CN114107703A - Method for recovering vanadium and tungsten from waste vanadium-titanium denitration catalyst - Google Patents
Method for recovering vanadium and tungsten from waste vanadium-titanium denitration catalyst Download PDFInfo
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- CN114107703A CN114107703A CN202010888761.0A CN202010888761A CN114107703A CN 114107703 A CN114107703 A CN 114107703A CN 202010888761 A CN202010888761 A CN 202010888761A CN 114107703 A CN114107703 A CN 114107703A
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- denitration catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000002699 waste material Substances 0.000 title claims abstract description 40
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000010937 tungsten Substances 0.000 title claims abstract description 36
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 35
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 31
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 18
- 239000002244 precipitate Substances 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 7
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims abstract description 6
- 238000004176 ammonification Methods 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 239000007791 liquid phase Substances 0.000 claims abstract description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 15
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 15
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 15
- 239000001099 ammonium carbonate Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 239000000428 dust Substances 0.000 claims description 6
- 239000007790 solid phase Substances 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 3
- 231100000572 poisoning Toxicity 0.000 claims description 3
- 230000000607 poisoning effect Effects 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 238000007667 floating Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 23
- 238000011084 recovery Methods 0.000 description 20
- 239000000706 filtrate Substances 0.000 description 8
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010335 hydrothermal treatment Methods 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 229910019501 NaVO3 Inorganic materials 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000005576 amination reaction Methods 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910003206 NH4VO3 Inorganic materials 0.000 description 2
- 229910020350 Na2WO4 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- VQBIMXHWYSRDLF-UHFFFAOYSA-M sodium;azane;hydrogen carbonate Chemical group [NH4+].[Na+].[O-]C([O-])=O VQBIMXHWYSRDLF-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical compound [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
- C22B34/225—Obtaining vanadium from spent catalysts
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
- C22B34/365—Obtaining tungsten from spent catalysts
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a method for recovering vanadium and tungsten from a waste vanadium-titanium denitration catalyst, which comprises the following steps: (1) processing the pretreated waste vanadium-titanium system denitration catalyst into particles with a certain mesh number; (2) carrying out hydrothermal ammonification treatment on the particles obtained in the step (1) in a pressure-resistant container, carrying out solid-liquid separation after the treatment is finished, standing the separated liquid phase for a period of time, separating out a precipitate which is ammonium metavanadate, and separating out the ammonium metavanadate to obtain a tungsten-containing solution; (3) and adjusting the pH value of the tungsten-containing solution to 2-5, separating out a precipitate, and washing and removing impurities from the precipitate to obtain the tungstic acid. The method adopts a one-step hydrothermal method and simple separation, can effectively recover vanadium and tungsten in the waste catalyst, and has the advantages of simple process, low investment cost and environmental protection.
Description
Technical Field
The invention relates to a method for recovering vanadium and tungsten from a waste vanadium-titanium denitration catalyst.
Background
The SCR denitration technology is the most applied and mature denitration technology in the world at present. The denitration method has the characteristics of high denitration efficiency, strong adaptability, high reliability and the like, and is widely applied. And SCR denitrationThe core of the system is a denitration catalyst, and a vanadium-titanium denitration catalyst is generally adopted. The denitration catalyst can be invalid due to poisoning, sintering, aging, abrasion, blockage and the like in the operation process of the catalyst, and although the catalyst can recover the activity through regeneration, the regeneration is not infinite. With the wide application of the SCR technology, the usage amount of the catalyst is multiplied, and the waste catalyst is more and more. The waste vanadium-titanium denitration catalyst is a dangerous waste containing a certain amount of TiO2、WO3And V2O5And alkali metals, molybdenum, nickel and the like can cause serious pollution to the environment when being improperly treated. Simultaneously, vanadium and tungsten5And are expensive raw materials for producing the catalyst. Therefore, the method has remarkable economic benefit and good environmental benefit when the vanadium and the tungsten are recovered.
CN103484678A discloses a method for recovering vanadium, tungsten and titanium from waste vanadium-tungsten-titanium-based denitration catalyst, which comprises the steps of preparing the catalyst into powder with the particle size of less than 100 meshes, and adding concentrated alkali liquor; heating to react vanadium, tungsten and titanium with alkali to generate slightly soluble titanate, water-soluble vanadate and tungstate; filtering to obtain titanate filter cake, and preparing titanate or titanic acid from the filter cake; adding ammonium salt into the filtrate to separate out ammonium metavanadate, and filtering to obtain ammonium metavanadate and new filtrate; adding concentrated acid into the new filtrate to prepare the solid tungstic acid.
CN102557142A discloses a method for recovering tungsten trioxide and ammonium metavanadate from SCR denitration catalyst, which comprises the steps of crushing and sieving the SCR denitration catalyst to prepare catalyst powder, adding sodium carbonate, fully and uniformly stirring, then putting the mixed powder into a sintering furnace to be calcined into sintering material, preserving heat for 1 hour, crushing and sieving to prepare sintering material powder, and then pouring warm water to ensure that Na in the sintering material powder is contained2WO4And NaVO3Dissolving completely, filtering, removing precipitate to obtain Na2WO4And NaVO3Mixing the solution; adjusting the pH value to 6.5-7.5, adding ammonia water to separate out ammonium metavanadate precipitate, washing for 2-3 times by using a dilute ammonium bicarbonate solution after filtering, then washing for 1-2 times by using 30% ethanol, and drying to obtain an ammonium metavanadate finished product; the residue is leftNa in the remaining solution2WO4Converted to ammonium paratungstate, the remaining solution is evaporated to obtain ammonium paratungstate crystals, which are then calcined to obtain tungsten trioxide.
The method for recovering tungsten and vanadium from SCR denitration catalyst in the prior art mainly uses alkali substances to convert V into V2O5And WO3Conversion to soluble Na2WO4And NaVO3Adding precipitant to make NaVO3And (4) after the precipitate is converted into ammonium metavanadate, filtering and separating the ammonium metavanadate, and recovering tungsten from the filtered solution. Although the method can effectively recover tungsten and vanadium, the process is relatively complex and is not easy to be applied industrially.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for recovering vanadium and tungsten from a waste vanadium-titanium denitration catalyst, the method adopts a one-step hydrothermal method and simple separation, can effectively recover the vanadium and the tungsten in the waste catalyst, and has the advantages of simple process, low investment cost and environmental protection.
The method for recovering vanadium and tungsten from the waste vanadium-titanium denitration catalyst comprises the following steps:
(1) processing the pretreated waste vanadium-titanium system denitration catalyst into particles with a certain mesh number;
(2) carrying out hydrothermal ammonification treatment on the particles obtained in the step (1) in a pressure-resistant container, carrying out solid-liquid separation after the treatment is finished, standing the separated liquid phase for a period of time, separating out a precipitate which is ammonium metavanadate, and separating out the ammonium metavanadate to obtain a tungsten-containing solution;
(3) and adjusting the pH value of the tungsten-containing solution to 2-5, separating out a precipitate, and washing and removing impurities from the precipitate to obtain the tungstic acid.
In the method of the present invention, the waste vanadium-titanium denitration catalyst described in the step (1) is a waste vanadium-titanium denitration catalyst whose denitration performance is reduced due to dust deposition on the surface of the catalyst or due to clogging, poisoning, damage to a physical structure, and the like. The vanadium-titanium denitration catalyst contains a certain amount of active components such as vanadium and tungsten.
In the method of the present invention, the pretreatment in step (1) refers to removal of floating dust on the surface and dust deposition in the pore channels of the waste vanadium-titanium denitration catalyst, and generally adopts air purging, water washing, and other processes.
In the method of the present invention, the processing procedure described in step (1) is well known to those skilled in the art, and generally adopts the procedures of pulverizing, sieving, etc., and the mesh number is 140 meshes or more, preferably 200 meshes or more, and more preferably 400 meshes or 900 meshes.
In the method, the hydrothermal ammonification material system in the step (2) comprises the slurry of the particulate matters, the ammonium bicarbonate and the water obtained in the step (1), and the treatment conditions are as follows: the temperature is 120-160 ℃, and the time is 4-8 hours. The pressure-resistant container is generally a high-pressure reaction kettle; wherein the mass ratio of the particles to the ammonium bicarbonate is 1:8-1:4, the mass ratio of the solid phase to the water is 1:4-1:2, and the mass of the solid phase refers to the total mass of the ammonium bicarbonate and the particles before being dissolved in the water. The particles, ammonium bicarbonate and water can be added and mixed in any order, the mixing temperature is generally room temperature, the temperature can be properly increased in order to further facilitate the dissolution of the ammonium bicarbonate in the water, but the operation is not necessary.
In the method of the present invention, the solid-liquid separation method in step (2) may be filtration, centrifugation or the like.
In the method of the present invention, the standing in the step (2) may be performed at room temperature, generally not lower than 0 ℃, not higher than 30 ℃, preferably at a standing temperature of 1 to 10 ℃, and the standing time is preferably such that the weight of the crystal precipitated from the solution is not increased, generally 72 to 168 hours.
In the method of the present invention, hydrochloric acid or sulfuric acid may be used to adjust the pH in step (3), and hydrochloric acid is preferred.
The method of the invention adopts a hydrothermal ammonification treatment process to remove WO in the waste catalyst in one step3And V2O5Conversion to NH4VO3And (NH)4) 2WO4. In a closed hydrothermal system, NH4VO3First dissolved in the mixed solution, and NH is generated when the mixed solution is stood at low temperature in the later period4VO3Precipitated from the solution in the form of crystals and filtered to obtain a solution containing tungsten. When the vanadium is recovered by the conventional method, the vanadium needs to be firstly recoveredThen adding ammonium salt into the soluble vanadium salt solution to separate out vanadium in the form of ammonium metavanadate. Compared with the conventional method, the method can be used for preparing V in one step2O5Directly converted into ammonium metavanadate to be precipitated. The method has simple process, high recovery rate of vanadium and tungsten, and good purity.
Detailed Description
The following examples are provided to further illustrate the technical solutions of the present invention, but the present invention is not limited to the following examples.
Vanadium recovery = (0.78 × m)1）÷（m2X a%) where m1: mass m of ammonium metavanadate precipitated from the solution2: mass of waste catalyst added in hydrothermal treatment, a%: the mass percentage of vanadium pentoxide in the waste vanadium-titanium denitration catalyst.
Tungsten recovery = (0.93 × m)3）÷（m2X c%) where m3: mass of tungstic acid, m2: mass of waste catalyst added in hydrothermal treatment, c%: the mass percentage of tungsten oxide in the waste vanadium-titanium denitration catalyst.
XRF characterization: the components of the waste catalyst, the target material Rh and the light path atmosphere are analyzed by using a Japanese ZSX100e type X-ray fluorescence spectrometer: and (4) vacuum conditions.
WO is contained in the waste vanadium-titanium denitration catalyst adopted in the embodiment3：6.3wt%，V2O5: 3.4 wt%. Firstly, flushing with compressed air, then washing with deionized water to remove impurities such as fly ash on the surface of the waste catalyst, and finally drying. Ammonium bicarbonate, analytical pure grade, produced by far reaching chemical reagents limited, Tianjin.
Example 1
(1) Crushing and sieving the waste vanadium-titanium-containing denitration catalyst to prepare catalyst powder with 200-400 meshes;
(2) weighing 50 g of the waste vanadium-titanium denitration catalyst powder and 240 g of ammonium bicarbonate, adding 1000 g of distilled water into the materials, stirring for 20 minutes, transferring the mixed materials into a high-pressure kettle, heating to 135 ℃, and carrying out hydrothermal amination treatment for 7 hours. Filtering the material subjected to hydrothermal amination, standing the filtrate at 5 ℃ for 100 hours, filtering the filtrate after standing to obtain a crystal and a solution, wherein the crystal is determined as an ammonium metavanadate crystal by XRD, and the solution is determined as a tungsten-containing solution by chemical titration and ion chromatography;
(3) adding a hydrochloric acid solution into the solution in the step (2), controlling the pH value of the solution to be 2.3, separating out a precipitate, washing the precipitate to remove impurities, and determining that the precipitate is tungstic acid by XRD; through calculation, the recovery rate of tungsten in the treated waste vanadium-titanium denitration catalyst is 84.3%, and the recovery rate of vanadium is 90.1%.
Example 2
The same as example 1, except that the amount of ammonium bicarbonate added was 310 g, the hydrothermal treatment temperature was 145 ℃ and the treatment time was 5 hours, the filtrate was allowed to stand at 6 ℃ and 120 hours, and the pH of the solution was controlled to 2.6; through calculation, the recovery rate of tungsten in the treated waste vanadium-titanium denitration catalyst is 85.1%, and the recovery rate of vanadium is 91.2%.
Example 3
In the same manner as in example 1, except that the amount of ammonium hydrogencarbonate added was 340 g, the hydrothermal treatment temperature was 125 ℃ and the treatment time was 7.5 hours, the filtrate was allowed to stand at 10 ℃ and the solution was allowed to stand for 150 hours, the pH of the solution was controlled to 3.1, and it was found that the recovery rate of tungsten in the treated waste vanadium-titanium denitration catalyst was 84.9% and the recovery rate of vanadium was 89.7%.
Example 4
The same as example 1, except that the amount of ammonium bicarbonate added was 210 g, the hydrothermal treatment temperature was 115 ℃ and the treatment time was 4 hours, the filtrate was allowed to stand at 3 ℃ and 90 hours, and the pH of the solution was controlled to 4.1; through calculation, the recovery rate of tungsten in the treated waste vanadium-titanium denitration catalyst is 83.6%, and the recovery rate of vanadium is 88.4%.
Comparative example 1
The same as example 1, except that the amount of ammonium hydrogen carbonate added in step (2) was 80 g, the recovery rate of tungsten in the treated waste vanadium-titanium denitration catalyst was 18.7% and the recovery rate of vanadium was 8.5%.
Comparative example 2
The same as example 1, except that the hydrothermal amination treatment temperature in the step (2) was 85 ℃, and the recovery rate of tungsten in the treated waste vanadium-titanium denitration catalyst was 25.3% and the recovery rate of vanadium was 13.4% by calculation.
Comparative example 3
The same as example 1, except that the hydrothermal amination temperature in the step (2) was 210 ℃, and the recovery rate of tungsten in the treated waste vanadium-titanium denitration catalyst was 66.4% and the recovery rate of vanadium was 73.8% by calculation.
In a comparative example 4,
in the same manner as in example 1, except that the hydrothermal time in step (2) was 2 hours, the recovery rate of tungsten in the treated waste vanadium-titanium denitration catalyst was 31.2% and the recovery rate of vanadium was 22.6%.
Comparative example 5
The same as example 1, except that ammonium bicarbonate was replaced with sodium carbonate and ammonium chloride in the step (2), the amount of sodium carbonate added was 27 g, the amount of ammonium chloride added was 13.5 g, no ammonium metavanadate crystal was precipitated from the treated solution, and the recovery rate of vanadium was 68.5%.
Claims (10)
1. A method for recovering vanadium and tungsten from a waste vanadium-titanium denitration catalyst is characterized by comprising the following steps: (1) processing the pretreated waste vanadium-titanium system denitration catalyst into particles with a certain mesh number; (2) carrying out hydrothermal ammonification treatment on the particles obtained in the step (1) in a pressure-resistant container, carrying out solid-liquid separation after the treatment is finished, standing the separated liquid phase for a period of time, separating out a precipitate which is ammonium metavanadate, and separating out the ammonium metavanadate to obtain a tungsten-containing solution; (3) and adjusting the pH value of the tungsten-containing solution to 2-5, separating out a precipitate, and washing and removing impurities from the precipitate to obtain the tungstic acid.
2. The method of claim 1, wherein: the waste vanadium-titanium denitration catalyst in the step (1) is a waste vanadium-titanium denitration catalyst with reduced denitration performance caused by surface dust deposition or pore channel blockage, poisoning and physical structure damage, and contains vanadium and tungsten metal components.
3. The method of claim 1, wherein: the pretreatment in the step (1) is to remove floating dust on the surface of the waste vanadium-titanium denitration catalyst and dust deposited in the pore channel.
4. The method of claim 1, wherein: the mesh number in the step (1) is more than 140 meshes, preferably more than 200 meshes.
5. The method of claim 1, wherein: the mesh number in the step (1) is 400-900 meshes.
6. The method of claim 1, wherein: the treatment conditions in the step (2) are as follows: the temperature is 120-160 ℃, and the time is 4-8 hours.
7. The method of claim 1, wherein: the mass ratio of the particles to the ammonium bicarbonate in the step (2) is 1:8-1:4, the mass ratio of the solid phase to the water is 1:4-1:2, and the mass of the solid phase refers to the total mass of the ammonium bicarbonate and the particles before being dissolved in the water.
8. The method of claim 1, wherein: and (3) filtering or centrifuging the solid-liquid separation mode in the step (2).
9. The method of claim 1, wherein: the standing temperature in the step (2) is not lower than 0 ℃ and not higher than 30 ℃.
10. The method of claim 1, wherein: the standing time in the step (2) is preferably 72 to 168 hours, so that the weight of the crystal precipitated from the solution is not increased any more.
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