CN106947864B - A kind of system and its processing method recycling heavy metal from discarded SCR catalyst - Google Patents
A kind of system and its processing method recycling heavy metal from discarded SCR catalyst Download PDFInfo
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- CN106947864B CN106947864B CN201610010045.6A CN201610010045A CN106947864B CN 106947864 B CN106947864 B CN 106947864B CN 201610010045 A CN201610010045 A CN 201610010045A CN 106947864 B CN106947864 B CN 106947864B
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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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- 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
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
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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
- C22B34/20—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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- 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
- C22B43/00—Obtaining mercury
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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
- 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 present invention provides a kind of from discarded SCR catalyst recycles the system and its processing method of heavy metal, the system comprises elution system, waste water treatment system and useless solid processing systems, wherein, the liquid-phase outlet of elution system is connected with waste water treatment system, and the solid-phase outlet of elution system is connected with useless solid processing system.Discarded SCR catalyst removes surface dust accumulation through elution system of the present invention, through useless solid processing system recycling high purity vanadic anhydride and sodium molybdate, realizes that vanadium, tungsten, molybdenum efficiently separate.Its technique waste water and elution waste water are enriched with through the magnetic nanometer adsorbent in waste water treatment system, greatly improve poisonous and harmful metal recovery recycling value in waste water, the metals such as arsenic, mercury, chromium, thallium in sewage can be recycled.Useless solid processing system leached mud titanium dioxide reuse is as magnetic absorption agent carrier in waste water treatment system.The technique is discharged without secondary residue, waste water, can reach the good result of various substance 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 one kind and recycles a huge sum of money from discarded SCR catalyst
The system and its processing method of category, more particularly to discarded SCR catalyst is rich in and surface carry heavy metal recycle
System and its processing method.
Background technique
China is the energy consumption big country based on thermal power generation, and a large amount of nitrogen oxides are generated in coal combustion process
(NOx).This kind of compound is one of major pollutants of atmospheric environment, brings serious danger to global ecological environment and human lives
Evil.For the discharge for controlling oxynitrides, State Ministry of Environmental Protection's regulation is after thermal power plant uses low-NO_x combustion technology, nitrogen oxides row
Flue gas denitrification equipment should be built by putting when concentration is unsatisfactory for overall control requirement.Selective catalytic reduction (SCR) technology is imitated because of denitration
Rate is high and is widely applied by domestic and international power plant.
The catalyst of coal fired power plant SCR system is the core of system.The initial cost cost of catalyst accounts for about project investment
40~60%, therefore catalyst will cause the dramatic increase of denitrating system cost once failing.In addition, SCR catalyst itself contains
There is a large amount of heavy metal, such as vanadium, tungsten, molybdenum and titanium, also containing a large amount of toxic heavy metals such as arsenic, mercury, beryllium, thalliums in the dust accumulation of surface.
Such as without recycling, which will seriously pollute environment.Therefore, with domestic discarded SCR catalyst quantity
Sharply increase, it is significant to the recycling of this kind of resource.
China handles waste and old SCR catalyst and starts late, and CN 102936049A proposes one kind from discarded SCR catalyst
The method for extracting tungsten, titanium, vanadium, discarded SCR catalyst is crushed and strong base solution is added by this method reacts, after being separated by filtration
Strong acid is added sodium tungstate, reacts to obtain wolframic acid and sodium salt, vanadic acid mixed solution in sodium vanadate mixed solution, and by sodium salt, vanadic acid
The pH value of mixed solution is adjusted to Precipitation and obtains ammonium vanadate, then sulfuric acid is added in the SCR catalyst of de- tungsten, vanadium and reacts to obtain sulfuric acid
The solids such as oxygen titanium solution and aluminium slag continue the addition water in titanyl sulfate solution and metatitanic acid and waste acid liquor are hydrolyzed to obtain, finally
Obtained ammonium vanadate, wolframic acid, metatitanic acid are carried out to calcining respectively can be obtained vanadic anhydride, tungstic acid and titanium dioxide.CN
103508491A discloses a kind of discarded honeycomb type denitrification catalyst regeneration and resource utilization method, and this method is using sodium roasting
It burns, 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 it is above-mentioned
Technique is only capable of processing recovery Pd, vanadium and the more heavy metal of tungsten equal size, other heavy metals and then enters in waste discharge.Cause
It is to cause more serious secondary pollution actually recycling certain heavy metal species on surface.The country also has part of the manufacturer using precipitating
Method handles the technique waste water, although realizing emission reduction sewage, produces precipitated metal, again results in secondary toxic useless
Slag.And a large amount of soda acids of consumption, production efficiency are low.
Summary of the invention
For the deficiencies in the prior art, the present invention provides one kind to recycle heavy metal from discarded SCR catalyst
System and its processing method, noble metal vanadium of the system and method in the discarded SCR catalyst of recycling, tungsten and molybdenum
Meanwhile the waste water that treatment process generates, the substantially concentration of heavy metal in waste water concentration is realized by magnetic enrichment, and then classify
Recycling.Not only utilization of waste as resource is realized, but also does not generate secondary pollution waste water and waste residue.Recycled simultaneously high-purity vanadium and
Molybdenum can be used for expensive SCR catalyst regeneration and produce.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the system that the present invention provides a kind of to recycle heavy metal from discarded SCR catalyst, the system packet
Include elution system, waste water treatment system and useless solid processing system, wherein the liquid-phase outlet of elution system and waste water treatment system phase
Even, the solid-phase outlet of elution system is connected with useless solid processing system.
It is used as currently preferred technical solution below, but not as the limitation of technical solution provided by the invention, passes through
Following technical scheme can preferably reach and realize technical purpose and beneficial effect of the invention.
As currently preferred technical solution, the waste water treatment system includes filter device, magnetic enrichment device, joint
Separator and solid phase sludge processing system；
Wherein, the liquid-phase outlet of filter device is sequentially connected with magnetic enrichment device and combined separation device, and filter device is consolidated
Mutually outlet 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 nano level active charcoal, alumina in Nano level, nano silicone diatomaceous earth and receives
Any one in meter level resin sorbent or at least two combination, the typical but non-limiting example of the combination has: nanometer
Grade active carbon and alumina in Nano level combination, the combination of alumina in Nano level and nano silicone diatomaceous earth, nano silicone diatomaceous earth and
The combination of nanoscale resin sorbent, the combination of nano level active charcoal, alumina in Nano level and nano silicone diatomaceous earth, nanoscale are living
Property charcoal, alumina in Nano level, nano silicone diatomaceous earth and combination of 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. combined separation device
The obtained purification waste water of processing be recycled to elution system and carry out reuse.
Preferably, the combined separation device is by adsorbing separation device, extraction separator, whizzer or precipitation and separation device
Any one or at least two compositions, combination typical case but non-limiting example has: by adsorbing separation device and extraction separator
Composition, is made of extraction separator and whizzer, is made of whizzer and precipitation and separation device, by adsorbing separation device and
Precipitation and separation device composition, is made of adsorbing separation device, whizzer and precipitation and separation device, by adsorbing separation device, extraction and separation
Device, whizzer and precipitation and separation device composition etc..
Preferably, the solid phase sludge processing system includes sequentially connected multistage water logging tower, first filter and biology
Degraded pond, wherein the solid-phase outlet of first filter is connected with the feed entrance in biodegradable pond, the liquid phase of first filter
Outlet is connected with the liquid phase entrance of magnetic enrichment device.
As currently preferred technical solution, the useless solid processing system includes the grinding device of connection, the first roasting
Furnace, water logging slot, the second filter and extracting system, wherein the first roaster is high-temperature roasting furnace, maturing temperature is up to 800
℃。
Preferably, the solid-phase outlet of second filter is successively connected with desalter and titanium slag storage tank, titanium slag storage tank
Discharge port be connected with the adsorbent entrance of magnetic enrichment device, i.e., the titanium dioxide titanium slag in titanium slag storage tank is as magnetic enrichment device
In raw material.
Preferably, the extracting system includes the vanadium extraction tower being sequentially connected in series, tungsten extraction tower, destilling tower and condensation
Device, the extracting system further include the first back extraction tower and the second back extraction tower, and the organic phase discharge port of vanadium extraction tower and first is stripped
The organic phase feed inlet of tower connects, and the organic phase discharge port of tungsten extraction tower is connect with the organic phase feed inlet of the second back extraction tower.
Preferably, the extracting system includes vanadium extractant slot and tungsten extractant slot, the discharge port and vanadium of vanadium extractant slot
The organic phase feed inlet of extraction tower is connected, and the discharge port of tungsten extractant slot is connected with the organic phase feed inlet of tungsten extraction tower；First
The organic phase discharge port of back extraction tower is connected with the feed inlet of vanadium extractant slot, and the organic phase discharge port and tungsten of the second back extraction tower extract
The feed inlet of agent slot is connected.
Preferably, the extracting system includes the second roaster, the solid-phase outlet and the second roaster of the first back extraction tower
Feed inlet is connected.
Preferably, the liquid phase entrance of the vanadium extraction tower of the liquid-phase outlet and extracting system of second filter is connected.
Preferably, the first back extraction tower, the second back extraction tower and the liquid-phase outlet of condenser and the liquid of elution system enter
Mouth is connected.
As currently preferred technical solution, the filtering of the liquid-phase outlet and waste water treatment system of the elution system is filled
The feed inlet set is connected, and the solid-phase outlet of elution system is connected with the feed inlet of the grinding device of useless solid processing system.
Second aspect, the method that the present invention provides a kind of to recycle heavy metal from discarded SCR catalyst, the method packet
Include following steps:
(1) elution processing is carried out to discarded SCR catalyst, obtains eluent and elution solid；
(2) eluent that step (1) obtains is filtered processing, and the filtrate that filtration treatment obtains is through magnetic enrichment and joint point
From heavy metal product is obtained, the purification waste water circulation obtained through combined separation carries out elution processing；The filter residue that filtration treatment obtains
It handles to obtain harmless sludge through solid phase sludge；
(3) the elution solid that step (1) obtains obtains leached mud and leachate through crushing, roasting, water logging and filtration treatment,
Leached mud obtains titanium slag after desalting processing, and leachate isolates vanadium, tungsten and sodium molybdate through extraction processing.
Wherein, carrying out elution processing to discarded SCR catalyst in step (1) is the table in order to remove discarded SCR catalyst
Area dirt；The harmful heavy metal in sewage can be concentrated in magnetic enrichment in step (2), and combined separation processing is isolated in technique waste water
The metals such as arsenic, mercury, molybdenum, chromium and thallium, pollutant and heavy metal in solid phase sludge processing removing sludge, discharge it is harmless
Sludge can be used for preparing it is non-burning brick, can be used for the engineering constructions such as sewage treatment use；Desalting processing in step (3) primarily to
Remove sodium salt.
As currently preferred technical solution, magnetic enrichment uses magnetic nanometer adsorbent in step (2).
Preferably, the magnetic nanometer adsorbent is nano level active charcoal, alumina in Nano level, nano silicone diatomaceous earth and receives
Any one in meter level resin sorbent or at least two combination, the typical but non-limiting example of the combination has: nanometer
Grade active carbon and alumina in Nano level combination, the combination of alumina in Nano level and nano silicone diatomaceous earth, nano silicone diatomaceous earth and
The combination of nanoscale resin sorbent, the combination of nano level active charcoal, alumina in Nano level and nano silicone diatomaceous earth, nanoscale are living
Property charcoal, alumina in Nano level, nano silicone diatomaceous earth and combination of nanoscale resin sorbent etc..
Preferably, the carrier that magnetic enrichment uses in step (2) is titaniferous magnetic particle.
As currently preferred technical solution, the processing of solid phase sludge described in step (2) successively includes at multistage water logging
Reason, filtration treatment and biodegrade processing, wherein solid phase sludge can remove most gold in sludge through multistage Soaking treatment
Belong to ion, biodegrade processing is carried out after filtration treatment through the sludge of multistage Soaking treatment can further remove organic contamination
Object and a small amount of heavy metal.
Preferably, the filtrate cycle that filtration treatment obtains in the solid phase sludge treatment process carries out magnetic enrichment processing, takes off
Except the heavy metal carried secretly in sludge, secondary pollution is avoided.
As currently preferred technical solution, it is roasted in step (3) and carries out sodium roasting with alkaline mixt；
Preferably, the alkaline mixt is sodium hydroxide, calcium hydroxide, any one in sodium carbonate or at least two
Combination, the typical but non-limiting example of combination have: the combination of sodium hydroxide and calcium hydroxide, calcium hydroxide and sodium carbonate
Combination, sodium hydroxide, calcium hydroxide and combination of 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
Deng but being not limited to cited numerical value, other temperature values in given range are feasible.
Preferably, the time of the roasting is 1~3h, such as 1h, 1.5h, 2h, 2.5h or 3h etc., but is not limited to listed
Numerical value is lifted, other temperature values in given range 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 solution, the method for extracting vanadium is CN 103540745A in step (3) extraction processing
Middle method, process are as follows:
(a) acid is added in obtained leachate, it is miscellaneous more to form phosphorus tungsten, phosphorus tungsten vanadium, silicon tungsten, molybdenum vanadium arsenic and tungsten arsenic etc.
Acid removes solution impurities using the heteropoly acid in amine extractant and synergic reagent compounding synergic solvent extraction leachate, obtains pure
The raffinate containing vanadium changed；
(b) will contain vanadium raffinate to be concentrated by evaporation to vanadium unit cellulose content is 20~60g/L, and ammonium salt is added and obtains ammonium metavanadate
Solid, then calcine to obtain vanadic anhydride of the purity greater than 99.99% by pure water, drying and oxygen atmosphere；Organic phase
Regeneration cycle can be stripped using aqueous slkali.
Preferably, the method for step (3) extraction processing separating tungsten and sodium molybdate is method in CN 103320612A, process
It is as follows:
The tungstenic obtained after extracting vanadium is handled using the organic extractant phase that serotonin-hydroxyl oxime extractant and diluent are made into
Molybdenum salting liquid, salting liquid containing tungsten uses diluted acid or dilute alkaline soln to adjust in pH value to 3~6 ranges before extraction, and is in temperature
Organic phase is mixed with salting liquid containing tungsten at 10~50 DEG C, is extracted and is stripped processing sub-argument and go out tungsten, what back extraction was handled
Organic phase is regenerated, and high-purity sodium molybdate can be made in raffinate evaporative crystallization, and tungsten separation is greater than 105。
As currently preferred technical solution, the described method comprises the following steps:
(1) it discards SCR catalyst and carries out elution processing in elution system, obtain eluent and elution solid；
(2) filter device that the eluent that step (1) obtains enters in waste water treatment system is filtered processing, at filtering
The filtrate that reason obtains carries out progress combined separation in magnetic enrichment and combined separation device in magnetic enrichment device and obtains heavy metal product,
The purification waste water obtained through combined separation is recycled to elution system and carries out elution processing；The filter residue that filtration treatment obtains enters solid phase
It handles to obtain harmless sludge through multistage water logging tower, first filter and biodegradable pond in sludge treating system；
(3) the elution solid that step (1) obtains through grinding device crush, the first roaster roasted, water logging slot into
Row water logging obtains leached mud and leachate through the second filter filtration treatment again, and leached mud is after desalter carries out desalting processing
Titanium slag is obtained, leachate goes out through the second roaster baking separation in extracting system through vanadium extraction tower and the first back extraction tower processing again
Vanadium, raffinate in extracting system through tungsten extraction tower (16), second back extraction tower (21) and destilling tower (17) processing isolate tungsten with
Sodium molybdate, technique waste water are recycled back to washing device reuse.
Compared with prior art, the invention has the following advantages:
(1) processing system and method for the present invention can process discarded SCR catalyst and discarded SCR catalyst
Heavy metal in the waste water generated in journey all recycles, and realizes various substance closed cycles in denitrating flue gas industrial chain, increases
Add the utilization of resources to be worth, avoids secondary environmental pollution.
(2) present invention through magnetic enrichment can substantially concentration technology heavy metal in waste water concentration, improve heavy metal in waste water
Recycling value, and the magnetic absorption agent carrier of the higher cost used in the process of magnetic enrichment also derives from the system and method
Itself, and recoverable.Classical acid, alkali precipitation concentration method are compared, the method for the invention is simple, and it is pollution-free, it is greatly reduced
Cost.
(3) through system and method for the present invention, the rate of recovery of vanadium, tungsten and molybdenum in discarded SCR catalyst can be made to be respectively
90%, 89% and 87% or more, for the purity of the vanadium metal recycled up to 99.9wt% or more, the purity of tungsten is reachable
99wt% or more, the purity of sodium molybdate is up to 99.99wt%；Meanwhile the rate of recovery of the metals such as arsenic, mercury, lead and thallium is 86%
More than, the purity of the metals such as arsenic, mercury, lead and thallium for recycling also is 85wt% or more.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 more difficult isolated tungsten and molybdenum, so
The technique can also handle the V routinely applied2O5-WO3/TiO2, V2O5-MoO3/TiO2V2O5-WO3-MoO3/TiO2It is useless etc. a variety of
Catalyst system.
Detailed description of the invention
Fig. 1 is the system and device schematic diagram of the present invention that heavy metal is recycled from discarded SCR catalyst；
Wherein, 1- elution system, 2- filter device, 3- magnetic enrichment device, 4- enrichment liquid storage tank, 5- combined separation device, 6- are more
Grade water logging tower, 7- first filter, 8- biodegrade pond, 9- grinding device, the first roaster of 10-, 11- water logging slot, 12- second
Filter, 13- desalter, 14- titanium slag storage tank, 15- vanadium extraction tower, 16- tungsten extraction tower, 17- destilling tower, 18- vanadium extractant
Slot, 19- tungsten extractant slot, 20- first are stripped tower, and 21- second is stripped tower, 22- condenser, the second roaster of 23-.
Specific embodiment
Below in conjunction with several specific embodiments, exemplary illustration and help further understand the present invention, but embodiment has
Body details does not represent whole technical solutions under present inventive concept merely to illustrate the present invention, therefore should not be construed as to this
Total technical solution is invented to limit, it is some to be changed for the technician without departing from the unsubstantiality of inventive concept, such as to have
There is the technical characteristic of same or similar technical effect simply to change or replace, the category scope of the present invention.
As shown in Figure 1, the system that the present invention provides a kind of to recycle heavy metal from discarded SCR catalyst, the system
Including elution system 1, waste water treatment system and useless solid processing system, wherein the liquid-phase outlet of elution system 1 and wastewater treatment system
System is connected, and the solid-phase outlet of elution system 1 is connected with useless solid processing system.
The waste water treatment system includes filter device 2, magnetic enrichment device, combined separation device 5 and solid phase sludge processing system
System, wherein the liquid-phase outlet of filter device 2 is sequentially connected with magnetic enrichment device and combined separation device 5, the solid phase of filter device 2
Outlet 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 Nano is wherein used in magnetic enrichment device 3
Adsorbent.
The magnetic nanometer adsorbent is nano level active charcoal, alumina in Nano level, nano silicone diatomaceous earth and nanoscale tree
Any one in rouge adsorbent or at least two combination.
Carrier is titaniferous magnetic particle in the magnetic enrichment device 3.
The combined separation device 5 is any one in adsorbing separation device, extraction separator, whizzer or precipitation and separation device
Kind or at least two combination.
The solid phase sludge processing system includes sequentially connected multistage water logging tower 6, first filter 7 and biodegradable pond
8, wherein the solid-phase outlet of first filter 7 is connected with the feed entrance in biodegradable pond 8, the liquid-phase outlet of first filter 7
It is connected with the liquid phase entrance of magnetic enrichment device 3.
The useless solid processing system includes the grinding device 9 of connection, the first roaster 10, water logging slot 11, the second filter
12 and extracting system.
The solid-phase outlet of second filter 12 is successively connected with desalter 13 and titanium slag storage tank 14, titanium slag storage tank 14
Discharge port be connected with the adsorbent material entrance of magnetic enrichment device.
The extracting system includes the vanadium extraction tower 15 being sequentially connected in series, tungsten extraction tower 16, destilling tower 17 and condenser
22, the extracting system further includes the first back extraction tower and the second back extraction tower, and the organic phase discharge port of vanadium extraction tower and first is stripped
The organic phase feed inlet of tower connects, and the organic phase discharge port of tungsten extraction tower is connect with the organic phase feed inlet of the second back extraction tower.
The extracting system further includes vanadium extractant slot 18 and tungsten extractant slot 19, the discharge port and vanadium of vanadium extractant slot 18
The organic phase feed inlet of extraction tower 15 is connected, the organic phase feed inlet phase of the discharge port and tungsten extraction tower 16 of tungsten extractant slot 19
Even；The organic phase discharge port of first back extraction tower 20 is connected with the feed inlet of vanadium extractant slot 18, the organic phase of the second back extraction tower 21
Discharge port is connected with the feed inlet of tungsten extractant slot 19.
The extracting system further includes the second roaster 23, the solid-phase outlet and the second roaster 23 of the first back extraction tower 20
Feed inlet is connected.
The liquid phase entrance of the vanadium extraction tower 15 of the liquid-phase outlet and extracting system of second filter 12 is connected.
The first back extraction tower 20, second is stripped tower 21 and the liquid-phase outlet of condenser 22 and the liquid of elution system 1 enters
Mouth is connected.
Embodiment 1:
A kind of system that heavy metal is recycled from discarded SCR catalyst is present embodiments provided, the system comprises elutions
System 1, waste water treatment system and useless solid processing system, wherein the filtering of the liquid-phase outlet and waste water treatment system of elution system 1
The feed inlet of device 2 is connected, and the solid-phase outlet of elution system 1 is connected with the feed inlet of the grinding device 9 of useless solid processing system.
The waste water treatment system includes filter device 2, magnetic enrichment device, combined separation device 5 and solid phase sludge processing system
System, wherein the liquid-phase outlet of filter device 2 is sequentially connected with magnetic enrichment device and combined separation device 5, the solid phase of filter device 2
Outlet 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 nanoscale oxygen is wherein used in magnetic enrichment device 3
The mixture for changing aluminium and nanoscale resin sorbent is used as magnetic nanometer adsorbent, and carrier is titaniferous magnetic in the magnetic enrichment device 3
Particle.
The combined separation device 5 is the combination of adsorbing separation device and precipitation and separation device.
The solid phase sludge processing system includes sequentially connected multistage water logging tower 6, first filter 7 and biodegradable pond
8, wherein the solid-phase outlet of first filter 7 is connected with the feed entrance in biodegradable pond 8, the liquid-phase outlet of first filter 7
It is connected with the liquid phase entrance of magnetic enrichment device.
The useless solid processing system includes the grinding device 9 of connection, the first roaster 10, water logging slot 11, the second filter
12 and extracting system.
The solid-phase outlet of second filter 12 is successively connected with desalter 13 and titanium slag storage tank 14, titanium slag storage tank 14
Discharge port be connected with the liquid inlet of magnetic enrichment device.
The extracting system includes the vanadium extraction tower 15 being sequentially connected in series, tungsten extraction tower 16, destilling tower 17 and condenser
22, the extracting system further includes the first back extraction tower 20 and the second back extraction tower 21, the organic phase discharge port of vanadium extraction tower 15 and the
One back extraction tower 20 organic phase feed inlet connection, the organic phase discharge port of tungsten extraction tower 16 with second be stripped tower 21 organic phase into
Material mouth connection.
The extracting system further includes vanadium extractant slot 18 and tungsten extractant slot 19, the discharge port and vanadium of vanadium extractant slot 18
The organic phase feed inlet of extraction tower 15 is connected, the organic phase feed inlet phase of the discharge port and tungsten extraction tower 16 of tungsten extractant slot 19
Even；The organic phase discharge port of first back extraction tower 20 is connected with the feed inlet of vanadium extractant slot 18, the organic phase of the second back extraction tower 21
Discharge port is connected with the feed inlet of tungsten extractant slot 19.
The extracting system further includes the second roaster 23, the solid-phase outlet and the second roaster 23 of the first back extraction tower 20
Feed inlet is connected.
The liquid phase entrance of the vanadium extraction tower 15 of the liquid-phase outlet and extracting system of second filter 12 is connected.
The first back extraction tower 20, second is stripped tower 21 and the liquid-phase outlet of condenser 22 and the liquid of elution system 1 enters
Mouth is connected.
Embodiment 2:
Mixing in addition to using nano level active charcoal, alumina in Nano level and nanoscale resin sorbent in magnetic enrichment device 3
For object as magnetic nanometer adsorbent, the combined separation device 5 is the combination of adsorbing separation device, extraction separator and precipitation and separation device
Outside, the connection type of other apparatus structures and device is in the same manner as in Example 1.
Embodiment 3:
In addition to using nanoscale resin sorbent as magnetic nanometer adsorbent, the combined separation device 5 in magnetic enrichment device 3
Outside for whizzer, the connection type of other apparatus structures and device is in the same manner as in Example 1.
Embodiment 4:
In addition to using nano silicone diatomaceous earth as magnetic nanometer adsorbent in magnetic enrichment device 3, the combined separation device 5 is to inhale
Outside attached separator, the connection type of other apparatus structures and device is in the same manner as in Example 1.
Embodiment 5:
The present embodiment is recycled in discarded SCR catalyst using system described in embodiment 1 and recycles heavy metal.
Discarded SCR catalyst used is in the present embodiment with TiO2For carrier, with V2O5-WO3For active constituent, belong to metal oxygen
Compound type catalyst, it is cellular.The SCR catalyst surface abrasion, arsenic poisoning is serious, non-renewable.Table is enriched in denitrification process
The bright a large amount of dust accumulations of absorption, specific heavy metal component and content are shown in Table 1.
Processing method is as follows:
(1) by discarded SCR catalyst feeding elution system 1 carry out elution processing removal surface dust accumulation, obtain eluent and
Elute solid；
(2) for the eluent that step (1) obtains after filter device 2 removes solid sludges, the liquid being obtained by filtration enters magnetic
The harmful heavy metal content in sewage is concentrated in enricher 3, and pregnant solution enters enrichment liquid storage tank 4 again through the joint point of combined separation device 5
The metals such as arsenic, mercury, lead and the thallium in technique waste water are separated out, the heavy metal purity of recycling is referring to table 2.Combined separation device 5 is discharged
Purified waste water (concentration is referring to table 1) enter elution system 1 recycled.
The solid sludges being obtained by filtration through filter device 2 are through multistage water logging tower 6, first filter 7 and biodegrade Chi8Chu
Reason removing pollutant and heavy metal, the harmless sludge of discharge prepare non-burning brick (its content of beary metal is referring to table 1)；Through a filter
The heavy metal-containing waste water of 7 discharges is sent into magnetic enrichment device 3 and is handled.
(3) the elution solid that step (1) obtains is crushed through grinding device 9, carries out sodium roasting into the first roaster 10,
Then water logging is carried out in water logging slot 11 obtain leached mud and leachate through 12 filtration treatment of the second filter again.Leached mud is through desalination
Device 13 removes sodium salt, and into titanium slag storage tank 14, the purification titanium slag in titanium slag storage tank 14 enters magnetic enrichment device 3 and carries as adsorbent
Body recycles.Leachate goes out height through 23 baking separation of the second roaster again through vanadium extraction tower 15 and the first back extraction 20 extraction processing of tower
Pure vanadium；The raffinate for isolating vanadium goes out tungsten through tungsten extraction tower 16 and the second back extraction 21 sub-argument of tower, and raffinate is crystallized through destilling tower 17
High-purity sodium molybdate out, the vapor distilled out are condensed into liquid phase through condenser 22, are stripped 21 row of tower with the first back extraction tower 20, second
Liquid out enters 1 reuse of elution pool, 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, volume
Percent concentration is respectively 4%, 0.7%, 0.8% and 94.5%.Extraction conditions: 25 DEG C of temperature, time 15min, load is organic
Regeneration is mutually stripped using 5% sodium hydroxide, ammonium chloride precipitation temperature is 30 DEG C, stirs 120 minutes, it is dry to be placed in high temperature furnace
3 hours.
Tungsten extractant is the mixture of primary amine Primene 81R, secondary amine 7202, BK992 and kerosene, and volume ratio is respectively
1.5%, 0.5%, 0.5% and 97.5%.Extraction conditions: 10% sodium hydroxide is stripped at 18 DEG C of temperature, time 20min, 30 DEG C
45min, organic phase regeneration.
Heavy metal in untreated discarded SCR catalyst in the present embodiment, and treated waste water and product contains
As shown in table 1, the purity of obtained heavy metal product is as shown in table 2 for amount.
Table 1: the content of beary metal table in discarded SCR catalyst and treated waste water and product
Note: "-" representative is not detected.
Table 2: the purity table of heavy metal product
Embodiment 6:
The present embodiment is recycled in discarded SCR catalyst using system described in embodiment 2 and recycles heavy metal.
Discarded SCR catalyst used is in the present embodiment with TiO2For carrier, with V2O5-WO3-MoO3For active constituent, belong to gold
Belong to oxide type catalyst, corrugated plate dst.SCR catalyst sintering and heat inactivation, non-renewable, enrichment shows in denitrification process
A large amount of dust accumulations are adsorbed, specific heavy metal component and content are shown in Table 3.
Processing method is as follows:
In addition to vanadium extractant is the mixing of primary amine N1923, oximes extractant LIX63, n-octyl alcohol and kerosene in step (3)
Object, concentration of volume percent are respectively 4%, 0.7%, 0.8% and 94.5%；Tungsten extractant is primary amine Primene 81R, secondary amine
7202, the mixture of BK992 and kerosene, volume ratio be respectively outside 1.5%, 0.5%, 0.5% and 97.5%, other steps with
It is identical in embodiment 5.
Heavy metal in untreated discarded SCR catalyst in the present embodiment, and treated waste water and product contains
As shown in table 3, the purity of obtained heavy metal product is as shown in table 4 for amount.
Table 3: the content of beary metal table in discarded SCR catalyst and treated waste water and product
Note: "-" representative is not detected.
Table 4: the purity table of heavy metal product
The result of integrated embodiment 1-6 can be seen that through system and method for the present invention, can make discarded SCR catalyst
The rate of recovery of middle vanadium, tungsten and molybdenum is up to 90%, 89% and 87% or more, and the purity of the vanadium metal recycled is up to 99.9wt%
More than, the purity of tungsten is up to 99wt% or more, and the purity of sodium molybdate is up to 99.99wt%；Meanwhile arsenic, mercury, lead and thallium etc.
The rate of recovery of metal is 86% or more, and the purity of the metals such as arsenic, mercury, lead and thallium for recycling also is 85wt% or more,
The added value of metal is higher, realizes the secondary higher value application of waste resource.Meanwhile the present invention can substantially concentration technology through magnetic enrichment
The concentration of heavy metal in waste water improves heavy metal in waste water recycling value, and the higher cost used in the process of magnetic enrichment
Magnetic absorption agent carrier also derive from described system and method itself, and recoverable.It is rich to compare classical acid, alkali precipitation
Collection method, the method for the invention is simple, pollution-free, and cost is greatly reduced, and realizes that various substances are closed circuit in denitrating flue gas industrial chain
Circulation increases utilization of resources value, avoids secondary environmental pollution.
The Applicant declares that the present invention is explained by the above embodiments method detailed of the invention, but the present invention not office
Be limited to above-mentioned method detailed, that is, do not mean that the invention must rely on the above detailed methods to implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (25)
1. a kind of system for recycling heavy metal from discarded SCR catalyst, which is characterized in that the system comprises elution systems
(1), waste water treatment system and useless solid processing system, wherein the liquid-phase outlet of elution system (1) is connected with waste water treatment system,
The solid-phase outlet of elution system (1) is connected with useless solid processing system；
The waste water treatment system includes filter device (2), magnetic enrichment device, combined separation device (5) and solid phase sludge processing system
System；Wherein, the liquid-phase outlet of filter device (2) is sequentially connected with magnetic enrichment device and combined separation device (5), filter device (2)
Solid-phase outlet be connected with solid phase sludge processing system；
The magnetic enrichment device includes magnetic enrichment device (3) and enrichment liquid storage tank (4), is inhaled in magnetic enrichment device (3) using magnetic Nano
Attached dose, the magnetic nanometer adsorbent includes nanoscale resin sorbent；
The combined separation device (5) is by any one in adsorbing separation device, extraction separator, whizzer or precipitation and separation device
Or at least two composition；
The solid phase sludge processing system includes sequentially connected multistage water logging tower (6), first filter (7) and biodegradable pond
(8), wherein the solid-phase outlet of first filter (7) is connected with the feed entrance of biodegradable pond (8), first filter (7)
Liquid-phase outlet is connected with the liquid phase entrance of magnetic enrichment device；
The useless solid processing system includes the grinding device (9), the first roaster (10), water logging slot (11), the second filtering of connection
Device (12) and extracting system.
2. the system of recycling heavy metal according to claim 1, which is characterized in that the magnetic nanometer adsorbent is nanometer
Grade active carbon, alumina in Nano level, any one in nano silicone diatomaceous earth and nanoscale resin sorbent or at least two group
It closes.
3. the system of recycling heavy metal according to claim 1, which is characterized in that carrier is in the magnetic enrichment device (3)
Titaniferous magnetic particle.
4. the system of recycling heavy metal according to claim 1, which is characterized in that the liquid phase of the combined separation device (5)
Outlet is connected with the liquid inlet of elution system (1).
5. the system of recycling heavy metal according to claim 1, which is characterized in that the solid phase of second filter (12)
Outlet is successively connected with desalter (13) and titanium slag storage tank (14), the suction of the discharge port and magnetic enrichment device of titanium slag storage tank (14)
Attached dose of entrance is connected.
6. the system of recycling heavy metal according to claim 1, which is characterized in that the extracting system includes being sequentially connected in series
The vanadium extraction tower (15) of connection, tungsten extraction tower (16), destilling tower (17) and condenser (22), the extracting system further include first
It is stripped tower (20) and the second back extraction tower (21), the organic phase of the organic phase discharge port of vanadium extraction tower (15) and the first back extraction tower (20)
Feed inlet connection, the organic phase discharge port of tungsten extraction tower (16) are connect with the organic phase feed inlet of the second back extraction tower (21).
7. the system of recycling heavy metal according to claim 1, which is characterized in that the extracting system includes vanadium extractant
Slot (18) and tungsten extractant slot (19), the organic phase feed inlet phase of the discharge port and vanadium extraction tower (15) of vanadium extractant slot (18)
Even, the discharge port of tungsten extractant slot (19) is connected with the organic phase feed inlet of tungsten extraction tower (16)；First back extraction tower (20) has
Machine phase discharge port is connected with the feed inlet of vanadium extractant slot (18), the organic phase discharge port and tungsten extractant of the second back extraction tower (21)
The feed inlet of slot (19) is connected.
8. the system of recycling heavy metal according to claim 1, which is characterized in that the extracting system includes the second roasting
The solid-phase outlet of furnace (23), the first back extraction tower (20) is connected with the feed inlet of the second roaster (23).
9. the system of recycling heavy metal according to claim 1, which is characterized in that the liquid phase of second filter (12)
Outlet is connected with the liquid phase entrance of the vanadium extraction tower (15) of extracting system.
10. the system of recycling heavy metal according to claim 6, which is characterized in that first back extraction tower (20), second
The liquid-phase outlet of back extraction tower (21) and condenser (22) is connected with the liquid inlet of elution system (1).
11. the system of recycling heavy metal according to claim 1, which is characterized in that the liquid phase of the elution system (1) goes out
Mouth is connected with the feed inlet of the filter device (2) of waste water treatment system, the solid-phase outlet of elution system (1) and useless solid processing system
Grinding device (9) feed inlet be connected.
12. a kind of method for recycling heavy metal from discarded SCR catalyst using system described in claim 1, which is characterized in that
It 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) obtains is filtered processing, and the filtrate that filtration treatment obtains obtains through magnetic enrichment and combined separation
To heavy metal product, the purification waste water circulation obtained through combined separation carries out elution processing；The filter residue that filtration treatment obtains is through solid
Phase Treatment of Sludge obtains harmless sludge；
(3) the elution solid that step (1) obtains obtains leached mud and leachate through crushing, roasting, water logging and filtration treatment, leaches
Slag obtains titanium slag after desalting processing, and leachate isolates vanadium, tungsten and sodium molybdate through extraction processing.
13. the method for recycling heavy metal according to claim 12, which is characterized in that magnetic enrichment uses magnetic in step (2)
Property nano adsorber.
14. the method for recycling heavy metal according to claim 13, which is characterized in that the magnetic nanometer adsorbent is to receive
Any one in meter level active carbon, alumina in Nano level, nano silicone diatomaceous earth and nanoscale resin sorbent or at least two
Combination.
15. the method for recycling heavy metal according to claim 12, which is characterized in that magnetic enrichment uses in step (2)
Carrier is titaniferous magnetic particle.
16. the method for recycling heavy metal according to claim 12, which is characterized in that solid phase sludge described in step (2)
Processing successively includes multistage Soaking treatment, filtration treatment and biodegrade processing.
17. the method for recycling heavy metal according to claim 16, which is characterized in that in the solid phase sludge treatment process
The filtrate cycle that filtration treatment obtains carries out magnetic enrichment processing.
18. the method for recycling heavy metal according to claim 12, which is characterized in that be roasted in step (3) with alkalinity
Mixture carries out sodium roasting.
19. the method for recycling heavy metal according to claim 18, which is characterized in that the alkaline mixt is hydroxide
Any one in sodium, calcium hydroxide or sodium carbonate or at least two combination.
20. it is according to claim 18 recycling heavy metal method, which is characterized in that the temperature of the roasting be 400~
800℃。
21. the method for recycling heavy metal according to claim 18, which is characterized in that the time of the roasting is 1~3h.
22. the method for recycling heavy metal according to claim 12, which is characterized in that the titanium slag that the step (3) obtains
It returns as the absorption carrier raw material in magnetic enrichment.
23. the method for recycling heavy metal according to claim 12, which is characterized in that extracted in step (3) extraction processing
The method of vanadium are as follows:
(a) acid is added in leachate, heteropoly acid is formed, using miscellaneous in amine extractant and synergic reagent synergic solvent extraction leachate
Polyacid removes solution impurities, the raffinate containing vanadium purified；
(b) will contain vanadium raffinate to be concentrated by evaporation to vanadium unit cellulose content is 20~60g/L, and ammonium salt is added and obtains ammonium metavanadate solid,
It calcines to obtain vanadic anhydride of the purity greater than 99.99% by pure water, drying and oxygen atmosphere again；Organic phase uses alkali
Solution is stripped regeneration cycle.
24. the method for recycling heavy metal according to claim 12, which is characterized in that step (3) extraction processing separating tungsten
With the method for sodium molybdate are as follows:
The salt containing tungsten obtained after extracting vanadium is handled using the organic extractant phase that serotonin-hydroxyl oxime extractant and diluent are made into
Solution, salting liquid containing tungsten are adjusted before extraction in pH value to 3~6 ranges, and temperature be 10~50 DEG C at by organic phase with
The mixing of salting liquid containing tungsten, is extracted and tungsten is isolated in back extraction processing, and the organic phase that back extraction is handled is regenerated, raffinate
High-purity sodium molybdate is made in evaporative crystallization.
25. the method for recycling heavy metal according to claim 12, which is characterized in that the described method comprises the following steps:
(1) it discards SCR catalyst and carries out elution processing in elution system (1), obtain eluent and elution solid；
(2) filter device (2) that the eluent that step (1) obtains enters in waste water treatment system is filtered processing, at filtering
The filtrate that reason obtains carries out progress combined separation in magnetic enrichment and combined separation device (5) in magnetic enrichment device and obtains heavy metal production
Object, the purification waste water obtained through combined separation are recycled to elution system (1) and carry out reuse；The filter residue that filtration treatment obtains enters solid
It handles through multistage water logging tower (6), first filter (7) and biodegradable pond (8) in phase sludge treating system and obtains harmless sludge；
(3) the elution solid that step (1) obtains is crushed through grinding device (9), the first roaster (10) is roasted, in water logging slot
(11) it carries out water logging and obtains leached mud and leachate through the second filter (12) filtration treatment again, leached mud is through desalter (13)
Titanium slag is obtained after carrying out desalting processing, leachate is handled again in extracting system through vanadium extraction tower (15) and the first back extraction tower (20)
Go out vanadium through the second roaster (23) baking separation, raffinate is in extracting system through tungsten extraction tower (16), the second back extraction tower (21)
Tungsten and sodium molybdate are isolated with destilling tower (17) processing, technique waste water is recycled back to washing device reuse.
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| CN108456782A (en) * | 2018-05-23 | 2018-08-28 | 广州大学 | The recycling piece-rate system and method for heavy metal in a kind of solid waste |
| CN110817944B (en) * | 2019-11-06 | 2022-05-03 | 北京华电光大环境股份有限公司 | Recovery method of waste SCR denitration catalyst |
| CN113385159A (en) * | 2020-03-13 | 2021-09-14 | 石家庄天旭环保科技有限公司 | Novel process for regenerating rolling oil-containing waste diatomite of aluminum processing enterprise |
| CN111589473B (en) * | 2020-06-24 | 2021-11-26 | 清华大学 | Regeneration and resource utilization method of thallium-poisoned SCR denitration catalyst |
| CN111715210A (en) * | 2020-07-09 | 2020-09-29 | 江苏龙净科杰环保技术有限公司 | Regeneration method of cement kiln thallium poisoning SCR denitration catalyst |
| CN112481507A (en) * | 2020-12-15 | 2021-03-12 | 江苏龙源催化剂有限公司 | Method for recovering metallic lead and thallium components from waste denitration catalyst |
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