CN106011503A - Method for recycling tungsten, vanadium and titanium from SCR waste catalysts - Google Patents
Method for recycling tungsten, vanadium and titanium from SCR waste catalysts Download PDFInfo
- Publication number
- CN106011503A CN106011503A CN201610517677.1A CN201610517677A CN106011503A CN 106011503 A CN106011503 A CN 106011503A CN 201610517677 A CN201610517677 A CN 201610517677A CN 106011503 A CN106011503 A CN 106011503A
- Authority
- CN
- China
- Prior art keywords
- tungsten
- vanadium
- titanium
- extraction
- organic facies
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- C22B34/30—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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/16—Sintering; Agglomerating
-
- 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
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
-
- 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
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for recycling tungsten, vanadium and titanium from SCR waste catalysts. The method comprises the following steps: after the SCR waste catalysts are cleaned, the SCR waste catalysts are smashed and screened, sodium carbonate is doped into the SCR waste catalysts to be evenly stirred, mixed powder is sintered at a high temperature to obtain a sintered material, water is added for leaching out, and a sodium salt mixed solution containing tungsten and vanadium is obtained; under the condition that the pH value of the solution is large than 12, tungsten is selectively extracted, and an ammonium salt solution is used for reverse extraction to obtain an ammonium tungstate solution; under the condition that the pH value of raffinate obtained after tungsten extraction ranges from 10 to 11.5, vanadium is extracted, and a sodium hydroxide solution is used for reverse extraction to obtain a sodium vanadate solution containing a small amount of tungsten; and titanium is left in leaching residues to obtain a rich-titanium material. According to the method, separation of tungsten and vanadium from impurities such as phosphorus, arsenic and silicon is achieved, and primary separation and efficient enrichment of tungsten, vanadium and titanium are achieved.
Description
Technical field
The present invention relates to a kind of recovery tungsten, vanadium, method of titanium from SCR denitration dead catalyst, belong to nonferrous metals recycling field.
Background technology
Nitrogen oxides (NOx) is one of source of atmospheric pollution, constitutes human health and threatens greatly.Thermal power plant is one of main source of NOx discharge, and the method for the dry method flue gas denitration used at present is mainly selective catalytic reduction (SCR).SCR method denitration is under the effect of special catalyst, with ammonia or other reducing agents, NOx is optionally reduced to N2 and H2O: 4NO+4NH2+O2 harmless → 4N2+6H2O；4NH3+2NO2+O2
→ 3N2+6H2O ；NO2+NO+2NH3
→ 2N2+3H2O.Catalyst is the parts of most critical in SCR system.SCR catalyst is typically with TiO2 as carrier, with rare metal oxides such as WO3, V2O5 as active component.Wherein WO3 content is 2～about 10%, and V2O5 content is more than 0.5%, and TiO2 content is more than 70%, and the total content of WO3, V2O5 and TiO2 is often higher than 90%, additionally contains the impurity such as a certain amount of P, As, Si.SCR catalyst must be changed after using 3 years, owing to containing substantial amounts of metallic element in dead catalyst, deals with improperly and environment can be caused severe contamination.This dead catalyst contains appreciable high added value valuable metal titanium, tungsten and vanadium etc., is a kind of valuable secondary resource extracting above-mentioned valuable metal.
At present the processing mode of SCR dead catalyst there are two kinds, are the regeneration of dead catalyst and returning of dead catalyst respectively
Receive.Regeneration techniques cost is high, regenerated catalyst performance is difficult to ensure that, effective just for the inactivation caused because of flue dust blocking, catalyst poisoning, invalid to the inactivation caused because of Physical Damage and sintering, and regenerated catalyst inactivates again, cannot carry out Regeneration Treatment again.Therefore, SCR dead catalyst regeneration techniques cannot fundamentally solve the process problem of following large batch of dead catalyst.
Abroad, such as U.S., German and Japanese etc., the recovery technology of valuable metal in SCR dead catalyst is more paid attention to, starting is relatively early, the most general employing " leaching of oxidizing roasting alkali " makes tungsten, vanadium enter leachate, then acid adding adjusts pH to 2～4, then by solvent extraction or ion exchange enrichment, separating tungsten and vanadium.Though above two method can effectively extract tungsten and vanadium, but still has the shortcomings such as wastewater discharge is big, reagent consumption is high.
Domestic waste catalyst recovery industry is started late, and the recovery to SCR dead catalyst is paid close attention to less.Presently disclosed several patent applications still concentrate on traditional separation by precipitation.
Summary of the invention
The problem that it is an object of the invention to overcome prior art to exist, there is provided a kind of from SCR denitrating flue gas dead catalyst, reclaim tungsten, vanadium, the method for titanium, achieve tungsten, vanadium, titanium to separate with foreign matter of phosphor, arsenic, silicon etc. respectively, it is achieved that tungsten, vanadium, the initial gross separation of titanium and efficiently concentrating.
The present invention solves that the technical scheme that problem set forth above is used is:
A kind of recovery tungsten, vanadium, method of titanium from SCR denitrating flue gas dead catalyst, comprises the steps:
A, pretreatment: SCR dead catalyst is carried out, dries and crushes, levigate to granularity less than 150 μm；B, soda sinter: sinter under high temperature after being mixed homogeneously with sodium carbonate by step a gained SCR dead catalyst powder, obtain sintering feed；C, leaching: adding water in the sintering feed of step b gained and carry out heated and stirred leaching tungsten, vanadium, the leachate that solid-liquid separation obtains is the sodium salt mixed solution of tungstenic and vanadium, and leached mud is rich-titanium material；D, extraction tungsten: the leachate of step c gained is adjusted pH to more than 12, leachate is contacted with organic facies and carries out multitple extraction tungsten, tungsten enters organic facies, and vanadium and foreign matter of phosphor, arsenic, silicon etc. are stayed in the raffinate after extraction tungsten, i.e. obtains the raffinate after negative tungsten organic facies and extraction tungsten；Described negative tungsten organic facies ammonium salt solution carries out single-stage or multistage back extraction tungsten, and the aqueous phase after gained back extraction tungsten is the ammonium tungstate solution containing a small amount of vanadium, and organic facies after gained back extraction tungsten is repeatable to be used in step d；E, extracting vanadium: the raffinate after the extraction tungsten of step d gained is adjusted pH to 9.5～11.5, this solution is contacted with organic facies and carries out multitple extraction vanadium, vanadium enters organic facies, foreign matter of phosphor, arsenic, silicon etc. are stayed in the raffinate after extracting vanadium, i.e. obtain the raffinate after negative vanadium organic facies and extracting vanadium；Described negative vanadium organic facies strong alkali solution carries out single-stage or multistage back extraction, and the aqueous phase after the back extraction vanadium of gained is the sodium vanadate solution containing a small amount of tungsten, and organic facies after gained back extraction vanadium is the most repeatable to be used in step e.
By such scheme, in step e, raffinate after the extracting vanadium of gained adds a small amount of NaOH or Calx, and freezing and crystallizing separates out Na2CO3, repeatable is used in step b.
By such scheme, in step b, the addition of described sodium carbonate be SCR dead catalyst powder weight 10%～
50%, sintering temperature is 500～850 DEG C, and temperature retention time is 0.5～5 hour.
By such scheme, in step c, the volume of described water and the mass ratio of sintering feed are (1～3) L/1kg, and extraction temperature is 20～100 DEG C, and extraction time is 0.1～2 hour.
By in such scheme, step d and step e, described tune pH uses sodium hydroxide or sodium bicarbonate solid or water-soluble
Liquid.
By in such scheme, step d and step e, containing extractant, polarity improving agent and diluent in described organic facies,
The percent by volume of each component is extractant 10～60%, polarity improving agent 10～35%, diluent 5～80%, wherein extractant is one or both compositions of methyltrialkylammonium carbonate or methyltrialkylammonium bicarbonate, by such scheme, in the rapid d of skill, described ammonium salt solution is the mixed solution of ammonium hydrogen carbonate and ammonia, wherein the concentration range of ammonium hydrogen carbonate is 1.0～3.5mol/L, and the concentration range of ammonia is 0.5～1.5mol/L.
The technological principle of the present invention is broadly divided into the following three stage:
First stage, the technique that the present invention provides uses Na2CO3 to sinter water logging production breakdown SCR dead catalyst.Tungsten and vanadium in SCR dead catalyst react with Na2CO3, are converted into Na2WO4
Entering liquid phase in leaching process with NaVO3, obtain the leachate of tungstenic and vanadium, titanium is stayed in slag, obtains rich-titanium material, and the rich-titanium material obtained can be used for producing Rutile type titanium dioxide after HCl treatment.
Second stage, the present invention extracts tungsten and vanadium at solution pH value more than 12 with under conditions of solution pH value 9.5～11.5 respectively successively.In the leachate that Na2CO3 sintering water logging technique obtains in addition to W, V, possibly together with impurity such as P, As, Si.Under faintly acid and neutrallty condition, W, V not only itself are easily formed the many acid groups of polymerization but also are prone to the impurity such as same P, As, Si and form various heteropoly compound, it is difficult to realize removing impurity while extraction tungsten, vanadium.But in alkaline medium, tungsten exists with the tungstate radicle of monomer, and vanadium exists with metavanadic acid root or vanadic acid root morphology, with P, As, Si etc., chemical combination does not occurs.Using HCO3-or CO32-or HCO3-and CO32-mixed type N263 is extractant, extractant is bigger than PO43-, AsO43-, SiO44-with the binding ability of WO42-, VO3-or VO43-, thus can preferentially extract tungsten, vanadium and impurity P, As, Si are stayed raffinate, thus realize tungsten, vanadium separates with impurity P, As, Si.Under different pH values, under conditions of the ionic forms variant pH value that tungsten, vanadium exist in aqueous is more than 12, extractant preferentially extracts tungsten；Under conditions of pH value 9.5～11.5, the preferential extracting vanadium of extractant.Therefore, it can realize the extraction successively of tungsten and vanadium under different pH values.
Phase III, the raffinate after extracting vanadium, extracting vanadium of the raffinate after the aforementioned extraction tungsten mentioned can return to leach.Owing to extractant is HCO3-or CO32-or HCO3-and CO32-mixed type N263, during extraction tungsten and extracting vanadium, there is HCO3-, CO32-
With the exchange of WO42-, VO3-or VO43-, the raffinate after extracting vanadium contains substantial amounts of CO32-
Or HCO3-, add a small amount of NaOH and neutralize or after lime causticization, Na2CO3 in raffinate
Chilled crystallization can return to sintering and leaches operation.Therefore, the technique that the present invention provides can realize the closed cycle of water and alkali, without arranging outside waste water.
Compared with prior art, the invention has the beneficial effects as follows:
1, the present invention can realize the extraction successively of tungsten, vanadium in the basic conditions, realize tungsten, be separated from each other and tungsten, the vanadium of vanadium separate with impurity P, As, Si etc., respectively obtain the higher ammonium tungstate solution of purity and sodium vanadate solution, the most industrial more ripe evaporative crystallization technique can be respectively adopted and produced ammonium paratungstate (APT) by ammonium tungstate solution
Product, ammonium salt precipitation technique are produced ammonium metavanadate product by sodium vanadate solution；
2, the leached mud that the present invention obtains is rich-titanium material, can be used for preparing Rutile type titanium dioxide after HCl treatment, the raffinate of extraction process neutralizes or can return to after lime causticization sintering through NaOH and leaches operation, it is possible to achieve recycling of water and alkali, full technique, without arranging outside waste water, produces without waste residue；
3, present invention achieves tungsten, vanadium, titanium to separate with foreign matter of phosphor, arsenic, silicon etc. respectively, achieve tungsten, vanadium, the initial gross separation of titanium and efficiently concentrating, the extraction repeatable utilization of organic facies, there is the advantages such as clean environment firendly, metal recovery rate height, product purity height, low cost, be especially suitable for industrialization promotion.
Detailed description of the invention
The present invention is containing reclaiming tungsten, vanadium, the technique of titanium from SCR dead catalyst, and detailed comprises the steps:
1, pretreatment: SCR dead catalyst is carried out, dries and crushes, levigate；Wherein, SCR dead catalyst is containing WO32～10%, V2O50.5～5%, TiO265～the honeycomb fashion dead catalyst of 85%, levigate to granularity less than 150 μm；
2, soda sintering: at high temperature sinter after the SCR dead catalyst powder from step 1 is stirred with Na2CO3 powder, held for some time, obtain sintering feed；Wherein, the addition of sodium carbonate is the 10%～50% of catalyst fines weight；Sintering temperature is 500～850 DEG C, and the sintered heat insulating time is 0.5～5 hour；
3, leach: the sintering feed from step 2 adds water and leaches at a certain temperature, obtains the leachate containing sodium tungstate and vanadic acid sodium, and the leached mud rich in titanium after solid-liquid separation, and this leached mud is used for producing Rutile type titanium dioxide after HCl treatment；Wherein, the quality of the volume/dead catalyst of water=(1～3) L/1kg；Extraction temperature is 20～100 DEG C, and leaching temperature retention time is 0.1～2 hour；
4, extraction tungsten: the leachate of step 3 gained is adjusted pH to more than 12.0, leachate is contacted with organic facies and carries out multitple extraction tungsten, tungsten enters organic facies, and vanadium and foreign matter of phosphor, arsenic, silicon etc. are stayed in the raffinate after extraction tungsten, i.e. obtains the raffinate after negative tungsten organic facies and extraction tungsten；Described negative tungsten organic facies ammonium salt solution carries out single-stage or multistage back extraction tungsten, and the aqueous phase after gained back extraction tungsten is ammonium tungstate solution, and organic facies after gained back extraction tungsten is repeatable to be used in this step；
5 extracting vanadium: the raffinate after the extraction tungsten of step 4 gained is adjusted pH to 9.5～11.5, this solution is contacted with organic facies and carries out multitple extraction vanadium, vanadium enters organic facies, foreign matter of phosphor, arsenic, silicon etc. are stayed in the raffinate after extracting vanadium, i.e. obtain the raffinate after negative vanadium organic facies and extracting vanadium；Described negative vanadium organic facies strong alkali solution carries out single-stage or multistage back extraction, and the aqueous phase after the back extraction vanadium of gained is sodium vanadate solution, and organic facies after gained back extraction vanadium is the most repeatable to be used in this step.
6, the raffinate after the extracting vanadium of step 5 gained being added a small amount of NaOH or Calx, freezing and crystallizing separates out Na2CO3,
Repeatable it is used in step 2.
Below by embodiment, the detailed description of the invention of the present invention is described further, but the most therefore protection scope of the present invention is limited in the following embodiments.
Embodiment 1
A kind of reclaim tungsten from SCR dead catalyst, vanadium, the method for titanium in turn include the following steps:
(1) pretreatment: SCR dead catalyst contains WO32.76%, V2O51.23%, TiO274.3%, through high pressure water washing ash disposal, dry, crush, grinding to granularity is less than 150 μm；
(2) soda sintering: take this SCR dead catalyst of 10kg, mixes Na2CO3 powder 4kg, sinters after stirring at 750 DEG C, is incubated 3h, obtains sintering feed；
(3) leach: from the sintering feed of (2) by the volume of water: the mass ratio of dead catalyst is 1.5L/kg
Add water, leach 2 hours at 90 DEG C, after solid-liquid separation, obtain the leachate containing sodium tungstate and vanadic acid sodium, and the leached mud rich in titanium；Wherein containing WO315.6g/L, V2O56.88g/L in the leachate containing sodium tungstate and vanadic acid sodium, pH value is 13.10；Leached mud weight rich in titanium is 10.86kg, wherein containing WO30.38%, and V2O50.18%, TiO268.5%；
(4) extraction tungsten: containing WO315.6g/L, V2O56.88g/L in the leachate of (3), pH value is 13.10, this leachate is contacted with organic facies and carries out 9 stage countercurrent extraction tungsten, the ratio of the volume flow of organic facies and aqueous phase is 1/2, i.e. obtain the raffinate after negative tungsten organic facies and extraction tungsten, wherein the raffinate after this extraction tungsten contains WO30.14g/L, V2O56.57g/L；Described negative tungsten organic facies ammonium salt solution carries out 14 stage countercurrent back extraction tungsten, the ratio of the volume flow of organic facies and aqueous phase is 2/1, aqueous phase after gained back extraction tungsten is ammonium tungstate solution, organic facies after gained back extraction tungsten is repeatable is used in this step, wherein this ammonium tungstate solution, wherein containing WO360.1g/L, the impurity content such as V2O50.37g/L, P, As, Si meets evaporative crystallization and produces the needs of APT product；
Described in this step in organic facies the percent by volume of each component be extractant N26340%, sec-octyl alcohol 20%, sulfonated kerosene 40%, wherein N263 is the commercial disignation of domestic Arquad, it it is a kind of adogen, wherein the carbon atom in three alkyl is respectively 8～10, the most in advance by 2.0mol/L (NH4) 2CO3
Solution carries out multistage cross flow extraction by comparing 2/1, makes the adogen in organic facies be converted into the carbonate of methyltrialkylammonium；In the ammonium salt solution of back extraction tungsten described in this step, the concentration of ammonium hydrogen carbonate is 3mol/L, concentration 1mol/L of ammonia；
(5) extracting vanadium: from the raffinate after the extraction tungsten of (4) containing WO30.14g/L, V2O56.57g/L, pH
It is 12.6, uses NaHCO3
Adjust its pH to 10.00, being contacted with organic facies by this solution and carry out 9 stage countercurrent extracting vanadium, the ratio of the volume flow of organic facies and aqueous phase is 1/2.5, i.e. obtains the raffinate after negative vanadium organic facies and extracting vanadium, wherein the raffinate after this extracting vanadium contains WO30.02g/L, V2O50.51g/L；Described negative vanadium organic facies 2.5mol/LNaOH
Solution carries out 14 stage countercurrent back extraction, the ratio of the volume flow of organic facies and aqueous phase is 2.5/1, and the aqueous phase after the back extraction vanadium of gained is sodium vanadate solution, wherein containing WO30.47g/L, V2O537.8g/L, organic facies after gained back extraction vanadium is the most repeatable is used in this step；
Described in this step in organic facies the percent by volume of each component be extractant N26340%, sec-octyl alcohol 20%, sulfonated kerosene 40%, the most in advance by organic facies and 2.5mol/LNH4HCO3 and 1.0mol/L (NH4) 2CO3
Mixing ammonium salt solution multiple-contact, makes the adogen in organic facies be converted into the carbonate of methyltrialkylammonium and the salt-mixture of bicarbonate, wherein the salt-mixture of the bicarbonate of methyltrialkylammonium and carbonate mol ratio be about 8:1；In this step, the organic facies after back extraction vanadium regenerates with 0.25mol/L NaHCO3 solution, regenerates progression 5 grades, and the ratio of the volume flow of organic facies and aqueous phase is 1/4.
The above is only the preferred embodiment of the present invention, it is noted that for the person of ordinary skill of the art, without departing from the concept of the premise of the invention, it is also possible to make some modifications and variations, and these broadly fall into protection scope of the present invention.
Claims (7)
1. one kind is reclaimed tungsten, vanadium, the method for titanium from SCR denitrating flue gas dead catalyst, it is characterised in that comprise the steps: a, pretreatment: SCR dead catalyst is carried out, dries and crushes, levigate to granularity less than 150 μm；B, soda sinter: sinter under high temperature after being mixed homogeneously with sodium carbonate by step a gained SCR dead catalyst powder, obtain sintering feed；C, leaching: adding water in the sintering feed of step b gained and carry out heated and stirred leaching tungsten, vanadium, the leachate that solid-liquid separation obtains is the sodium salt mixed solution of tungstenic and vanadium, and leached mud is rich-titanium material；D, extraction tungsten: the leachate of step c gained is adjusted pH to more than 12, is contacted with organic facies by leachate and carry out multitple extraction tungsten, i.e. obtain the raffinate after negative tungsten organic facies and extraction tungsten；Described negative tungsten organic facies ammonium salt solution carries out single-stage or multistage back extraction tungsten, and the aqueous phase after gained back extraction tungsten is ammonium tungstate solution, and the organic facies after gained back extraction tungsten is re-used in step d；E, extracting vanadium: the raffinate after the extraction tungsten of step d gained is adjusted pH to 9.5～11.5, this solution is contacted with organic facies and carries out multitple extraction vanadium, i.e. obtain the raffinate after negative vanadium organic facies and extracting vanadium；Described negative vanadium organic facies strong alkali solution carries out single-stage or multistage back extraction, and the aqueous phase after the back extraction vanadium of gained is sodium vanadate solution, and the organic facies after gained back extraction vanadium is re-used in step e after regeneration.
2. from SCR denitrating flue gas dead catalyst, reclaim tungsten, vanadium, the method for titanium according to a kind of described in claim 1, it is characterised in that in step e, the raffinate after the extracting vanadium of gained adds a small amount of NaOH or Calx, and freezing and crystallizing separates out Na2CO3.
3. from SCR denitrating flue gas dead catalyst, reclaim tungsten, vanadium, the method for titanium according to a kind of described in claim 1, it is characterized in that in step b, the addition of described sodium carbonate is the 10%～50% of SCR dead catalyst powder weight, sintering temperature is 500～850 DEG C, and temperature retention time is 0.5～5 hour.
4. from SCR denitrating flue gas dead catalyst, reclaim tungsten, vanadium, the method for titanium according to a kind of described in claim 1, it is characterized in that in step c, the volume of described water and the mass ratio of sintering feed are (1～3) L/1kg, extraction temperature is 20～100 DEG C, and extraction time is 0.1～2 hour.
5. according to a kind of recovery tungsten, vanadium, the method for titanium from SCR denitrating flue gas dead catalyst described in claim 1, it is characterised in that in step d and step e, described tune pH value uses NaOH or NaHCO3 to adjust pH value.
6. from SCR denitrating flue gas dead catalyst, reclaim tungsten according to a kind of described in claim 1, vanadium, the method of titanium, it is characterized in that in step d and step e, containing extractant in described organic facies, polarity improving agent and diluent, the percent by volume of each component is extractant 10～60%, polarity improving agent 10～35%, diluent 5～80%, wherein extractant is one or both compositions of methyltrialkylammonium carbonate or methyltrialkylammonium bicarbonate, structure such as formula 1, shown in formula 2, R1, R2 and R3 is independently chosen from the linear paraffin base of C8～C12；Polarity improving agent is the higher alcohols of C8～C13；Diluent is sulfonated kerosene.
7. from SCR denitrating flue gas dead catalyst, reclaim tungsten, vanadium, the method for titanium according to a kind of described in claim 1, it is characterised in that in the rapid d of skill, described ammonium salt solution is the mixed solution of ammonium hydrogen carbonate and ammonia, and wherein the concentration range of ammonium hydrogen carbonate is 1.0
～3.5mol/L, the concentration range of ammonia is 0.5～1.5mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610517677.1A CN106011503A (en) | 2016-07-05 | 2016-07-05 | Method for recycling tungsten, vanadium and titanium from SCR waste catalysts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610517677.1A CN106011503A (en) | 2016-07-05 | 2016-07-05 | Method for recycling tungsten, vanadium and titanium from SCR waste catalysts |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106011503A true CN106011503A (en) | 2016-10-12 |
Family
ID=57106791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610517677.1A Pending CN106011503A (en) | 2016-07-05 | 2016-07-05 | Method for recycling tungsten, vanadium and titanium from SCR waste catalysts |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106011503A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106512716A (en) * | 2016-11-15 | 2017-03-22 | 东莞市联洲知识产权运营管理有限公司 | Low-temperature flue gas SCR denitration and tungsten, vanadium and titanium comprehensive recovery method |
| CN107512734A (en) * | 2017-08-01 | 2017-12-26 | 洛阳理工学院 | A kind of method that tungsten vanadium and titanium dioxide are reclaimed from discarded SCR denitration |
| CN108950249A (en) * | 2018-07-16 | 2018-12-07 | 武汉科技大学 | A kind of vanadium aluminum separation method of vanadium-containing shale pickle liquor |
| CN109750156A (en) * | 2019-03-15 | 2019-05-14 | 华北电力大学 | A method of recycling vanadium, tungsten/molybdenum and titanium elements from discarded SCR denitration |
| CN111235409A (en) * | 2020-03-09 | 2020-06-05 | 广西大学 | Method for extracting vanadium from vanadium-containing sodium carbonate leaching solution |
| CN111996394A (en) * | 2020-08-20 | 2020-11-27 | 兰立华 | Efficient extraction and separation method for vanadium and tungsten in alkali leaching solution of waste denitration catalyst |
| CN112921191A (en) * | 2021-01-26 | 2021-06-08 | 厦门钨业股份有限公司 | Method for recovering tungsten from ammonium phosphate slag containing tungsten |
| CN113046562A (en) * | 2021-03-08 | 2021-06-29 | 北京华电光大环境股份有限公司 | Method for recovering tungsten element in waste catalyst |
| CN113981249A (en) * | 2020-07-27 | 2022-01-28 | 中国石油化工股份有限公司 | Method for recovering vanadium from waste catalyst |
| CN114058853A (en) * | 2021-11-26 | 2022-02-18 | 中南大学 | Method for recovering titanium, vanadium and tungsten from waste SCR denitration catalyst |
| CN115445639A (en) * | 2022-09-14 | 2022-12-09 | 北京科技大学 | Solid super acidic catalyst, preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB470540A (en) * | 1935-12-05 | 1937-08-17 | Ig Farbenindustrie Ag | Improvements in or relating to the extraction of heavy metals from phosphatic ores, slags, and like materials containing them |
| CN104263946A (en) * | 2014-10-10 | 2015-01-07 | 武汉凯迪电力环保有限公司 | Method for recovering tungsten, vanadium and titanium from waste SCR (selective catalytic reduction) denitration catalyst |
| CN104831075A (en) * | 2015-05-22 | 2015-08-12 | 北京赛科康仑环保科技有限公司 | Method for separating and purifying vanadium and molybdenum of waste vanadium-molybdenum SCR (selective catalytic reduction) 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 |
| CN104862485A (en) * | 2015-05-22 | 2015-08-26 | 北京赛科康仑环保科技有限公司 | Vanadium and tungsten separating and purifying method for spent vanadium and tungsten SCR (selective catalytic reduction) catalysts |
-
2016
- 2016-07-05 CN CN201610517677.1A patent/CN106011503A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB470540A (en) * | 1935-12-05 | 1937-08-17 | Ig Farbenindustrie Ag | Improvements in or relating to the extraction of heavy metals from phosphatic ores, slags, and like materials containing them |
| CN104263946A (en) * | 2014-10-10 | 2015-01-07 | 武汉凯迪电力环保有限公司 | Method for recovering tungsten, vanadium and titanium from waste SCR (selective catalytic reduction) 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 |
| CN104831075A (en) * | 2015-05-22 | 2015-08-12 | 北京赛科康仑环保科技有限公司 | Method for separating and purifying vanadium and molybdenum of waste vanadium-molybdenum SCR (selective catalytic reduction) catalyst |
| CN104862485A (en) * | 2015-05-22 | 2015-08-26 | 北京赛科康仑环保科技有限公司 | Vanadium and tungsten separating and purifying method for spent vanadium and tungsten SCR (selective catalytic reduction) catalysts |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106512716A (en) * | 2016-11-15 | 2017-03-22 | 东莞市联洲知识产权运营管理有限公司 | Low-temperature flue gas SCR denitration and tungsten, vanadium and titanium comprehensive recovery method |
| CN107512734A (en) * | 2017-08-01 | 2017-12-26 | 洛阳理工学院 | A kind of method that tungsten vanadium and titanium dioxide are reclaimed from discarded SCR denitration |
| CN108950249A (en) * | 2018-07-16 | 2018-12-07 | 武汉科技大学 | A kind of vanadium aluminum separation method of vanadium-containing shale pickle liquor |
| CN109750156A (en) * | 2019-03-15 | 2019-05-14 | 华北电力大学 | A method of recycling vanadium, tungsten/molybdenum and titanium elements from discarded SCR denitration |
| CN111235409A (en) * | 2020-03-09 | 2020-06-05 | 广西大学 | Method for extracting vanadium from vanadium-containing sodium carbonate leaching solution |
| CN113981249A (en) * | 2020-07-27 | 2022-01-28 | 中国石油化工股份有限公司 | Method for recovering vanadium from waste catalyst |
| CN113981249B (en) * | 2020-07-27 | 2023-01-10 | 中国石油化工股份有限公司 | Method for recovering vanadium from waste catalyst |
| CN111996394A (en) * | 2020-08-20 | 2020-11-27 | 兰立华 | Efficient extraction and separation method for vanadium and tungsten in alkali leaching solution of waste denitration catalyst |
| CN112921191A (en) * | 2021-01-26 | 2021-06-08 | 厦门钨业股份有限公司 | Method for recovering tungsten from ammonium phosphate slag containing tungsten |
| CN113046562A (en) * | 2021-03-08 | 2021-06-29 | 北京华电光大环境股份有限公司 | Method for recovering tungsten element in waste catalyst |
| CN114058853A (en) * | 2021-11-26 | 2022-02-18 | 中南大学 | Method for recovering titanium, vanadium and tungsten from waste SCR denitration catalyst |
| CN115445639A (en) * | 2022-09-14 | 2022-12-09 | 北京科技大学 | Solid super acidic catalyst, preparation method and application thereof |
| CN115445639B (en) * | 2022-09-14 | 2023-08-22 | 北京科技大学 | Solid super acidic catalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104263946B (en) | A kind of method reclaiming tungsten, vanadium, titanium from SCR denitration dead catalyst | |
| CN106011503A (en) | Method for recycling tungsten, vanadium and titanium from SCR waste catalysts | |
| CN109750156B (en) | Method for recovering vanadium, tungsten/molybdenum and titanium elements from waste SCR denitration catalyst | |
| CN104831075B (en) | A kind of vanadium of useless vanadium molybdenum system SCR catalyst, molybdenum are separated and method of purification | |
| CN106048230B (en) | The separation of tungsten and vanadium, recovery method in a kind of useless SCR denitration | |
| CN103436704B (en) | A kind of method reclaiming vanadium and tungsten from the vanadium titanium base waste denitration catalyst of tungstenic | |
| CN106435197B (en) | A kind of SCR denitration dead catalyst valuable metal alkaline extraction retracting device and technique | |
| CN104195342B (en) | A kind of method reclaiming Vanadium Pentoxide in FLAKES composition in waste and old SCR denitration | |
| CN104862485B (en) | A kind of vanadium of useless vanadium tungsten system SCR catalyst, tungsten separation and method of purification | |
| CN107419104B (en) | The comprehensive recovering process of useless SCR denitration | |
| JP2018524171A (en) | Recycling method of used SCR denitration catalyst | |
| CN104118911B (en) | A kind of method reclaiming tungstic oxide in discarded SCR catalyst completely | |
| CN113198457B (en) | Medium-low temperature denitration catalyst prepared from waste SCR catalyst and preparation method thereof | |
| CN105838885B (en) | A kind of comprehensive reutilization method of useless SCR catalyst | |
| CN110817944B (en) | Recovery method of waste SCR denitration catalyst | |
| CN106622284A (en) | Recovery and utilization technology of waste titanium-vanadium based SCR catalyst capable of being applied to reproduction | |
| CN107164634B (en) | The method that tungsten vanadium component is recycled from cellular useless SCR catalyst for denitrating flue gas | |
| CN105274341A (en) | Method for leaching metallic vanadium and metallic tungsten in waste selective catalytic reduction (SCR) denitration catalyst | |
| CN111778398A (en) | Method for extracting vanadium and tungsten from waste SCR denitration catalyst | |
| CN114774701A (en) | Resource utilization method of industrial waste salt and waste denitration catalyst | |
| CN103088217A (en) | Method for recovering tungsten component from selective catalytic reduction denitrification catalyst | |
| CN105771997A (en) | Preparation method and application of dealkalized red mud | |
| CN106277043A (en) | The method extracting separating metal oxide from catalyst for denitrating flue gas | |
| CN106807401A (en) | A kind of renovation process of denitrating catalyst and a kind of regeneration denitrating catalyst and its application | |
| CN110760683A (en) | Method for extracting vanadium from waste SCR catalyst and preparing alkali metal fluotitanate, product and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20161012 |
|
| WD01 | Invention patent application deemed withdrawn after publication |