CN111996394A - Efficient extraction and separation method for vanadium and tungsten in alkali leaching solution of waste denitration catalyst - Google Patents
Efficient extraction and separation method for vanadium and tungsten in alkali leaching solution of waste denitration catalyst Download PDFInfo
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- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
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Abstract
The invention discloses a high-efficiency extraction and separation method of vanadium and tungsten in an alkali leaching solution of a waste denitration catalyst, and relates to the technical field of hazardous waste resource utilization. The invention comprises the following steps: s1: adding dilute sulfuric acid into the waste denitration catalyst alkaline leaching solution, adjusting the pH value of the waste denitration catalyst alkaline leaching solution to 2-5, and filtering the waste denitration catalyst alkaline leaching solution with well-adjusted pH value to obtain a solution I and tungstic acid; s2: and adding an oxidant into the solution I for oxidation regulation to obtain a solution II. According to the invention, through multiple extraction and back extraction, vanadium and tungsten in the alkali immersion liquid of the waste denitration catalyst are efficiently extracted and separated, the vanadium and tungsten separation coefficient is high, the extraction recovery rate is high, the product quality is good, the production flow is short, the cost of the extraction agent is low, and the problems that the existing chemical precipitation method is low in recovery rate, large in acid and alkali consumption, much in wastewater, complicated in production process, the ion exchange method can only enrich vanadium and tungsten, effective separation is not obtained, the cost of the extraction agent adopted by the existing extraction method is high, and the subsequent vanadium and tungsten separation is not complete are solved.
Description
Technical Field
The invention belongs to the technical field of hazardous waste resource utilization, and particularly relates to a high-efficiency extraction and separation method of vanadium and tungsten in alkali leaching solution of a waste denitration catalyst.
Background
Since 8 months in 2014, the national ministry of environmental protection manages the waste denitration catalyst as dangerous waste, which is currently classified as HW50, in the actual operation of the denitration catalyst device, the reduction of the activity of the catalyst and the reduction of the service life are caused by various reasons, the effect of treating the nitrogen oxide does not reach the standard, for example, the catalyst poisoning caused by alkali metal in flue gas, the blockage of catalyst holes, the damage caused by catalyst abrasion or flue gas impact and the like, the first considered treatment mode of the failed catalyst is the regeneration of the catalyst, only part of the failed catalyst can be recycled through the regeneration mode, if the activity of the failed catalyst cannot be recovered through the regeneration mode, only the failed catalyst can be scrapped, so that more than 15 ten thousand tons of waste denitration catalyst per year needs to be treated, and the main components of the denitration catalyst comprise 70-80% of TiO2, 3-10% of WO3 and 1-3% of V2O5, 2-10% of SiO2, 1-3% of Al2O3 and 1-3% of CaO, wherein the TiO2 has extremely high market value, and the WO3 is less, and the waste catalyst contains part of toxic and harmful elements, such as vanadium pentoxide, and the random disposal of the waste catalyst inevitably causes secondary pollution to the environment.
At present, vanadium and tungsten are extracted and separated by an extraction method after alkali roasting, a resin exchange method or a chemical precipitation method in China.
Chemical precipitation method
CN102936049A discloses a method for extracting tungsten, titanium and vanadium from waste SCR catalyst, which comprises: crushing the waste SCR catalyst to a particle size of 100-200 meshes, adding a strong base solution with a mass percentage concentration of 20-30%, reacting at a temperature of 150-200 ℃ for 3-6h, filtering and separating to obtain the SCR catalyst for removing tungsten and vanadium and a mixed solution of sodium tungstate and sodium vanadate, preparing the SCR catalyst into a strong acid solution with a mass percentage concentration of 70-80% according to the mass ratio of 1:3-6 of the strong acid to the sodium tungstate solution and the sodium vanadate solution, adding the mixed solution of sodium tungstate and sodium vanadate, reacting at a temperature of 150-300 ℃ for 1-4h, filtering and separating to obtain a tungstic acid solid and a mixed solution of sodium salt and vanadate, adding ammonia water into the mixed solution of sodium tungstate and sodium vanadate to regulate the pH value to 7-8, precipitating, filtering and separating to obtain an ammonium vanadate solution, concentrating, cooling and crystallizing to obtain an ammonium salt solid, and then reacting the SCR catalyst subjected to tungsten and vanadium removal with a concentrated sulfuric acid solution under a heating condition, filtering and separating to obtain a titanyl sulfate solution, aluminum slag and other solids, hydrolyzing titanyl sulfate to obtain a titanic acid solid and a waste acid solution, and calcining the obtained ammonium vanadate, tungstic acid and titanic acid to respectively obtain vanadium pentoxide, tungsten trioxide and titanium dioxide. The process has the defects of low recovery rate, high acid and alkali consumption, more waste water, complicated production process and the like.
Solvent extraction process
The separation of vanadium and tungsten is realized by utilizing the solubility difference of vanadium and tungsten in an aqueous phase and an organic phase. For example, the invention patent CN104862485A discloses a vanadium and tungsten separation and purification method of a waste vanadium-tungsten SCR catalyst, which comprises the steps of firstly, extracting and separating a vanadium-tungsten solution to obtain a vanadium-rich raffinate, and then, treating the vanadium-rich raffinate to obtain vanadium pentoxide; and (3) performing secondary extraction to extract tungsten from the tungsten-rich organic obtained by separation after back extraction, performing back extraction to obtain an ammonium tungstate solution, and performing treatment to obtain the ammonium paratungstate with the purity of 99%. However, the method preferentially extracts the tungsten with the highest content in the solution, so that the extraction load is large and the production cost is high.
CN106048230A is prepared by crushing and drying the waste SCR catalyst, mixing with Na2CO3, roasting at high temperature, and leaching in dilute sulfuric acid; secondly, extracting W and V in the leachate by utilizing a kerosene solution of tri-n-octylamine and isodecyl alcohol, and then separating the W and V from the extracted organic phase by taking NaOH as a stripping agent; finally, adding H2SO4 into the back extraction solution to adjust the pH value, adding excessive NH4Cl to precipitate vanadium, filtering to obtain ammonium metavanadate precipitate, and roasting to obtain a V2O5 product; and (3) continuously adding sulfuric acid into the secondary filtrate after vanadium precipitation to adjust the pH value, adding excessive CaCl2 to precipitate tungsten, and filtering to obtain CaWO4 precipitate, pickling with hydrochloric acid, and roasting to obtain a WO3 product. The method can realize the high-efficiency separation and recovery of tungsten and vanadium in the waste SCR catalyst, but the cost of the medicament in the extraction process is high, calcium tungstate contains calcium vanadate due to incomplete vanadium precipitation, and the product quality is not high.
Ion exchange process
CN109536721A adopts crushed waste denitration catalyst and strong base solution to perform ultrasonic pressure alkali leaching, then the waste denitration catalyst and the strong base solution are treated by a liquid-solid separation device, vanadium, tungsten and other impurities enter liquid in an ion form, titanium enters filter residues to become a primary byproduct, strong-base large-channel anion exchange resin is adopted to treat filtrate I, vanadium and tungsten in the filtrate are adsorbed on the ion exchange resin, the pH value of the filtrate before ion exchange is controlled within 8.0-14, the resin after vanadium and tungsten ion adsorption is analyzed by adopting a mixed solution of Na0H and NaCl as desorption solution, the concentration of NaOH and NaCl is controlled within 0.5-2.0 mol/L, the concentration ratio of NaOH and NaCl in the solution is controlled within 0.8-1.3, precipitator is added into the desorption solution after ion exchange resin desorption to form corresponding tungstate and vanadate precipitates, 410g of titanium-rich solid is obtained (containing TiO296.6%, WO 30.6%, V2O50.38%, SiO21.19%, CaO0.24%, Al2O30.03%, MgO 0.29%, other 0.67%), to obtain vanadium-and tungsten-containing compounds 52.8g (wherein calcium vanadate is 3.47%, calcium tungstate 84.05%, water content is 10.4%, other 2.08%). The method only enriches vanadium and tungsten, and tungsten and vanadium are not really separated.
There is therefore a need for improvements in the prior art to address the above-mentioned problems.
Disclosure of Invention
The invention aims to provide a high-efficiency extraction and separation method of vanadium and tungsten in waste denitration catalyst alkali immersion liquid, which efficiently extracts and separates vanadium and tungsten in the waste denitration catalyst alkali immersion liquid through multiple times of extraction and back extraction, has high vanadium and tungsten separation coefficient, high extraction recovery rate, good product quality, short production flow and low cost of extraction reagents, and solves the problems that the existing chemical precipitation method is low in recovery rate, large in acid and alkali consumption, more in wastewater, complicated in production process, high in cost of an extractant adopted by the existing extraction method, and incomplete in subsequent vanadium and tungsten separation, and an ion exchange method only can enrich vanadium and tungsten and is capable of effectively separating the vanadium and tungsten.
In order to solve the technical problems, the invention is realized by the following technical scheme:
the invention relates to a high-efficiency extraction and separation method of vanadium and tungsten in alkali leaching solution of a waste denitration catalyst, which comprises the following steps:
s1: adding dilute sulfuric acid into the waste denitration catalyst alkaline leaching solution, adjusting the pH value of the waste denitration catalyst alkaline leaching solution to 2-5, and filtering the waste denitration catalyst alkaline leaching solution with well-adjusted pH value to obtain a solution I and tungstic acid;
s2: adding an oxidant into the first solution for oxidation regulation to obtain a second solution;
s3: adding an extracting agent 1 into the solution II for extraction to obtain tungsten-containing residual liquid and a vanadium-loaded organic phase;
s4: adding an extracting agent 2 into the tungsten-containing residual liquid for extraction and enrichment to obtain a tungsten-loaded organic phase and a tungsten extraction residual liquid;
s5: adding a stripping agent 2 into the tungsten-loaded organic phase for stripping to obtain a tungsten-rich solution, and adding a stripping agent 1 into the vanadium-loaded organic phase for stripping to obtain a vanadium-rich solution;
s6: adding dilute sulfuric acid into the vanadium-rich solution, adjusting the pH value of the vanadium-rich solution to 8-9, then adding ammonium sulfate, precipitating to obtain ammonium metavanadate, and returning and combining the solution after vanadium precipitation to the waste denitration catalyst alkali immersion solution;
s7: and concentrating, evaporating and centrifugally dewatering the tungsten-rich solution to obtain ammonium paratungstate, and returning the mother solution to back-extract tungsten.
Further, the oxidant in the S2 is one or a mixture of two of hydrogen peroxide and sodium chlorate.
Furthermore, the extractant 1 in the S3 and the extractant 2 in the S4 are both prepared by mixing one or more of N235, N263 and a modifier L with the No. 260 solvent oil.
Further, the concentration of the extracting agent 1 in the S3 and the concentration of the extracting agent 2 in the S4 are both 5% -25%, and the extracting temperature is set to be 20-40 ℃.
Further, the extraction and back-extraction processes in the S3, S4 and S5 adopt the steps of firstly carrying out countercurrent and then carrying out cross-flow to carry out sectional extraction.
Further, in the S5, the stripping agent 1 is set to be a mixture of 1mol/L-2 mol/L NaOH solution and 0mol/L-2 mol/L sodium chloride solution, and the stripping agent 2 is set to be ammonia water.
The invention has the following beneficial effects:
the method has the advantages of high vanadium-tungsten separation coefficient, high extraction recovery rate, good product quality, high V2O5 content of over 99.5%, high WO3 content of over 98%, short production flow and low cost of extraction reagents.
Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, the present invention is a method for efficiently extracting and separating vanadium and tungsten from alkaline leaching solution of waste denitration catalyst, comprising the following steps:
s1: adding dilute sulfuric acid into the waste denitration catalyst alkaline leaching solution, adjusting the pH value of the waste denitration catalyst alkaline leaching solution to 2-5, and filtering the waste denitration catalyst alkaline leaching solution with well-adjusted pH value to obtain a solution I and tungstic acid;
s2: adding an oxidant into the first solution for oxidation regulation to obtain a second solution, wherein the oxidant is one or a mixture of hydrogen peroxide and sodium chlorate;
s3: adding an extracting agent 1 into the solution II for extraction to obtain tungsten-containing residual liquid and a vanadium-loaded organic phase;
s4: adding an extracting agent 2 into the tungsten-containing residual liquid for extraction and enrichment to obtain a tungsten-loaded organic phase and a tungsten-extracted residual liquid, wherein the extracting agent 1 and the extracting agent 2 are both prepared from one or more of N235, N263 and a modifier L and No. 260 solvent oil, the concentrations of the extracting agent 1 and the extracting agent 2 are both 5% -25%, and the extraction temperature is set to be 20-40 ℃;
s5: adding a stripping agent 2 into the loaded tungsten organic phase for stripping to obtain a tungsten-rich liquid, adding a stripping agent 1 into the loaded vanadium organic phase for stripping to obtain a vanadium-rich liquid, wherein the stripping agent 1 is a mixture of 1mol/L-2 mol/L NaOH solution and 0mol/L-2 mol/L sodium chloride solution, and the stripping agent 2 is ammonia water;
s6: adding dilute sulfuric acid into the vanadium-rich solution, adjusting the pH value of the vanadium-rich solution to 8-9, then adding ammonium sulfate, precipitating to obtain ammonium metavanadate, and returning and combining the solution after vanadium precipitation to the waste denitration catalyst alkali immersion solution;
s7: and concentrating, evaporating and centrifugally dewatering the tungsten-rich solution to obtain ammonium paratungstate, and returning the mother solution to back-extract tungsten.
The main components of a spent SCR catalyst alkaline leach solution are shown in table 1:
example 1
Taking 1000 liters of alkaline leaching solution of the waste denitration catalyst in the table 1;
s1: adding dilute sulfuric acid into 1000 liters of waste denitration catalyst alkaline leaching solution, adjusting the pH value to 2.0, reacting for 1 hour, then carrying out centrifugal filtration separation to obtain tungstic acid precipitate and solution I, and selecting PAM as a filter aid during filtration;
s2: adding 5g of hydrogen peroxide into the first solution for oxidation regulation, reacting for 1 hour to obtain a second solution, measuring WO 31.98 g/L and V2O52.68 g/L in the second solution, and feeding the second solution into an extraction system;
s3: adding an extracting agent 1 into the solution II for extraction, and performing three-stage countercurrent extraction on the extracting agent 1 by using a separating funnel to obtain tungsten-containing residual liquid and a vanadium-loaded organic phase, wherein WO 31.58 g/L and V2O50.018 g/L are contained in the tungsten-containing residual liquid;
s4: adding an extracting agent 2 into the tungsten-containing residual liquid for extraction and enrichment to obtain a tungsten-loaded organic phase and a tungsten extraction residual liquid;
s5: adding a stripping agent 1 into the vanadium-loaded organic phase for stripping to obtain vanadium-rich liquid, wherein V2O542.8 g/L and WO 30.38 g/L of the vanadium-rich liquid are contained in the vanadium-rich liquid, and the stripping agent 1 is a mixture of 2 mol/L NaOH solution and 0.5mol/L sodium chloride solution;
s6: adding dilute sulfuric acid into the vanadium-rich solution, adjusting the pH value of the solution to 8.5, then adding ammonium sulfate, precipitating to obtain ammonium metavanadate, and returning and combining the solution after vanadium precipitation to the waste denitration catalyst alkali immersion solution;
s7: adding ammonia water as a stripping agent 2 into the loaded tungsten organic phase for stripping to obtain tungsten-rich liquid, wherein the tungsten-rich liquid is WO 330.7 g/L and V2O50.21 g/L, and the tungsten-rich liquid is concentrated, evaporated and centrifugally dehydrated to obtain ammonium paratungstate, and the mother solution is returned for stripping tungsten.
The whole extraction recovery rate of V2O5 is more than or equal to 99 percent, and the whole extraction recovery rate of WO3 is more than or equal to 98 percent.
Example 2
Taking 1000 liters of alkaline leaching solution of the waste denitration catalyst in the table 1;
s1: adding dilute sulfuric acid into 1000 liters of waste denitration catalyst alkaline leaching solution, adjusting the pH value to 2.52, reacting for 1 hour, then carrying out centrifugal filtration separation to obtain tungstic acid precipitate and solution I, and selecting PAM as a filter aid during filtration;
s2: adding 1g of sodium chlorate into the solution I for oxidation regulation, reacting for 1 hour to obtain a solution II, measuring WO 32.48 g/L and V2O52.71 g/L in the solution II, and entering an extraction system;
s3: adding an extracting agent 1 into the solution II for extraction, and performing three-stage countercurrent extraction on the extracting agent 1 by using a separating funnel to obtain tungsten-containing residual liquid and a vanadium-loaded organic phase, wherein WO 32.09 g/L and V2O50.007 g/L are contained in the tungsten-containing residual liquid;
s4: adding an extracting agent 2 into the tungsten-containing residual liquid for extraction and enrichment to obtain a tungsten-loaded organic phase and a tungsten extraction residual liquid;
s5: adding a stripping agent 1 into the vanadium-loaded organic phase for stripping to obtain vanadium-rich liquid, wherein V2O553.1 g/L and WO 30.31 g/L of the vanadium-rich liquid are contained in the vanadium-rich liquid, and the stripping agent 1 is a mixture of 2 mol/L NaOH solution and 0.5mol/L sodium chloride solution;
s6: adding dilute sulfuric acid into the vanadium-rich solution, adjusting the pH value of the solution to 8.8, then adding ammonium sulfate, precipitating to obtain ammonium metavanadate, and returning and combining the solution after vanadium precipitation to the waste denitration catalyst alkali immersion solution;
s7: adding a stripping agent 2 ammonia water into the loaded tungsten organic phase for stripping to obtain a tungsten-rich solution, wherein WO 338.8 g/L and V2O50.11 g/L are contained in the tungsten-rich solution, concentrating, evaporating and centrifugally dewatering the tungsten-rich solution to obtain ammonium paratungstate, and returning mother liquor to strip tungsten.
The whole extraction recovery rate of V2O5 is more than or equal to 99 percent, and the whole extraction recovery rate of WO3 is more than or equal to 98 percent.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The above are only preferred embodiments of the present invention, and the present invention is not limited thereto, and any modifications to the technical solutions described in the above embodiments, and equivalents of some technical features are included in the scope of the present invention.
Claims (6)
1. A high-efficiency extraction separation method of vanadium and tungsten in alkali leaching solution of a waste denitration catalyst is characterized by comprising the following steps: the method comprises the following steps:
s1: adding dilute sulfuric acid into the waste denitration catalyst alkaline leaching solution, adjusting the pH value of the waste denitration catalyst alkaline leaching solution to 2-5, and filtering the waste denitration catalyst alkaline leaching solution with well-adjusted pH value to obtain a solution I and tungstic acid;
s2: adding an oxidant into the first solution for oxidation regulation to obtain a second solution;
s3: adding an extracting agent 1 into the solution II for extraction to obtain tungsten-containing residual liquid and a vanadium-loaded organic phase;
s4: adding an extracting agent 2 into the tungsten-containing residual liquid for extraction and enrichment to obtain a tungsten-loaded organic phase and a tungsten extraction residual liquid;
s5: adding a stripping agent 2 into the tungsten-loaded organic phase for stripping to obtain a tungsten-rich solution, and adding a stripping agent 1 into the vanadium-loaded organic phase for stripping to obtain a vanadium-rich solution;
s6: adding dilute sulfuric acid into the vanadium-rich solution, adjusting the pH value of the vanadium-rich solution to 8-9, then adding ammonium sulfate, precipitating to obtain ammonium metavanadate, and returning and combining the solution after vanadium precipitation to the waste denitration catalyst alkali immersion solution;
s7: and concentrating, evaporating and centrifugally dewatering the tungsten-rich solution to obtain ammonium paratungstate, and returning the mother solution to back-extract tungsten.
2. The method for efficiently extracting and separating vanadium and tungsten from the alkaline leaching solution of the waste denitration catalyst as claimed in claim 1, wherein the oxidant in S2 is one or a mixture of hydrogen peroxide and sodium chlorate.
3. The method for efficiently extracting and separating vanadium and tungsten from the alkaline leaching solution of the waste denitration catalyst as claimed in claim 1, wherein the extractant 1 in S3 and the extractant 2 in S4 are both prepared from one or more of N235, N263 and modifier L and No. 260 solvent oil.
4. The method for efficiently extracting and separating vanadium and tungsten from the alkaline leaching solution of the waste denitration catalyst as claimed in claim 1, wherein the concentrations of the extracting agent 1 in S3 and the extracting agent 2 in S4 are both 5% -25%, and the extracting temperature is set to be 20-40 ℃.
5. The method for efficiently extracting and separating vanadium and tungsten from the alkaline leaching solution of the waste denitration catalyst as claimed in claim 1, wherein the extraction and back extraction processes in S3, S4 and S5 all adopt a countercurrent flow and a cross flow for sectional extraction.
6. The method for efficiently extracting and separating vanadium and tungsten through the alkaline leaching solution of the spent denitration catalyst as claimed in claim 1, wherein the stripping agent 1 in the step S5 is a mixture of 1mol/L-2 mol/L NaOH solution and 0mol/L-2 mol/L NaCl solution, and the stripping agent 2 is ammonia water.
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| CN112941342A (en) * | 2021-01-29 | 2021-06-11 | 武汉科技大学 | Method for enriching vanadium by combining roasting, bioleaching and extraction of vanadium-containing shale |
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| CN102936049A (en) * | 2012-11-26 | 2013-02-20 | 西南民族大学 | Method for extracting tungsten, titanium and vanadium from waste SCR (selective catalytic reduction) catalyst |
| CN104118911A (en) * | 2014-07-11 | 2014-10-29 | 沈阳远大科技园有限公司 | Method capable of completely recycling tungsten trioxide from SCR catalyst |
| CN104772318A (en) * | 2015-02-11 | 2015-07-15 | 成都九洲利源科技有限公司 | Comprehensive utilization method for waste SCR denitration catalyst |
| CN104843788A (en) * | 2015-04-27 | 2015-08-19 | 苏州华电北辰环保技术有限公司 | Vanadium recovery method based on vanadium-containing solution extracted from waste SCR denitration catalyst |
| CN106011503A (en) * | 2016-07-05 | 2016-10-12 | 无锡市华东电力设备有限公司 | Method for recycling tungsten, vanadium and titanium from SCR waste catalysts |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112941342A (en) * | 2021-01-29 | 2021-06-11 | 武汉科技大学 | Method for enriching vanadium by combining roasting, bioleaching and extraction of vanadium-containing shale |
| CN112941342B (en) * | 2021-01-29 | 2022-08-30 | 武汉科技大学 | Method for enriching vanadium by combining roasting, bioleaching and extraction of vanadium-containing shale |
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