CN206319050U - A kind of SCR denitration dead catalyst valuable metal alkaline extraction retracting device - Google Patents
A kind of SCR denitration dead catalyst valuable metal alkaline extraction retracting device Download PDFInfo
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- 238000000605 extraction Methods 0.000 title claims abstract description 73
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 18
- 239000002184 metal Substances 0.000 title claims abstract description 18
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 118
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 118
- 239000010937 tungsten Substances 0.000 claims abstract description 118
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 109
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 108
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 63
- 239000010936 titanium Substances 0.000 claims abstract description 31
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 29
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 28
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 24
- 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 claims abstract description 23
- 239000002893 slag Substances 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000002425 crystallisation Methods 0.000 claims abstract description 12
- 230000008025 crystallization Effects 0.000 claims abstract description 12
- 238000002386 leaching Methods 0.000 claims description 64
- 239000012074 organic phase Substances 0.000 claims description 35
- 238000005406 washing Methods 0.000 claims description 26
- 238000006386 neutralization reaction Methods 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 21
- 229910052710 silicon Inorganic materials 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 18
- 239000010703 silicon Substances 0.000 claims description 18
- 239000002699 waste material Substances 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 15
- 238000005342 ion exchange Methods 0.000 claims description 13
- 238000007670 refining Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000011084 recovery Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- 238000001556 precipitation Methods 0.000 claims description 11
- 239000011268 mixed slurry Substances 0.000 claims description 9
- 230000001376 precipitating effect Effects 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 238000004064 recycling Methods 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 23
- 238000000926 separation method Methods 0.000 abstract description 17
- 239000006227 byproduct Substances 0.000 abstract description 4
- 230000018044 dehydration Effects 0.000 abstract 1
- 238000006297 dehydration reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- 239000003513 alkali Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- NWJUARNXABNMDW-UHFFFAOYSA-N tungsten vanadium Chemical compound [W]=[V] NWJUARNXABNMDW-UHFFFAOYSA-N 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
Classifications
-
- 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
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- Catalysts (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The utility model discloses a kind of SCR denitration dead catalyst valuable metal alkaline extraction retracting device, it uses NaOH solution, and the tungsten of SCR denitration dead catalyst, vanadium are leached into leachate, and titanium is stayed in leached mud, realizes the separation of tungsten, vanadium and titanium；Then using the tungsten and vanadium in alkaline extraction technique separation leachate；Refined again by processes such as crystallization, dehydration, drying, obtain meeting the ammonium paratungstate and ammonium metavanadate of national standard high-purity, while obtaining byproduct Ti-enriched slag.The utility model can reclaim the valuable metal in SCR denitration dead catalyst, can obtain meeting the ammonium paratungstate and ammonium metavanadate of the high-purity of national standard, while obtaining byproduct Ti-enriched slag.
Description
Technical Field
The utility model belongs to the technical field of industry solid waste handles, a SCR denitration spent catalyst resourceful treatment technique is related to, concretely relates to SCR denitration spent catalyst valuable metal alkaline extraction recovery unit.
Background
The Selective Catalytic Reduction (SCR) method is the mainstream technology of flue gas denitration of the existing thermal power plant, and is the denitration technology which has the highest denitration efficiency, is the most mature and is most applied at present. This technique is widely used with TiO2As a carrier, WO3、V2O5And rare metal oxides as active components.
After several years of use, the activity of the SCR denitration catalyst is reduced to a certain extent, and the SCR denitration catalyst cannot meet the SCR denitration requirement, so that the SCR denitration catalyst needs to be regenerated or replaced. The regeneration can prolong the service life of the catalyst, but the catalyst can be discarded because the catalyst cannot be regenerated indefinitely due to structural damage and the like. The SCR denitration waste catalyst is a pollutant harmful to the environment and is listed in the national hazardous waste listHowever, such a spent catalyst contains valuable metals such as tungsten, vanadium, and titanium. The mainstream SCR denitration catalyst in the current market contains WO3About 2 to 10% of V2O5About 1 to 5 percent of TiO2About 70-90%, from the perspective of resource recovery, SCR denitration spent catalyst is a valuable resource, retrieves tungsten, vanadium and titanium among them and can produce considerable economic benefits, and the product that changes into tungsten, vanadium, titanium from dangerous solid useless through handling spent catalyst utilizes once more simultaneously, has good environmental benefit.
The recovery of valuable metals in the SCR denitration spent catalyst is started earlier abroad, such as America, Germany, Japan and the like, at present, tungsten and vanadium are firstly introduced into a leaching solution by adopting 'oxidation roasting-alkaline leaching', and then tungsten is extracted mainly by adopting an ion exchange method or an acid extraction method. The technologies are relatively laggard, and the reason is that on one hand, the reserves of tungsten ore in China are the first in the world, and the smelting technology of tungsten in China is in the leading position internationally; on the other hand, the total content of tungsten contained in the SCR denitration spent catalyst is small relative to tungsten ore.
The domestic waste catalyst recycling industry starts late, and the recycling attention to the SCR denitration waste catalyst is less. Chinese utility model patent applications CN104384167A and CN104772318A both disclose a method for recovering SCR denitration spent catalyst by firstly leaching vanadium with acid and then leaching tungsten with alkali to extract tungsten and vanadium step by step, which not only has high consumption of acid and alkali reagents, but also has low leaching rate. Chinese utility model patent applications CN103160690B and CN103484678A all disclose a method for recovering SCR denitration waste catalyst by firstly using alkaline leaching to extract tungsten and vanadium, and then precipitating ammonium metavanadate and tungstic acid from the leachate respectively by using ammonium salt and concentrated acid, which not only consumes a large amount of acid, but also easily coprecipitates tungsten and vanadium, resulting in poor separation effect and low product yield. Chinese patent CN104862485A discloses a method for recovering SCR denitration spent catalyst, in which tungsten and vanadium are extracted by roasting and leaching, and then tungsten is extracted from the leachate by acidic extraction, the separation effect of tungsten and vanadium is good, but the acidic extraction has poor removal effect on impurities such as P, Si, etc., the leachate is alkaline, a large amount of acid is consumed for adjusting the pH value, and a large amount of wastewater is generated by acid-base neutralization. The two latter methods extract tungsten and vanadium simultaneously by leaching, and then separate tungsten and vanadium by using the traditional precipitation method or acid extraction, although the leaching rate is higher, the method has defects in tungsten and vanadium separation.
Chinese utility model patent application CN104263946A discloses a method for recovering tungsten, vanadium and titanium from SCR denitration waste catalyst by adopting alkaline extraction process, firstly passing through Na2CO3And (3) extracting tungsten and vanadium simultaneously by sintering and water leaching, then sequentially extracting tungsten and vanadium by alkaline extraction, and leaving titanium in leaching slag to obtain a titanium-rich material, thereby realizing the separation of tungsten, vanadium and titanium. The alkaline extraction can simultaneously realize the separation of tungsten and vanadium and the separation of impurities such as tungsten, vanadium, P, Si and the like under the alkaline condition, and overcomes the defects of poor tungsten and vanadium separation and impurity removal effects, large consumption of acid-base reagents, large amount of wastewater and the like in the traditional separation method, however, Na is adopted in the method2CO3The tungsten and vanadium are leached in a sintering and water leaching mode, energy consumption is high in the sintering process, a small amount of waste gas is generated, alkali used for sintering is difficult to recycle, the concentration of the tungsten and vanadium in the obtained leaching solution is low, a small amount of acid-base reagent is still needed to adjust the pH value before subsequent alkaline tungsten extraction and vanadium extraction, and a part of the acid-base reagent is consumed.
Chinese utility model patent application CN104760998A discloses a tungsten recovery method based on tungsten-containing solution of SCR denitration spent catalyst, it adopts alkaline extraction to extract tungsten from the alkaline immersion liquid of SCR denitration spent catalyst, the purity of the ammonium metatungstate or the tungsten trioxide that finally obtain all can reach more than 98%, but this method only retrieves tungsten, vanadium in the SCR denitration spent catalyst on the one hand, valuable metals such as titanium do not obtain make full use of, contain toxic metals such as vanadium in the residual liquid of on the other hand alkaline extraction, it can produce new pollution sources not to deal with well. Therefore, compared with the traditional method, the alkaline extraction method has the advantages that the tungsten-vanadium separation effect is greatly improved, but the existing process still has the defects of cleanness, energy conservation and comprehensive recovery of tungsten, vanadium and titanium resources.
In summary, the following problems exist in the prior art for recovering the denitration waste catalyst, aiming at recovering valuable metals from the SCR denitration waste catalyst:
1. the consumption of acid and alkali reagents is large, and the leaching rate is low;
2. the tungsten and vanadium separation efficiency is low, the impurity removal effect is poor, and a large amount of wastewater is generated by acid-base neutralization;
3、Na2CO3sintering and water leaching have high energy consumption, sintering waste gas is generated, alkali is difficult to recycle, and the concentration of tungsten and vanadium in the leaching solution is low;
4. the recovery and purification of three valuable metals of tungsten, vanadium and titanium can not be realized simultaneously.
SUMMERY OF THE UTILITY MODEL
An object of the utility model is to provide a valuable metal alkaline extraction recovery unit of useless catalyst of SCR denitration, it adopts NaOH to leach + the valuable metal among the useless catalyst of SCR denitration is retrieved to alkaline extraction technology, can obtain the high-purity ammonium paratungstate and the ammonium metavanadate that accord with national standard, obtains the rich titanium sediment of byproduct simultaneously.
The utility model provides a technical scheme that its technical problem adopted is:
an SCR denitration spent catalyst valuable metal alkaline extraction recovery device comprises a NaOH leaching system, an alkaline extraction system and a product refining system; wherein,
the NaOH leaching system is used for separating tungsten, vanadium and titanium, and comprises a raw material tank, a high-pressure leaching kettle, a belt filter and a first dryer which are sequentially connected, wherein the raw material tank is used for fully mixing input SCR denitration waste catalyst powder subjected to ash removal and crushing with NaOH and water to form mixed slurry, the high-pressure leaching kettle is used for enabling the mixed slurry to react at a certain temperature and pressure to leach the tungsten and the vanadium, the belt filter is used for washing and filtering the reacted slurry to obtain leachate containing the tungsten and the vanadium and leaching slag containing titanium dioxide, an outlet of the belt filter is connected with an inlet of the raw material tank to return the leachate containing the tungsten and the vanadium to the raw material tank, and the first dryer is used for drying the leaching slag containing the titanium dioxide to obtain titanium-rich slag;
the alkaline extraction system is used for separating tungsten and vanadium, and comprises an extraction tank, a washing tank and a back extraction tank which are sequentially connected, wherein the extraction tank is used for enabling leachate containing tungsten and vanadium obtained by a belt filter to react with a blank organic phase to obtain a tungsten-rich organic phase and a vanadium-rich raffinate, the washing tank is used for washing the tungsten-rich organic phase with pure water, and the back extraction tank is used for reacting the washed tungsten-rich organic phase with a back extractant to obtain a tungsten-rich back extract and a blank organic phase;
the product refining system is used for refining high-purity ammonium paratungstate and ammonium metavanadate, and comprises a tungsten making subsystem and a vanadium making subsystem, wherein the tungsten making subsystem comprises an ion exchange column, an evaporation crystallization kettle and a second dryer which are sequentially connected, the ion exchange column is used for deeply removing vanadium from a tungsten-rich strip liquor obtained by a strip bath, the evaporation crystallization kettle is used for crystallizing the tungsten-rich strip liquor subjected to deep vanadium removal to obtain an ammonium paratungstate crystal, the second dryer is used for drying the ammonium paratungstate crystal to obtain ammonium paratungstate, the vanadium making subsystem comprises a neutralization silicon removal kettle, a vanadium precipitation reaction kettle and a third dryer which are sequentially connected, the neutralization silicon removal kettle is used for precipitating the vanadium-rich raffinate obtained by an extraction bath, and the vanadium precipitation reaction kettle is used for precipitating the vanadium-rich raffinate after silicon removal to obtain an ammonium metavanadate precipitate, and the third dryer is used for drying the ammonium metavanadate precipitate to obtain the ammonium metavanadate.
According to the technical scheme, the outlet of the washing tank is also connected with the inlet of the neutralization silicon removal kettle and is used for enabling washing water to flow into the neutralization silicon removal kettle.
According to the technical scheme, the outlet of the back extraction tank is also connected with the inlet of the extraction tank and is used for returning the blank organic phase to the extraction tank for recycling.
According to the technical scheme, the outlet of the ion exchange column is also connected with the inlet of the neutralization and silicon removal kettle and is used for enabling vanadium removal liquid to flow into the neutralization and silicon removal kettle.
The utility model discloses, following beneficial effect has:
1. the utility model discloses a NaOH solution leaches the separation that realizes tungsten, vanadium and titanium, leaches the leaching solution with tungsten, the vanadium of SCR denitration spent catalyst, and titanium stays in leaching the sediment, can high-efficiently leach tungsten, vanadium, does not need the calcination, therefore can not produce calcination waste gas, saved the calcination power consumption, avoided TiO energy dissipation2The reaction with alkali is carried out in the roasting process, high titanium slag meeting the national standard can be obtained, and the leachate containing tungsten and vanadium can be returned to leaching, so that the recycling of water and alkali is simply realized, the concentration of tungsten and vanadium in the leachate is increased, and the subsequent alkaline extraction and product purification are facilitated;
2. the utility model discloses an alkaline extraction tungsten can realize the separation of tungsten and vanadium and the separation of tungsten and impurities such as P, Si simultaneously, obtains high-purity sodium tungstate solution and sodium vanadate solution, finally obtains ammonium paratungstate and ammonium metavanadate product that accord with national standard, and tungsten, vanadium, three kinds of valuable metals of titanium are retrieved simultaneously, produce good economic benefits, and the cyclic utilization of extraction organic phase has further reduced technology cost, is fit for industrial production;
3. the utility model discloses a combined process of NaOH leaching + alkaline extraction, the leaching solution need not adjust pH, can directly carry out alkaline extraction, need not add the free alkali in a large amount of sour neutralization leaching solutions to avoid producing the waste water that contains inorganic salt in a large number.
Drawings
The invention will be further explained with reference to the drawings and examples, wherein:
fig. 1 is a schematic structural diagram of an embodiment of the present invention.
In the figure: 1-raw material tank, 2-high pressure leaching kettle, 3-belt filter, 4-first dryer, 5-extraction tank, 6-washing tank, 7-back extraction tank, 8-ion exchange column, 9-evaporative crystallization kettle, 10-second dryer, 11-neutralization desilication kettle, 12-vanadium precipitation reaction kettle, and 13-third dryer.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the invention.
In the preferred embodiment of the present invention, an SCR denitration spent catalyst valuable metal alkaline extraction recovery device, as shown in fig. 1, comprises a NaOH leaching system, an alkaline extraction system and a product refining system; wherein,
the NaOH leaching system is used for separating tungsten, vanadium and titanium, and comprises a raw material tank 1, a high-pressure leaching kettle 2, a belt filter 3 and a first dryer 4 which are connected in sequence, wherein the raw material tank 1 is used for fully mixing input SCR denitration waste catalyst powder subjected to ash removal and crushing with NaOH and water to form mixed slurry, the high-pressure leaching kettle 2 is used for enabling the mixed slurry to react at a certain temperature and pressure to leach tungsten and vanadium, the belt filter 3 is used for washing and filtering the reacted slurry to obtain a leaching solution containing tungsten and vanadium and leaching slag containing titanium dioxide, an outlet of the belt filter 3 is connected with an inlet of the raw material tank 1 to return the leaching solution containing tungsten and vanadium to the raw material tank 1, and the first dryer 4 is used for drying the leaching slag containing titanium dioxide to obtain titanium-rich slag;
the alkaline extraction system is used for separating tungsten and vanadium, and comprises an extraction tank 5, a washing tank 6 and a back extraction tank 7 which are sequentially connected, wherein the extraction tank 5 is used for enabling leachate containing tungsten and vanadium obtained by the belt filter 3 to react with a blank organic phase to obtain a tungsten-rich organic phase and a vanadium-rich raffinate, the washing tank 6 is used for washing the tungsten-rich organic phase with pure water, and the back extraction tank 7 is used for reacting the washed tungsten-rich organic phase with a back extraction agent to obtain a tungsten-rich back extraction solution and a blank organic phase;
the product refining system is used for refining high-purity ammonium paratungstate and ammonium metavanadate, and comprises a tungsten making subsystem and a vanadium making subsystem, wherein the tungsten making subsystem comprises an ion exchange column 8, an evaporation crystallization kettle 9 and a second dryer 10 which are sequentially connected, the ion exchange column 8 is used for deeply removing vanadium from a tungsten-rich strip liquor obtained from a stripping tank 7, the evaporation crystallization kettle 9 is used for crystallizing the tungsten-rich strip liquor subjected to deep vanadium removal to obtain an ammonium paratungstate crystal, the second dryer 10 is used for drying the ammonium paratungstate crystal to obtain ammonium paratungstate, the vanadium making subsystem comprises a neutralization silicon removal kettle 11, a vanadium precipitation reaction kettle 12 and a third dryer 13 which are sequentially connected, the neutralization silicon removal kettle 11 is used for precipitating and removing silicon from the vanadium-rich strip liquor obtained from an extraction tank 5, and the vanadium precipitation raffinate reaction kettle 12 is used for precipitating the vanadium-rich strip liquor subjected to silicon removal to obtain an ammonium metavanadate precipitate, the third dryer 13 is used for drying the ammonium metavanadate precipitate to obtain ammonium metavanadate.
In the preferred embodiment of the present invention, as shown in FIG. 1, the outlet of the washing tank 6 is also connected to the inlet of the neutralization desiliconization vessel 11 for allowing the washing water to flow into the neutralization desiliconization vessel.
In the preferred embodiment of the present invention, as shown in fig. 1, the outlet of the stripping tank 7 is further connected to the inlet of the extraction tank 5 for returning the blank organic phase to the extraction tank for recycling.
In the preferred embodiment of the present invention, as shown in FIG. 1, the outlet of the ion exchange column 8 is also connected to the inlet of the neutralization desiliconization vessel 11 for flowing the vanadium-removing liquid into the neutralization desiliconization vessel.
Adopt the utility model discloses a valuable metal alkaline extraction recovery technology of SCR denitration spent catalyst, as shown in figure 1, include following step:
s1, NaOH leaching: uniformly mixing the ash-cleaned and crushed SCR denitration waste catalyst powder, NaOH and water in a raw material tank 1 to form mixed slurry, feeding the mixed slurry into a high-pressure leaching kettle 2, providing a certain temperature and pressure (higher temperature and pressure) by the high-pressure leaching kettle 3 to enable the mixed slurry to react to leach tungsten and vanadium, performing solid-liquid separation on the reacted slurry by a belt filter 3 to obtain a leaching solution containing tungsten and vanadium and leaching slag containing titanium dioxide, drying the leaching slag containing titanium dioxide by a first dryer 4 to obtain high-titanium slag, and returning the leaching solution containing tungsten and vanadium to the raw material tank 1 for leaching;
s2, alkaline extraction: the leachate containing tungsten and vanadium obtained in the step S1 directly contacts with a blank organic phase put into the extraction tank 5 to carry out multistage extraction of tungsten to obtain a tungsten-rich organic phase and a vanadium-rich raffinate, the tungsten-rich organic phase enters the washing tank 6 to be subjected to multistage counter-current washing by pure water, and then contacts with a stripping agent in the stripping tank 7 to carry out multistage counter-extraction of tungsten to obtain a tungsten-rich stripping solution and a blank organic phase;
s3, refining the product: after the tungsten-rich strip liquor obtained in the step S2 is subjected to deep vanadium removal through the ion exchange column 8, ammonium paratungstate crystals are obtained by crystallization in the evaporation crystallization kettle 9, the ammonium paratungstate crystals are dried by the second dryer 10 to obtain ammonium paratungstate meeting the national standard, the vanadium-rich raffinate obtained in the step S2 enters the neutralization and silicon removal kettle 11 to be precipitated and silicon removed, and then ammonium metavanadate precipitate is obtained by precipitation in the vanadium precipitation reaction kettle 12, and the ammonium metavanadate precipitate is dried by the third dryer 13 to obtain ammonium metavanadate meeting the national standard.
In the preferred embodiment of the present invention, as shown in fig. 1, in step S1, the mass ratio of water to the SCR denitration spent catalyst powder in the raw material tank 1 is 150% to 350%, and the amount of sodium hydroxide added is 10% to 40% of the mass of the SCR denitration spent catalyst powder when first leached and 5% to 20% of the mass of the SCR denitration spent catalyst powder when back leached.
In a preferred embodiment of the present invention, as shown in fig. 1, in step S1, the reaction temperature in the high-pressure leaching kettle 2 is 180 to 320 ℃, the reaction pressure is 1.0 to 2.5MPa, and the reaction time is 1 to 4 hours.
In a preferred embodiment of the present invention, as shown in fig. 1, in step S2, the components and the volume percentages of the components of the blank organic phase are 10% -60% of the polarity-improving agent and 10% -30% of the diluent, 10% -60%, wherein the extracting agent is CO3 2-Quaternary ammonium salts or HCO3 -One or two quaternary ammonium salts, the polarity improver is high-carbon alcohol, the diluent is kerosene, the flow ratio of a blank organic phase to a leaching solution containing tungsten and vanadium is 1/1-5/1, and the extraction stage number of the extraction tank is 2-12.
In the preferred embodiment of the present invention, as shown in fig. 1, in step S2, the flow ratio of the tungsten-rich organic phase to the pure water in the washing tank 6 is 4/1 to 8/1, and the number of washing steps is 2 to 10.
In the preferred embodiment of the present invention, as shown in fig. 1, in step S2, the stripping agent is a mixed solution of 2.0-3.5 mol/L ammonium bicarbonate and 0.5-1.5 mol/L ammonia water, the flow ratio of the tungsten-rich organic phase to the stripping agent is 1/1-5/1, and the number of stripping stages is 5-18.
The utility model discloses when specifically using, as shown in fig. 1, go on according to following step:
s1, NaOH leaching: the SCR denitration waste catalyst contains 5.04 percent of WO32.98% of V2O5And 86.47% TiO2The method comprises the steps of cleaning and crushing the waste catalyst into powder, adding 500kg of denitration waste catalyst powder into a raw material tank through a screw conveyor, adding 100kg of sodium hydroxide and 1500L of water, uniformly stirring to form slurry, conveying the slurry to a high-pressure leaching kettle through a pump, arranging a steam heating system on the high-pressure leaching kettle, leaching for 2 hours at the temperature of 300 ℃, reacting tungsten and vanadium with NaOH to leach the tungsten and vanadium, conveying the reacted slurry to a belt filter for washing and filtering to obtain a leaching solution containing tungsten and vanadium and leaching slag containing titanium dioxide, returning the leaching solution to the raw material tank, adding 500kg of denitration waste catalyst powder and 50kg of sodium hydroxide, leaching the waste catalyst powder again, returning for 5 times to improve the concentration of tungsten and vanadium in the leaching solution and simultaneously realize the concentration of tungsten and vanadium in the leaching solution and the concentration of titanium dioxideThe existing water and alkali are recycled, and the obtained leachate contains 73.50g/L of WO3And V of 44.20g/L2O5The leachate enters an alkaline extraction system to further separate tungsten and vanadium, and leached slag is dried to obtain 2880kg of four-grade high titanium slag meeting the national standard;
s2, alkaline extraction: the leachate from step S1 was mixed with a blank organic phase (50% N263+ 25% sec-octanol + 25% sulfonated kerosene) (organic phase transformed to CO before extraction3 2-And HCO3 -Mixed type) are put into an extraction tank together, the extraction tank is provided with stirring, the two phases are quickly mixed and then separated, the volume flow ratio of an organic phase to a leaching solution is adjusted to 1/1, the tungsten is extracted by 8 levels, and the obtained raffinate contains 1.10g/L of WO3And V of 43.71g/L2O5The obtained tungsten-rich organic phase enters a washing tank, the flow ratio of the organic phase to pure water is adjusted to 6/1, 3-stage washing is carried out, and the washed tungsten-rich organic phase and a stripping agent (2mol/L NH)4HCO3+1mol/LNH4OH) enters a stripping tank together, the stripping tank is stirred to ensure that two phases are separated after being rapidly mixed, the volume flow ratio of an organic phase and a stripping agent is adjusted to 3/1, 8-grade stripping tungsten is carried out, and the obtained stripping solution contains WO3216.98g/L、V2O51.32g/L, returning the obtained blank organic phase to the extraction tank for recycling, and allowing the tungsten-rich strip liquor and the vanadium-rich raffinate to enter a product refining system to prepare high-purity ammonium paratungstate and ammonium metavanadate;
s3, refining the product: and (3) after the stripping solution from the step S2 is subjected to deep vanadium removal through an ion exchange column, crystallizing ammonium paratungstate in an evaporation crystallization kettle, drying to obtain 110kg of a national standard-meeting 0-grade ammonium paratungstate product, precipitating and removing silicon from the raffinate from the step S2 in a neutralization silicon removal kettle, precipitating vanadium in an ammonium salt in a vanadium precipitation reaction kettle to precipitate ammonium metavanadate, and drying to obtain 51kg of a national standard-meeting 98-grade ammonium metavanadate product.
The utility model firstly adopts NaOH solution to leach tungsten and vanadium of the SCR denitration waste catalyst into leachate, and titanium is left in leached slag to realize the separation of tungsten, vanadium and titanium; then, alkaline extraction is adopted to separate tungsten and vanadium; finally, the high-purity ammonium paratungstate and ammonium metavanadate which meet the national standard are obtained through the refining processes of crystallization, drying and the like, and the byproduct titanium-rich slag is obtained at the same time.
It will be understood that modifications and variations can be made by persons skilled in the art in light of the above teachings and all such modifications and variations are considered to be within the scope of the invention as defined by the following claims.
Claims (4)
1. An SCR denitration spent catalyst valuable metal alkaline extraction recovery device is characterized by comprising a NaOH leaching system, an alkaline extraction system and a product refining system; wherein,
the NaOH leaching system is used for separating tungsten, vanadium and titanium, and comprises a raw material tank, a high-pressure leaching kettle, a belt filter and a first dryer which are sequentially connected, wherein the raw material tank is used for fully mixing input SCR denitration waste catalyst powder subjected to ash removal and crushing with NaOH and water to form mixed slurry, the high-pressure leaching kettle is used for enabling the mixed slurry to react at a certain temperature and pressure to leach the tungsten and the vanadium, the belt filter is used for washing and filtering the reacted slurry to obtain leachate containing the tungsten and the vanadium and leaching slag containing titanium dioxide, an outlet of the belt filter is connected with an inlet of the raw material tank to return the leachate containing the tungsten and the vanadium to the raw material tank, and the first dryer is used for drying the leaching slag containing the titanium dioxide to obtain titanium-rich slag;
the alkaline extraction system is used for separating tungsten and vanadium, and comprises an extraction tank, a washing tank and a back extraction tank which are sequentially connected, wherein the extraction tank is used for enabling leachate containing tungsten and vanadium obtained by a belt filter to react with a blank organic phase to obtain a tungsten-rich organic phase and a vanadium-rich raffinate, the washing tank is used for washing the tungsten-rich organic phase with pure water, and the back extraction tank is used for reacting the washed tungsten-rich organic phase with a back extractant to obtain a tungsten-rich back extract and a blank organic phase;
the product refining system is used for refining high-purity ammonium paratungstate and ammonium metavanadate, and comprises a tungsten making subsystem and a vanadium making subsystem, wherein the tungsten making subsystem comprises an ion exchange column, an evaporation crystallization kettle and a second dryer which are sequentially connected, the ion exchange column is used for deeply removing vanadium from a tungsten-rich strip liquor obtained by a strip bath, the evaporation crystallization kettle is used for crystallizing the tungsten-rich strip liquor subjected to deep vanadium removal to obtain an ammonium paratungstate crystal, the second dryer is used for drying the ammonium paratungstate crystal to obtain ammonium paratungstate, the vanadium making subsystem comprises a neutralization silicon removal kettle, a vanadium precipitation reaction kettle and a third dryer which are sequentially connected, the neutralization silicon removal kettle is used for precipitating the vanadium-rich raffinate obtained by an extraction bath, and the vanadium precipitation reaction kettle is used for precipitating the vanadium-rich raffinate after silicon removal to obtain an ammonium metavanadate precipitate, and the third dryer is used for drying the ammonium metavanadate precipitate to obtain the ammonium metavanadate.
2. The apparatus of claim 1, wherein the outlet of the washing tank is further connected with the inlet of the neutralization desiliconization kettle for allowing washing water to flow into the neutralization desiliconization kettle.
3. The apparatus of claim 1, wherein the outlet of the stripping tank is further connected to the inlet of the extraction tank for returning the empty organic phase to the extraction tank for recycling.
4. The apparatus of claim 1, wherein the outlet of the ion exchange column is further connected to the inlet of the neutralization desilication kettle for flowing the vanadium removal liquid into the neutralization desilication kettle.
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| CN106435197A (en) * | 2016-12-09 | 2017-02-22 | 武汉凯迪电力环保有限公司 | Process and device for alkaline extraction and recovery from waste catalysts in SCR (selective catalytic reduction) denitrification |
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| CN106435197A (en) * | 2016-12-09 | 2017-02-22 | 武汉凯迪电力环保有限公司 | Process and device for alkaline extraction and recovery from waste catalysts in SCR (selective catalytic reduction) denitrification |
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