CN106947864A - A kind of system and its processing method that heavy metal is reclaimed from discarded SCR catalyst - Google Patents
A kind of system and its processing method that heavy metal is reclaimed from discarded SCR catalyst Download PDFInfo
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- 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
- C22B7/009—General processes for recovering metals or metallic compounds from spent catalysts
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- 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
- C22B13/00—Obtaining lead
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
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- 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
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- 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
- C22B34/34—Obtaining molybdenum
- C22B34/345—Obtaining molybdenum from spent catalysts
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- 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
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B43/00—Obtaining mercury
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B61/00—Obtaining metals not elsewhere provided for in this subclass
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- 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
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Abstract
The invention provides a kind of system and its processing method that heavy metal is reclaimed from discarded SCR catalyst, the system includes elution system, Waste Water Treatment and useless solid processing system, wherein, the liquid-phase outlet of elution system is connected with Waste Water Treatment, and the solid-phase outlet of elution system is connected with useless solid processing system.Discarded SCR catalyst removes surface laying dust through elution system of the present invention, reclaims high purity vanadic anhydride and sodium molybdate through useless solid processing system, realizes that vanadium, tungsten, molybdenum are efficiently separated.Its technique waste water and elution waste water are enriched with through the magnetic nanometer adsorbent in Waste Water Treatment, are greatly improved poisonous and harmful metal recovery recycling in waste water and are worth, the metal such as arsenic, mercury, chromium, thallium in recyclable sewage.Useless solid processing system leached mud titanium dioxide reuse is used as magnetic absorption agent carrier in Waste Water Treatment.The technique is discharged without secondary residue, waste water, can reach the good result of various material closed cycles in denitrating flue gas industrial chain.
Description
Technical field
The invention belongs to discard SCR catalyst recovery technology field, it is related to a kind of system and its processing method that heavy metal is reclaimed from discarded SCR catalyst, more particularly to discarding system and its processing method that the heavy metal that SCR catalyst is rich in and surface is carried is reclaimed.
Background technology
China is the energy resource consumption big country based on thermal power generation, and a large amount of nitrogen oxides (NO are produced in coal combustion processx).This kind of compound is one of major pollutants of atmospheric environment, and serious harm is brought to global ecological environment and human lives.To control the discharge of oxynitrides, national environmental protection portion regulation should build flue gas denitrification equipment after thermal power plant uses low-NO_x combustion technology when discharged nitrous oxides concentration is unsatisfactory for overall control requirement.SCR (SCR) technology is because of denitration efficiency height by domestic and international power plant's extensive use.
The catalyst of coal fired power plant SCR system is the core of system.The initial cost cost of catalyst accounts for the 40~60% of project investment, therefore catalyst will cause the dramatic increase of denitrating system cost once failing.In addition, SCR catalyst contains in substantial amounts of heavy metal, such as vanadium, tungsten, molybdenum and titanium, its surface laying dust also containing a large amount of toxic heavy metals such as arsenic, mercury, beryllium, thallium in itself.Such as without recycling, the waste catalyst is by severe contamination environment.Therefore, drastically increasing with domestic discarded SCR catalyst quantity, the recycling to this kind of resource is significant.
China handles waste and old SCR catalyst and started late, CN 102936049A propose that one kind extracts tungsten from discarded SCR catalyst, titanium, the method of vanadium, discarded SCR catalyst is crushed and add strong base solution by this method is reacted, strong acid is added into sodium tungstate after being separated by filtration, wolframic acid and sodium salt are reacted to obtain in sodium vanadate mixed solution, vanadic acid mixed solution, and by sodium salt, the pH value of vanadic acid mixed solution is adjusted to Precipitation and obtains ammonium vanadate, sulfuric acid is added into de- tungsten again, the solid such as titanyl sulfate solution and aluminium slag is reacted to obtain in the SCR catalyst of vanadium, continue the addition water in titanyl sulfate solution and metatitanic acid and waste acid liquor is hydrolyzed to obtain, finally by obtained ammonium vanadate, wolframic acid, metatitanic acid carries out calcining respectively can obtain vanadic anhydride, tungstic acid and titanium dioxide.CN 103508491A disclose a kind of discarded honeycomb type denitrification catalyst regeneration and resource utilization method, and this method uses sodium roasting, then hydrolyzes the leachate that roasting material is similarly obtained the acid containing heavy metal.
Above method extracts the heavy metals such as vanadium, tungsten and titanium from SCR catalyst, and low for equipment requirements.But above-mentioned technique is only capable of processing recovery Pd, vanadium and the more heavy metal of tungsten equal size, other heavy metals are then entered in waste discharge.Cause to be to reclaim certain heavy metal species, more serious secondary pollution is caused actually on surface.The country also has part producer to be handled using the precipitation method the technique waste water, although realizes emission reduction sewage, but generates precipitated metal, again results in secondary poisonous waste residue.And a large amount of soda acids are consumed, production efficiency is low.
The content of the invention
For the deficiencies in the prior art, the invention provides a kind of system and its processing method that heavy metal is reclaimed from discarded SCR catalyst, the system and method is while the noble metal vanadium in reclaiming discarded SCR catalyst, tungsten and molybdenum, the waste water that handling process is produced, the significantly concentration of heavy metal in waste water concentration is realized by magnetic enrichment, and then carries out classification recovery.Both utilization of waste as resource is realized, and does not produce secondary pollution waste water and waste residue.High-purity vanadium and molybdenum is reclaimed simultaneously, available for the production of expensive SCR catalyst regeneration.
For up to this purpose, the present invention uses following technical scheme：
First aspect, the invention provides a kind of system that heavy metal is reclaimed from discarded SCR catalyst, the system includes elution system, Waste Water Treatment and useless solid processing system, wherein, the liquid-phase outlet of elution system is connected with Waste Water Treatment, and the solid-phase outlet of elution system is connected with useless solid processing system.
Below as currently preferred technical scheme, but the limitation of the technical scheme provided not as the present invention, by the following technical programs, it can preferably reach and realize the technical purpose and beneficial effect of the present invention.
As currently preferred technical scheme, the Waste Water Treatment includes filter, magnetic enrichment device, combined separation device and solid phase sludge processing system；
Wherein, the liquid-phase outlet of filter is sequentially connected with magnetic enrichment device and combined separation device, and the solid-phase outlet of filter is connected with solid phase sludge processing system.
Preferably, the magnetic enrichment device includes magnetic enrichment device and enrichment liquid storage tank.
Preferably, magnetic nanometer adsorbent is used in the magnetic enrichment device.
Preferably, the magnetic nanometer adsorbent is any one in nano level active charcoal, alumina in Nano level, nano silicone diatomaceous earth and nanoscale resin sorbent or at least two combination, and the typical but non-limiting example of combination has：The combination of nano level active charcoal and alumina in Nano level, alumina in Nano level and the diatomaceous combination of nanoscale, the combination of nano silicone diatomaceous earth and nanoscale resin sorbent, the diatomaceous combination of nano level active charcoal, alumina in Nano level and nanoscale, nano level active charcoal, alumina in Nano level, combination of nano silicone diatomaceous earth and nanoscale resin sorbent etc..
Preferably, carrier is titaniferous magnetic particle in the magnetic enrichment device.
Preferably, the liquid-phase outlet of the combined separation device is connected with the liquid inlet of elution system, i.e. purification waste water circulation to the elution system that the processing of combined separation device is obtained carries out reuse.
Preferably, the combined separation device is made up of any one in adsorbing separation device, extraction separator, whizzer or precipitation separator or at least two, and the combination is typical but non-limiting examples have：It is made up of adsorbing separation device and extraction separator, it is made up of extraction separator and whizzer, it is made up of whizzer and precipitation separator, it is made up of adsorbing separation device and precipitation separator, it is made up of, is made up of adsorbing separation device, extraction separator, whizzer and precipitation separator adsorbing separation device, whizzer and precipitation separator.
Preferably, the solid phase sludge processing system includes the multistage water logging tower, the first filter and biodegradable pond being sequentially connected, wherein, the solid-phase outlet of the first filter is connected with the feed entrance in biodegradable pond, and the liquid-phase outlet of the first filter is connected with the liquid phase entrance of magnetic enrichment device.
As currently preferred technical scheme, the useless solid processing system includes reducing mechanism, the first roaster, water logging groove, the second filter and the extracting system of connection, wherein the first roaster is high-temperature roasting furnace, its sintering temperature is up to 800 DEG C.
Preferably, the solid-phase outlet of second filter is connected with desalter and titanium slag storage tank successively, and the discharging opening of titanium slag storage tank is connected with the adsorbent entrance of magnetic enrichment device, i.e., the titanium dioxide titanium slag in titanium slag storage tank is used as the raw material in magnetic enrichment device.
Preferably, the extracting system includes vanadium extraction tower, tungsten extraction tower, destilling tower and the condenser being sequentially connected in series, the extracting system also includes the first back extraction tower and the second back extraction tower, the organic phase discharging opening of vanadium extraction tower is connected with the organic phase charging aperture of the first back extraction tower, and the organic phase discharging opening of tungsten extraction tower is connected with the organic phase charging aperture of the second back extraction tower.
Preferably, the extracting system includes vanadium extractant groove and tungsten extractant groove, and the discharging opening of vanadium extractant groove is connected with the organic phase charging aperture of vanadium extraction tower, and the discharging opening of tungsten extractant groove is connected with the organic phase charging aperture of tungsten extraction tower；The organic phase discharging opening of first back extraction tower is connected with the charging aperture of vanadium extractant groove, and the organic phase discharging opening of the second back extraction tower is connected with the charging aperture of tungsten extractant groove.
Preferably, the extracting system includes the second roaster, and the solid-phase outlet of the first back extraction tower is connected with the charging aperture of the second roaster.
Preferably, the liquid-phase outlet of second filter is connected with the liquid phase entrance of the vanadium extraction tower of extracting system.
Preferably, the first back extraction tower, the second back extraction tower and the liquid-phase outlet of condenser are connected with the liquid inlet of elution system.
As currently preferred technical scheme, the liquid-phase outlet of the elution system is connected with the charging aperture of the filter of Waste Water Treatment, and the solid-phase outlet of elution system is connected with the charging aperture of the reducing mechanism of useless solid processing system.
Second aspect, the invention provides a kind of method that heavy metal is reclaimed from discarded SCR catalyst, the described method comprises the following steps：
(1) elution processing is carried out to discarded SCR catalyst, obtains eluent and elution solid；
(2) eluent that step (1) is obtained carries out filtration treatment, and the filtrate that filtration treatment is obtained obtains heavy metal product through magnetic enrichment and combined separation, and the purification waste water circulation obtained through combined separation carries out elution processing；The filter residue that filtration treatment is obtained handles through solid phase sludge and obtains harmless sludge；
(3) step (1) is obtained elution solid is size-reduced, roasting, water logging and filtration treatment obtain leached mud and leachate, and leached mud obtains titanium slag after desalting processing, and leachate isolates vanadium, tungsten and sodium molybdate through extraction processing.
Wherein, elution processing is carried out in step (1) to discarded SCR catalyst it is to remove the surface laying dust of discarded SCR catalyst；Magnetic enrichment in step (2) can concentrate the harmful heavy metal in sewage, the metals such as arsenic, mercury, molybdenum, chromium and thallium in technique waste water are isolated in combined separation processing, pollutant and heavy metal in solid phase sludge processing removing sludge, its harmless sludge discharged is non-burning brick available for preparing, and is used available for engineering constructions such as sewage disposals；Desalting processing in step (3) is primarily to removing sodium salt.
As currently preferred technical scheme, magnetic enrichment uses magnetic nanometer adsorbent in step (2).
Preferably, the magnetic nanometer adsorbent is any one in nano level active charcoal, alumina in Nano level, nano silicone diatomaceous earth and nanoscale resin sorbent or at least two combination, and the typical but non-limiting example of combination has：The combination of nano level active charcoal and alumina in Nano level, alumina in Nano level and the diatomaceous combination of nanoscale, the combination of nano silicone diatomaceous earth and nanoscale resin sorbent, the diatomaceous combination of nano level active charcoal, alumina in Nano level and nanoscale, nano level active charcoal, alumina in Nano level, combination of nano silicone diatomaceous earth and nanoscale resin sorbent etc..
Preferably, the carrier that magnetic enrichment is used in step (2) is titaniferous magnetic particle.
It is used as currently preferred technical scheme, the processing of solid phase sludge described in step (2) includes multistage Soaking treatment, filtration treatment and biodegradable processing successively, wherein, solid phase sludge can remove most metal ion in sludge through multistage Soaking treatment, and organic pollution and a small amount of heavy metal can further be removed by carrying out biodegradable processing after filtration treatment through the sludge of multistage Soaking treatment.
Preferably, the filtrate cycle that filtration treatment is obtained in the solid phase sludge processing procedure carries out the heavy metal carried secretly in magnetic enrichment processing, removing sludge, it is to avoid secondary pollution.
As currently preferred technical scheme, it is roasted in step (3) and carries out sodium roasting with alkaline mixt；
Preferably, the alkaline mixt is any one in NaOH, calcium hydroxide, sodium carbonate or at least two combination, and the typical but non-limiting example of combination has：The combination of the combination of NaOH and calcium hydroxide, calcium hydroxide and sodium carbonate, combination of NaOH, calcium hydroxide and sodium carbonate etc..
Preferably, the temperature of the roasting is 400~800 DEG C, such as 400 DEG C, 500 DEG C, 600 DEG C, 700 DEG C or 800 DEG C, but is not limited to cited numerical value, and other temperature values in the range of being given are feasible.
Preferably, the time of the roasting is 1~3h, such as 1h, 1.5h, 2h, 2.5h or 3h, but is not limited to cited numerical value, and other temperature values in the range of being given are feasible.
Preferably, the titanium slag that the step (3) obtains is returned as the absorption carrier raw material in magnetic enrichment.
As currently preferred technical scheme, the method for extracting vanadium is method in CN 103540745A in step (3) extraction processing, and process is as follows：
(a) acid is added in obtained leachate, form the heteropoly acids such as phosphorus tungsten, phosphorus tungsten vanadium, silicon tungsten, molybdenum vanadium arsenic and tungsten arsenic, solution impurities, the raffinate containing vanadium purified are removed using the heteropoly acid in amine extractant and synergic reagent compounding synergic solvent extraction leachate；
(b) it is 20~60g/L that will contain vanadium raffinate to be concentrated by evaporation to vanadium unit cellulose content, adds ammonium salt and obtains ammonium metavanadate solid, then obtains the vanadic anhydride that purity is more than 99.99% by the calcining of pure water, drying and oxygen atmosphere；Organic phase can be stripped regeneration cycle using aqueous slkali.
Preferably, the method for step (3) extraction processing separating tungsten and sodium molybdate is method in CN 103320612A, and process is as follows：
The salting liquid containing tungsten that the organic extractant phase being made into using serotonin-hydroxyl oxime extractant and diluent is obtained after being handled through extracting vanadium, salting liquid containing tungsten adjusts pH value in the range of 3~6 with diluted acid or dilute alkaline soln before extraction, and mix organic phase with salting liquid containing tungsten in the case where temperature is 10~50 DEG C, go out tungsten through extracting and being stripped processing sub-argument, the organic phase that back extraction processing is obtained is regenerated, high-purity sodium molybdate can be made in raffinate evaporative crystallization, and tungsten separation is more than 105。
As currently preferred technical scheme, it the described method comprises the following steps：
(1) discard SCR catalyst and carry out elution processing in elution system, obtain eluent and elution solid；
(2) filter that the eluent that step (1) is obtained enters in Waste Water Treatment carries out filtration treatment, the filtrate that filtration treatment is obtained carries out progress combined separation in magnetic enrichment and combined separation device in magnetic enrichment device and obtains heavy metal product, and the purification waste water circulation obtained through combined separation to elution system carries out elution processing；The filter residue that filtration treatment is obtained enters in solid phase sludge processing system obtains harmless sludge through multistage water logging tower, the first filter and biodegradable pond processing；
(3) the size-reduced device of elution solid that step (1) is obtained is crushed, first roaster is calcined, water logging, which is carried out, in water logging groove obtains leached mud and leachate through the second filter filtration treatment again, leached mud obtains titanium slag after carrying out desalting processing through desalter, leachate goes out vanadium through the second roaster baking separation again in extracting system through vanadium extraction tower and the first back extraction tower processing, raffinate is in extracting system through tungsten extraction tower (16), tungsten and sodium molybdate are isolated in second back extraction tower (21) and destilling tower (17) processing, technique waste water is recycled back to washing device reuse.
Compared with prior art, the invention has the advantages that：
(1) heavy metal in the waste water that processing system and method for the present invention will can be produced in discarded SCR catalyst and discarded SCR catalyst processing procedure is all recycled, realize various material closed cycles in denitrating flue gas industrial chain, increase utilization of resources value, it is to avoid secondary environmental pollution.
(2) present invention through magnetic enrichment can significantly concentration technology heavy metal in waste water concentration, improve heavy metal in waste water recycling value, and the higher magnetic absorption agent carrier of cost used in the process of magnetic enrichment also from the system and method in itself, and recoverable.Classical acid, alkali precipitation concentration method are compared, the method for the invention is simple, pollution-free, and cost is greatly reduced.
(3) through system and method for the present invention, the rate of recovery that vanadium, tungsten and molybdenum in discarded SCR catalyst can be made is respectively 90%, 89% and more than 87%, the purity of obtained vanadium metal is reclaimed up to more than 99.9wt%, the purity of tungsten is up to more than 99wt%, and the purity of sodium molybdate is up to 99.99wt%；Meanwhile, the rate of recovery of the metal such as arsenic, mercury, lead and thallium is more than 86%, and the purity of the metal such as arsenic, mercury, lead and thallium that recovery is obtained also is more than 85wt%.The added value of metal is higher, realizes the secondary higher value application of waste resource.
(4) applicability of system and method for the present invention is wide.Because that can be separated to the tungsten and molybdenum of more difficult separation, so the technique can also handle the V of conventional application2O5-WO3/TiO2, V2O5-MoO3/TiO2V2O5-WO3-MoO3/TiO2Etc. a variety of dead catalyst systems.
Brief description of the drawings
Fig. 1 is the system and device schematic diagram of the present invention that heavy metal is reclaimed from discarded SCR catalyst；
Wherein, 1- elution systems, 2- filters, 3- magnetic enrichment devices, 4- is enriched with liquid storage tank, 5- combined separation devices, 6- multistage water logging towers, the filters of 7- first, 8- biodegradations pond, 9- reducing mechanisms, the roasters of 10- first, 11- water logging grooves, the filters of 12- second, 13- desalters, 14- titanium slag storage tanks, 15- vanadium extraction towers, 16- tungsten extraction towers, 17- destilling towers, 18- vanadium extractant grooves, 19- tungsten extractant grooves, 20- first is stripped tower, the back extraction towers of 21- second, 22- condensers, the roasters of 23- second.
Embodiment
Below in conjunction with several specific embodiments; exemplary illustration and help further understand the present invention; but embodiment detail is merely to the explanation present invention; whole technical schemes under present inventive concept are not represented; therefore it should not be construed as the technical scheme total to the present invention to limit, some are changed in technical staff without departing from the unsubstantiality of inventive concept; for example simply change or replace with the technical characteristic with same or similar technique effect, belong to the scope of the present invention.
As shown in Figure 1, the invention provides a kind of system that heavy metal is reclaimed from discarded SCR catalyst, the system includes elution system 1, Waste Water Treatment and useless solid processing system, wherein, the liquid-phase outlet of elution system 1 is connected with Waste Water Treatment, and the solid-phase outlet of elution system 1 is connected with useless solid processing system.
The Waste Water Treatment includes filter 2, magnetic enrichment device, combined separation device 5 and solid phase sludge processing system, wherein, the liquid-phase outlet of filter 2 is sequentially connected with magnetic enrichment device and combined separation device 5, the solid-phase outlet of filter 2 is connected with solid phase sludge processing system, and the liquid-phase outlet of combined separation device 5 is connected with the liquid inlet of elution system 1.
The magnetic enrichment device includes magnetic enrichment device 3 and enrichment liquid storage tank 4, and magnetic nanometer adsorbent is used wherein in magnetic enrichment device 3.
The magnetic nanometer adsorbent is any one in nano level active charcoal, alumina in Nano level, nano silicone diatomaceous earth and nanoscale resin sorbent or at least two combination.
Carrier is titaniferous magnetic particle in the magnetic enrichment device 3.
The combined separation device 5 is adsorbing separation device, extraction separator, whizzer or precipitates any one in separator or at least two combination.
The solid phase sludge processing system includes the multistage water logging tower 6, the first filter 7 and biodegradable pond 8 being sequentially connected, wherein, the solid-phase outlet of first filter 7 is connected with the feed entrance in biodegradable pond 8, and the liquid-phase outlet of the first filter 7 is connected with the liquid phase entrance of magnetic enrichment device 3.
The useless solid processing system includes reducing mechanism 9, the first roaster 10, water logging groove 11, the second filter 12 and the extracting system of connection.
The solid-phase outlet of second filter 12 is connected with desalter 13 and titanium slag storage tank 14 successively, and the discharging opening of titanium slag storage tank 14 is connected with the adsorbent material entrance of magnetic enrichment device.
The extracting system includes vanadium extraction tower 15, tungsten extraction tower 16, destilling tower 17 and the condenser 22 being sequentially connected in series, the extracting system also includes the first back extraction tower and the second back extraction tower, the organic phase discharging opening of vanadium extraction tower is connected with the organic phase charging aperture of the first back extraction tower, and the organic phase discharging opening of tungsten extraction tower is connected with the organic phase charging aperture of the second back extraction tower.
The extracting system also includes vanadium extractant groove 18 and tungsten extractant groove 19, and the discharging opening of vanadium extractant groove 18 is connected with the organic phase charging aperture of vanadium extraction tower 15, and the discharging opening of tungsten extractant groove 19 is connected with the organic phase charging aperture of tungsten extraction tower 16；The organic phase discharging opening of first back extraction tower 20 is connected with the charging aperture of vanadium extractant groove 18, and the organic phase discharging opening of the second back extraction tower 21 is connected with the charging aperture of tungsten extractant groove 19.
The extracting system also includes the second roaster 23, and the solid-phase outlet of the first back extraction tower 20 is connected with the charging aperture of the second roaster 23.
The liquid-phase outlet of second filter 12 is connected with the liquid phase entrance of the vanadium extraction tower 15 of extracting system.
The liquid-phase outlet of first back extraction tower 20, the second back extraction tower 21 and condenser 22 is connected with the liquid inlet of elution system 1.
Embodiment 1：
Present embodiments provide a kind of system that heavy metal is reclaimed from discarded SCR catalyst, the system includes elution system 1, Waste Water Treatment and useless solid processing system, wherein, the liquid-phase outlet of elution system 1 is connected with the charging aperture of the filter 2 of Waste Water Treatment, and the solid-phase outlet of elution system 1 is connected with the charging aperture of the reducing mechanism 9 of useless solid processing system.
The Waste Water Treatment includes filter 2, magnetic enrichment device, combined separation device 5 and solid phase sludge processing system, wherein, the liquid-phase outlet of filter 2 is sequentially connected with magnetic enrichment device and combined separation device 5, the solid-phase outlet of filter 2 is connected with solid phase sludge processing system, and the liquid-phase outlet of combined separation device 5 is connected with the liquid inlet of elution system 1.
The magnetic enrichment device includes magnetic enrichment device 3 and enrichment liquid storage tank 4, using the mixture of alumina in Nano level and nanoscale resin sorbent as magnetic nanometer adsorbent wherein in magnetic enrichment device 3, and carrier is titaniferous magnetic particle in the magnetic enrichment device 3.
The combined separation device 5 is the combination of adsorbing separation device and precipitation separator.
The solid phase sludge processing system includes the multistage water logging tower 6, the first filter 7 and biodegradable pond 8 being sequentially connected, wherein, the solid-phase outlet of first filter 7 is connected with the feed entrance in biodegradable pond 8, and the liquid-phase outlet of the first filter 7 is connected with the liquid phase entrance of magnetic enrichment device.
The useless solid processing system includes reducing mechanism 9, the first roaster 10, water logging groove 11, the second filter 12 and the extracting system of connection.
The solid-phase outlet of second filter 12 is connected with desalter 13 and titanium slag storage tank 14 successively, and the discharging opening of titanium slag storage tank 14 is connected with the liquid inlet of magnetic enrichment device.
The extracting system includes vanadium extraction tower 15, tungsten extraction tower 16, destilling tower 17 and the condenser 22 being sequentially connected in series, the extracting system also includes the first back extraction back extraction tower 21 of tower 20 and second, the organic phase discharging opening of vanadium extraction tower 15 is connected with the organic phase charging aperture of the first back extraction tower 20, and the organic phase discharging opening of tungsten extraction tower 16 is connected with the organic phase charging aperture of the second back extraction tower 21.
The extracting system also includes vanadium extractant groove 18 and tungsten extractant groove 19, and the discharging opening of vanadium extractant groove 18 is connected with the organic phase charging aperture of vanadium extraction tower 15, and the discharging opening of tungsten extractant groove 19 is connected with the organic phase charging aperture of tungsten extraction tower 16；The organic phase discharging opening of first back extraction tower 20 is connected with the charging aperture of vanadium extractant groove 18, and the organic phase discharging opening of the second back extraction tower 21 is connected with the charging aperture of tungsten extractant groove 19.
The extracting system also includes the second roaster 23, and the solid-phase outlet of the first back extraction tower 20 is connected with the charging aperture of the second roaster 23.
The liquid-phase outlet of second filter 12 is connected with the liquid phase entrance of the vanadium extraction tower 15 of extracting system.
The liquid-phase outlet of first back extraction tower 20, the second back extraction tower 21 and condenser 22 is connected with the liquid inlet of elution system 1.
Embodiment 2：
Except the mixture in magnetic enrichment device 3 using nano level active charcoal, alumina in Nano level and nanoscale resin sorbent is used as magnetic nanometer adsorbent, the combined separation device 5 is that the connected mode of other apparatus structures and device is in the same manner as in Example 1 outside adsorbing separation device, extraction separator and the combination for precipitating separator.
Embodiment 3：
Except using nanoscale resin sorbent in magnetic enrichment device 3 as magnetic nanometer adsorbent, the combined separation device 5 is that the connected mode of other apparatus structures and device is in the same manner as in Example 1 outside whizzer.
Embodiment 4：
Except using nano silicone diatomaceous earth in magnetic enrichment device 3 as magnetic nanometer adsorbent, the combined separation device 5 is that the connected mode of other apparatus structures and device is in the same manner as in Example 1 outside adsorbing separation device.
Embodiment 5：
The present embodiment is reclaimed in discarded SCR catalyst using the system described in embodiment 1 and reclaims heavy metal.
Discarded SCR catalyst used is with TiO in the present embodiment2For carrier, with V2O5-WO3For active component, belong to metal-oxide catalyst, honeycomb fashion.The SCR catalyst surface abrasion, arsenic poisoning is serious, non-renewable.Enrichment shows to adsorb a large amount of laying dusts in denitrification process, and specific heavy metal component and content are shown in Table 1.
Processing method is as follows：
(1) discarded SCR catalyst feeding elution system 1 is subjected to elution processing and removes surface laying dust, obtain eluent and elution solid；
(2) after the eluent that step (1) is obtained removes solid sludges through filter 2, the harmful heavy metal content that the liquid being filtrated to get enters in the concentration sewage of magnetic enrichment device 3, pregnant solution enters the metals such as arsenic, mercury, lead and thallium that enrichment liquid storage tank 4 goes out in technique waste water through the combined separation of combined separation device 5 again, and the heavy metal purity of recovery is referring to table 2.Waste water (concentration is referring to table 1) after the purification that combined separation device 5 is discharged is circulated utilization into elution system 1.
The solid sludges being filtrated to get through filter 2 are through multistage water logging tower 6, the first filter 7 and the biodegradable processing of pond 8 removing pollutant and heavy metal, and the harmless sludge of discharge is prepared non-burning brick (its content of beary metal is referring to table 1)；The heavy metal-containing waste water feeding magnetic enrichment device 3 discharged through a filter 7 is handled.
(3) the size-reduced device 9 of elution solid that step (1) is obtained is crushed, and sodium roasting is carried out into the first roaster 10, and then carry out water logging in water logging groove 11 obtains leached mud and leachate through the filtration treatment of the second filter 12 again.Leached mud removes sodium salt through desalter 13, and into titanium slag storage tank 14, the purification titanium slag in titanium slag storage tank 14 is recycled into magnetic enrichment device 3 as adsorbing agent carrier.Leachate goes out high purity vanadium through the baking separation of the second roaster 23 again through the back extraction of vanadium extraction tower 15 and first extraction processing of tower 20；The raffinate for isolating vanadium goes out tungsten through the back extraction of tungsten extraction tower 16 and second sub-argument of tower 21, raffinate crystallizes out high-purity sodium molybdate through destilling tower 17, the condensed device 22 of vapor distilled out is condensed into liquid phase, the liquid discharged with the first back extraction back extraction tower 21 of tower 20, second enters the reuse of elution pool 1, and the purity of isolated high purity vanadium, tungsten and high-purity sodium molybdate is referring to table 2.
Wherein, vanadium extractant is the mixture of primary amine N1923, oximes extractant LIX63, n-octyl alcohol and kerosene, and its concentration of volume percent is respectively 4%, 0.7%, 0.8% and 94.5%.Extraction conditions：25 DEG C of temperature, time 15min, load organic phase is using 5% NaOH back extraction regeneration, and ammonium chloride precipitation temperature is 30 DEG C, is stirred 120 minutes, is positioned over high temperature furnace and dries 3 hours.
Tungsten extractant is the mixture of primary amine Primene 81R, secondary amine 7202, BK992 and kerosene, and its volume ratio is respectively 1.5%, 0.5%, 0.5% and 97.5%.Extraction conditions：18 DEG C of temperature, time 20min, 10% NaOH back extraction 45min at 30 DEG C, organic phase regeneration.
As shown in table 1, the purity of obtained heavy metal product is as shown in table 2 for waste water after undressed discarded SCR catalyst in the present embodiment, and processing and the content of beary metal in product.
Table 1：Waste water after discarded SCR catalyst and processing and the content of beary metal table in product
Note："-" is represented and is not detected by.
Table 2：The purity table of heavy metal product
Embodiment 6：
The present embodiment is reclaimed in discarded SCR catalyst using the system described in embodiment 2 and reclaims heavy metal.
Discarded SCR catalyst used is with TiO in the present embodiment2For carrier, with V2O5-WO3-MoO3For active component, belong to metal-oxide catalyst, corrugated plate dst.The SCR catalyst is sintered and heat inactivation, non-renewable, and enrichment shows to adsorb a large amount of laying dusts in denitrification process, and specific heavy metal component and content are shown in Table 3.
Processing method is as follows：
Except vanadium extractant is primary amine N1923, oximes extractant LIX63, n-octyl alcohol and coal in step (3)
The mixture of oil, concentration of volume percent is respectively 4%, 0.7%, 0.8% and 94.5%；Tungsten extractant is the mixture of primary amine Primene 81R, secondary amine 7202, BK992 and kerosene, and volume ratio is respectively that outside 1.5%, 0.5%, 0.5% and 97.5%, other steps are in the same manner as in Example 5.
As shown in table 3, the purity of obtained heavy metal product is as shown in table 4 for waste water after undressed discarded SCR catalyst in the present embodiment, and processing and the content of beary metal in product.
Table 3：Waste water after discarded SCR catalyst and processing and the content of beary metal table in product
Note："-" is represented and is not detected by.
Table 4：The purity table of heavy metal product
Integrated embodiment 1-6 result can be seen that, through system and method for the present invention, the rate of recovery of vanadium, tungsten and molybdenum in discarded SCR catalyst can be made up to 90%, 89% and more than 87%, the purity of obtained vanadium metal is reclaimed up to more than 99.9wt%, the purity of tungsten is up to more than 99wt%, and the purity of sodium molybdate is up to 99.99wt%；Meanwhile, the rate of recovery of the metal such as arsenic, mercury, lead and thallium is more than 86%, and the purity of the metal such as arsenic, mercury, lead and thallium that recovery is obtained also is more than 85wt%, and the added value of metal is higher, realizes the secondary higher value application of waste resource.Simultaneously, the present invention through magnetic enrichment can significantly concentration technology heavy metal in waste water concentration, heavy metal in waste water recycling is improved to be worth, and the higher magnetic absorption agent carrier of the cost used in the process of magnetic enrichment also derives from the system and method in itself, and recoverable.Classical acid, alkali precipitation concentration method are compared, the method for the invention is simple, pollution-free, and cost is greatly reduced, realize various material closed cycles in denitrating flue gas industrial chain, increase utilization of resources value, it is to avoid secondary environmental pollution.
Applicant states that the present invention illustrates the method detailed of the present invention by above-described embodiment, but the invention is not limited in above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., within the scope of all falling within protection scope of the present invention and being open.
Claims (10)
1. a kind of system that heavy metal is reclaimed from discarded SCR catalyst, it is characterised in that the system
Including elution system (1), Waste Water Treatment and useless solid processing system, wherein, elution system (1)
Liquid-phase outlet is connected with Waste Water Treatment, the solid-phase outlet of elution system (1) and useless solid processing system phase
Even.
2. the system according to claim 1 for reclaiming heavy metal, it is characterised in that at the waste water
Reason system includes filter (2), magnetic enrichment device, combined separation device (5) and solid phase sludge processing system
System；
Wherein, the liquid-phase outlet of filter (2) and magnetic enrichment device and combined separation device (5) phase successively
Even, the solid-phase outlet of filter (2) is connected with solid phase sludge processing system；
Preferably, the magnetic enrichment device includes magnetic enrichment device (3) and enrichment liquid storage tank (4)；
Preferably, magnetic nanometer adsorbent is used in the magnetic enrichment device (3)；
Preferably, the magnetic nanometer adsorbent is nano level active charcoal, alumina in Nano level, nano silicone
Any one in diatomaceous earth and nanoscale resin sorbent or at least two combination；
Preferably, carrier is titaniferous magnetic particle in the magnetic enrichment device (3)；
Preferably, the liquid-phase outlet and the liquid inlet phase of elution system (1) of the combined separation device (5)
Even；
Preferably, the combined separation device (5) by adsorbing separation device, extraction separator, whizzer or
Precipitate any one in separator or at least two compositions；
Preferably, the solid phase sludge processing system includes multistage water logging tower (6), the first mistake being sequentially connected
Filter (7) and biodegradable pond (8), wherein, solid-phase outlet and the biodegradation of the first filter (7)
The feed entrance in pond (8) is connected, and the liquid phase of the liquid-phase outlet and magnetic enrichment device of the first filter (7) enters
Mouth is connected.
3. the system according to claim 1 or 2 for reclaiming heavy metal, it is characterised in that described useless solid
Reducing mechanism (9) of the processing system including connection, the first roaster (10), water logging groove (11), second
Filter (12) and extracting system；
Preferably, the solid-phase outlet of second filter (12) successively with desalter (13) and titanium slag
Storage tank (14) is connected, and the discharging opening of titanium slag storage tank (14) is connected with the adsorbent entrance of magnetic enrichment device；
Preferably, the extracting system includes vanadium extraction tower (15), the tungsten extraction tower being sequentially connected in series
(16), destilling tower (17) and condenser (22), the extracting system also include the first back extraction tower (20)
With the second back extraction tower (21), the organic phase discharging opening of vanadium extraction tower (15) and first is stripped tower (20)
Organic phase charging aperture is connected, and the organic phase discharging opening of tungsten extraction tower (16) has with the second back extraction tower (21)
Machine phase charging aperture is connected；
Preferably, the extracting system includes vanadium extractant groove (18) and tungsten extractant groove (19), vanadium extraction
The discharging opening of agent groove (18) is taken to be connected with the organic phase charging aperture of vanadium extraction tower (15), tungsten extractant groove (19)
Discharging opening be connected with the organic phase charging aperture of tungsten extraction tower (16)；The organic phase of first back extraction tower (20)
Discharging opening is connected with the charging aperture of vanadium extractant groove (18), the organic phase discharging opening of the second back extraction tower (21)
It is connected with the charging aperture of tungsten extractant groove (19)；
Preferably, the extracting system includes the second roaster (23), the solid phase of the first back extraction tower (20)
Outlet is connected with the charging aperture of the second roaster (23)；
Preferably, the vanadium extraction tower (15) of the liquid-phase outlet of second filter (12) and extracting system
Liquid phase entrance be connected；
Preferably, the liquid of the first back extraction tower (20), the second back extraction tower (21) and condenser (22)
Mutually outlet is connected with the liquid inlet of elution system (1).
4. the system of the recovery heavy metal according to Claims 2 or 3, it is characterised in that the elution
The liquid-phase outlet of system (1) is connected with the charging aperture of the filter (2) of Waste Water Treatment, elution system
The solid-phase outlet of system (1) is connected with the charging aperture of the reducing mechanism (9) of useless solid processing system.
5. a kind of method that heavy metal is reclaimed from discarded SCR catalyst, it is characterised in that methods described
Comprise the following steps：
(1) elution processing is carried out to discarded SCR catalyst, obtains eluent and elution solid；
(2) eluent that step (1) is obtained carries out filtration treatment, and the filtrate that filtration treatment is obtained is rich through magnetic
Collection and combined separation obtain heavy metal product, and the purification waste water circulation obtained through combined separation is carried out at elution
Reason；The filter residue that filtration treatment is obtained handles through solid phase sludge and obtains harmless sludge；
(3) step (1) is obtained elution solid is size-reduced, roasting, water logging and filtration treatment are leached
Slag and leachate, leached mud obtain titanium slag after desalting processing, and leachate isolates vanadium, tungsten through extraction processing
And sodium molybdate.
6. the method according to claim 5 for reclaiming heavy metal, it is characterised in that in step (2)
Magnetic enrichment uses magnetic nanometer adsorbent；
Preferably, the magnetic nanometer adsorbent is nano level active charcoal, alumina in Nano level, nano silicone
Any one in diatomaceous earth and nanoscale resin sorbent or at least two combination；
Preferably, the carrier that magnetic enrichment is used in step (2) is titaniferous magnetic particle.
7. the method for the recovery heavy metal according to claim 5 or 6, it is characterised in that step (2)
Described in solid phase sludge processing include multistage Soaking treatment, filtration treatment and biodegradable processing successively；
Preferably, the filtrate cycle that filtration treatment is obtained in the solid phase sludge processing procedure is carried out at magnetic enrichment
Reason.
8. the method for the recovery heavy metal according to claim any one of 5-7, it is characterised in that step
(3) it is roasted in and carries out sodium roasting with alkaline mixt；
Preferably, the alkaline mixt be NaOH, calcium hydroxide or sodium carbonate in any one or extremely
Few two kinds combination；
Preferably, the temperature of the roasting is 400~800 DEG C；
Preferably, the time of the roasting is 1~3h；
Preferably, the titanium slag that the step (3) obtains is returned as the absorption carrier raw material in magnetic enrichment.
9. the method for the recovery heavy metal according to claim any one of 5-8, it is characterised in that step
(3) method of extracting vanadium is in extraction processing：
(a) acid is added in leachate, heteropoly acid is formed, using amine extractant and synergic reagent synergic solvent extraction
Heteropoly acid in leachate removes solution impurities, the raffinate containing vanadium purified；
(b) it is 20~60g/L that will contain vanadium raffinate to be concentrated by evaporation to vanadium unit cellulose content, adds ammonium salt and obtains inclined vanadium
Sour ammonium solid, then five oxygen that purity is more than 99.99% are obtained by the calcining of pure water, drying and oxygen atmosphere
Change two vanadium；Organic phase is stripped regeneration cycle using aqueous slkali；
Preferably, the method for step (3) extraction processing separating tungsten and sodium molybdate is：
Obtained after being handled using serotonin-hydroxyl oxime extractant with the organic extractant phase that diluent is made into through extracting vanadium
Salting liquid containing tungsten, salting liquid containing tungsten adjusts pH value in the range of 3~6 before extraction, and in temperature
To mix organic phase with salting liquid containing tungsten at 10~50 DEG C, go out tungsten through extracting and being stripped processing sub-argument, instead
The organic phase that extraction processing is obtained is regenerated, and high-purity sodium molybdate is made in raffinate evaporative crystallization.
10. the method for the recovery heavy metal according to claim any one of 5-9, it is characterised in that institute
The method of stating comprises the following steps：
(1) discard SCR catalyst and carry out elution processing in elution system (1), obtain eluent and elution
Solid；
(2) filter (2) that the eluent that step (1) is obtained enters in Waste Water Treatment was carried out
Filter is handled, and the filtrate that filtration treatment is obtained is carried out in magnetic enrichment and combined separation device (5) in magnetic enrichment device
Carry out combined separation and obtain heavy metal product, the purification waste water circulation obtained through combined separation to elution system
(1) reuse is carried out；The filter residue that filtration treatment is obtained enters in solid phase sludge processing system through multistage water logging tower
(6), the first filter (7) and biodegradable pond (8) processing obtain harmless sludge；
(3) the size-reduced device of elution solid (9) that step (1) is obtained is crushed, the first roaster (10)
It is calcined, is leached again through the second filter (12) filtration treatment in water logging groove (11) progress water logging
Slag and leachate, leached mud obtain titanium slag after carrying out desalting processing through desalter (13), leachate is in extraction
Take in system and roasted again through the second roaster (23) through vanadium extraction tower (15) and the first back extraction tower (20) processing
Burning isolates vanadium, and raffinate through tungsten extraction tower (16), the second back extraction tower (21) and steams in extracting system
Evaporate tower (17) processing and isolate tungsten and sodium molybdate, technique waste water is recycled back to washing device reuse.
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