), the molar ratio of zirconium chloride in the precipitating agent to tungsten element in the solution is 1-1.2: 1.
8. The method for recovering the high-efficiency waste SCR denitration catalyst according to claim 1, wherein the method comprises the following steps: the particle size of the waste catalyst powder in the step (1) is less than 300 meshes.
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