CN105536817B - A kind of method and system of discarded SCR denitration comprehensive reutilization - Google Patents

A kind of method and system of discarded SCR denitration comprehensive reutilization Download PDF

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Publication number
CN105536817B
CN105536817B CN201510943530.4A CN201510943530A CN105536817B CN 105536817 B CN105536817 B CN 105536817B CN 201510943530 A CN201510943530 A CN 201510943530A CN 105536817 B CN105536817 B CN 105536817B
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China
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filter
filtrate
reaction pot
hydrolytic reaction
main body
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CN105536817A (en
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黄丽明
王洪明
杨广华
余立清
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Longyan Cercis Innovation Research Institute
Fujian Cercis Environment Project Co Ltd
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Longyan Cercis Innovation Research Institute
Fujian Cercis Environment Project Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention discloses a kind of method and system of discarded SCR catalyst comprehensive reutilization, using brand-new acidleach oxidation technology, the vanadium in discarded SCR catalyst, titanium is converted into the pentavalent vanadium and titanyl sulfate of solubility, and reclaim WO3It is rough；Pentavalent vanadium hydrolyzes to obtain vanadium crude product, realizes the initial gross separation of vanadium and titanium；Titanyl sulfate hydrolysis produces metatitanic acid precipitation, and TiO is completed by filter washing drying and roasting2Recovery, the sulfuric acid of filtrate desalination concentration and recovery can recycle in step of acid dipping.Present invention recovery is efficiently, technique is simple, cost is low, and the recycling not only of spent acid solves waste water handling problem but also saved resource.

Description

A kind of method and system of discarded SCR denitration comprehensive reutilization
Technical field
The invention belongs to discard SCR denitration recycling field, and in particular to a kind of discarded SCR denitration synthesis The method and system of recycling.
Background technology
Nitrogen oxides (NOx)It is one of main component of atmosphere pollution, such material can trigger the severe environments such as acid rain Problem, while endanger human health.In numerous denitration technologies, selective catalytic reduction (SCR) is that commercial Application is most extensive Technology, have the characteristics that efficient, ripe.With the development of Denitration Industry, a large amount of SCR catalysis failed or discarded are generated Agent.Such material belongs to dangerous solid waste, and arbitrarily discarded bank up does not only take up the pollution such as a large amount of soils, heavy metal therein Thing also seriously endangers natural environment and human health.
Most commonly seen commercial SCR denitration is vanadium tungsten titanium-type, and wherein metal oxide constitutes about 90%.To its Discarded object carries out comprehensive reutilization, can not only effectively solve potential environmental problem, the metal oxide for reclaiming to obtain can also Recycle, produce preferable environmental benefit and economic benefit.
At present, roasting technique all is changed using high-temperature sodium (calcium) substantially to the Comprehensive Recovery Technology for discarding SCR denitration, Such as disclosed in the document such as CN201510083924.7, CN201410534406.8, CN201410084859.5, the technique High energy consumption and complex process.A kind of brand-new V is employed in document CN201410471988.X2O5Recovery process, i.e., in acid With reducing agent by V under the conditions of property5+It is reduced into water miscible V4+, so as to which vanadium be separated with catalyst other compositions, again will after separation V4+Aoxidize back V5+, adjusting pH enables its hydrolytic precipitation to reclaim.This technique rate of recovery is higher, but vanadium experienced reduction and oxidation Reciprocal process, slightly complicated.
It would therefore be highly desirable to development technology program is simpler, the rate of recovery is high, does not cause secondary pollution, cost of investment low and meets The new recovery technology of industrial process conditions.
The content of the invention
The present invention is for more than the problem of discarded SCR denitration recovery technology, there is provided a kind of efficient, simple, low The discarded SCR denitration Comprehensive Recovery Technology of cost, this technology not only solve the problems, such as universal high-temperature roasting, and technique journey Sequence is simpler, and the rate of recovery is high, does not cause secondary pollution, cost of investment is low, meets industrial condition；Specifically, it is described Technology can reclaim the metal oxide in the discarded SCR denitration with the higher rate of recovery, realize discarded SCR denitration The resource reutilization of catalyst, reduce the processing cost of discarded SCR denitration.
To achieve the above object, the present invention provides following technical scheme：
A kind of method of discarded SCR denitration comprehensive reutilization, methods described comprise the following steps：
(1) described discarded SCR denitration is crushed, adds in sulfuric acid and lead to oxidant, heating stirring, filter Filtrate I and WO containing vanadium, titanium3Rough filter cake I；
(2) alkali regulation pH to 1~2, heating stirring are added in the filtrate I obtained to step (1), insulation stands, filtered To filter cake II and filtrate II；It is mainly vanadium crude product precipitation in the filter cake II, while is also mixed with a small amount of metatitanic acid precipitation；It is described Filtrate II includes non-hydrolysing titanyl sulfate；
(3) add alkali to adjust pH to 6~8 in the filtrate II obtained to step (2), and add a small amount of crystal seed, heating stirring, protect Temperature is stood, and is boiled again, quick cooling, is filtrated to get metatitanic acid precipitation and filtrate II I；
(4) sulfate and sulfuric acid that the filtrate II I in step (3) is successively recycled through desalination concentration, the sulfuric acid return again Recycled into step (1)；
(5) metatitanic acid in step (3) precipitates scrubbed, dry roasting and obtains TiO2。
Wherein, also include pre-treatment step before step (1), be specially：Removed with compressed air purging SCR denitration Surface dust, then remove surface adsorbate (such as arsenic, mercury, alkali metal salt), drying for standby by being cleaned by ultrasonic.
Wherein, the process in step (1) or 100~200 are crushed to without the discarded SCR denitration of pretreatment Mesh.
Wherein, the concentration of the sulfuric acid in step (1) is 30~70g/L, and addition is discarded SCR denitration volume 1~3 times of volume.
Wherein, the temperature (being heated to) during stirring in step (1) is 80~100 DEG C, and mixing time is 0.5~2h.
Wherein, the oxidant described in step (1) is one kind in oxygen, ozone.
Wherein, alkali described in step (2) is NaOH or KOH, preferably NaOH；It is furthermore preferred that the mass percent of the alkali Concentration is 20%.
Wherein, the mixing speed in step (2) is 100~300r/min, and mixing time is 1~2h, and temperature is during stirring 50~70 DEG C.
Wherein, the insulation time of repose in step (2) is 10~90min.
Wherein, alkali described in step (3) is NaOH or KOH, preferably NaOH；It is furthermore preferred that the mass percent of the alkali Concentration is 20%.
Wherein, the step in step (3) after a small amount of crystal seed of addition is specially：200~400r/min of speed is kept stirring for, is added Heat stops stirring after boiling to graying point, insulation stands 10~90min, boils 2~4h again, be quickly cooled to 30~60 DEG C, It is filtrated to get metatitanic acid precipitation and filtrate II I.
Wherein, the crystal seed described in step (3) is Detitanium-ore-type TiO2, its addition is titanium quality in filtrate II (with TiO2 Meter) 0.5~1wt%.
Wherein, the sintering temperature in step (5) is 500~800 DEG C, and roasting time is 1~4h.
In the method for the discarded SCR denitration comprehensive reutilization of the present invention, V2O5And TiO2The rate of recovery be more than 90%th, WO3The rate of recovery be more than 95%；Even, V2O5The rate of recovery can reach 93%, TiO2The rate of recovery can reach 94%, WO3The rate of recovery can reach 99.5%.Moreover, the TiO wherein reclaimed2Purity is more than 99%.
The present invention also provides following technical scheme：
A kind of system of discarded SCR denitration comprehensive reutilization, it includes reducing mechanism, acidleach oxidation reaction Kettle, the first lautertuns, the first hydrolytic reaction pot, the second hydrolytic reaction pot and vacuum evaporation groove；
The discarded SCR denitration is transported to the acidleach oxygen after reducing mechanism crushing by conveyer belt Change reactor；
Treatment fluid A after acidleach oxidizing reactor processing enters first lautertuns by pipeline；
The filtrate of first lautertuns is pipelined to first hydrolytic reaction pot；
Treatment fluid B after first hydrolytic reaction pot processing enters second hydrolytic reaction pot by pipeline；
Treatment fluid C after second hydrolytic reaction pot processing enters the vacuum evaporation groove by pipeline；
After the vacuum evaporation groove processing, obtained sulfuric acid enters the acidleach oxidizing reactor by pipeline, carries out Recycle.
Wherein, pretreatment unit is also included before reducing mechanism, is crushed for entering in the discarded SCR denitration Pre-processed before device.Preferably, the pretreatment includes compressed air purging and ultrasonic cleaning.
Wherein, the acidleach oxidizing reactor includes charge door, blow vent, agitator, filling opening, discharge port and main body； Wherein, charge door and filling opening are located at the tip position of main body, and the blow vent for leading to the oxidant is arranged on main body Portion, agitator are located at body interior, and discharge port is arranged on the bottom of main body, appendix is sealedly connected with blow vent, by oxygen Agent is introduced directly into the lower section of the agitator.
Wherein, the acidleach oxidizing reactor also includes chuck and overfall.Preferably, in the chuck parcel main body Bottom, play heating and thermal insulation effect.It is highly preferred that the reactor also includes bearing.
Wherein, the described first or second hydrolytic reaction pot includes charge door, filling opening, discharge port, agitating device and main body； Wherein, charge door and filling opening are located at the tip position of main body, and agitating device is located at body interior, and discharge port is arranged on main body Bottom.
Wherein, chuck and overfall are also included in the described first or second hydrolytic reaction pot.
Wherein, interior cooling coil is also included in second hydrolytic reaction pot.
Wherein, the agitating device of the described first or second hydrolytic reaction pot includes agitating shaft, agitator and cross sphenocephaly, Cross sphenocephaly is located at stirrer bottom, and the agitating shaft can drive agitator to rotate, and can also drive on agitator and move down It is dynamic, the filter of the lower area positioned at the hydrolytic reaction pot main body is provided with the described first or second hydrolytic reaction pot. The filter is divided into two layers up and down, and lower floor's filter is fixed on the inside of main body, and upper level filter plate is rotatable, on every layer of filter Filter bores are equipped with, a pivot protrusion is connected on the center of upper level filter plate, there is cross recess, energy in the pivot protrusion It is enough to coordinate with described cross sphenocephaly, it is provided with one layer of filter cloth between upper and lower two layers of filter；During hydrolysis, cross sphenocephaly is with turning Dynamic raised separation, the filter bores sealing of two layers of filter；When being filtered after hydrolysis, the agitating shaft moves down so that cross wedge Forming head coordinates with cross recess, is rotated by agitating shaft and drives upper level filter plate to rotate, so that the mistake of upper and lower two layers of filter Filter opening is alignd, and forms filtration condition, and so hydrolytic reaction pot can be completed to hydrolyze and filtered simultaneously.
Wherein, hydrolytic reaction pot lower area is additionally provided with vacuum port, can speed up filtering.
Wherein, the second lautertuns, the first water can also be set between the first hydrolytic reaction pot and the second hydrolytic reaction pot Filtrate of the discharging (treatment fluid B) of the discharge port of solution reaction kettle after the filtering of the second lautertuns inputs second hydrolysis again The charge door of kettle.When first hydrolytic reaction pot includes above-mentioned filter, then without setting second filtering again Groove.
Wherein, the 3rd lautertuns can also be set between the second hydrolytic reaction pot and vacuum evaporation groove, and the second hydrolysis is instead Filtrate of the discharging (treatment fluid C) of the discharge port of kettle after the filtering of the 3rd lautertuns is answered to input the charging of the vacuum evaporation groove again Mouthful.When second hydrolytic reaction pot includes above-mentioned filter, then without setting the 3rd lautertuns again.
Said system is used for the method for realizing above-mentioned discarded SCR denitration comprehensive reutilization.
The present invention also provides following technical scheme：
A kind of acidleach oxidizing reactor, it includes charge door, blow vent, agitator, discharge port, filling opening and main body；Its In, charge door and filling opening are located at the tip position of main body, and blow vent is arranged on the top of main body, and agitator is located in main body Portion, discharge port are arranged on the bottom of main body, appendix are sealedly connected with blow vent, and oxidant is introduced directly into agitator Lower section.
Wherein, the reactor also includes chuck and overfall.
Wherein, the reactor also includes bearing.
Wherein, the middle and lower part of chuck parcel main body, heating and thermal insulation effect is played.
Wherein, overfall is located at the upper area of main body.
Wherein, bearing is located at the medium position of acidleach oxidizing reactor, for supporting acidleach oxidizing reactor.
The present invention also provides following technical scheme：
A kind of hydrolytic reaction pot, it includes charge door, filling opening, discharge port, agitating device and main body, the agitating device Including agitating shaft, agitator and cross sphenocephaly, cross sphenocephaly is located at stirrer bottom, and the agitating shaft can drive stirring Device rotates, and can also drive agitator to move up and down, is provided with the hydrolytic reaction pot positioned at the hydrolytic reaction pot main body Lower area filter, the filter is divided into two layers up and down, and lower floor's filter is fixed on the inside of main body, upper level filter plate Rotatably, filter bores are equipped with every layer of filter, a pivot protrusion, the rotation are connected on the center of upper level filter plate There is cross recess in projection, coordinate with described cross sphenocephaly, have one layer of filter cloth between upper and lower two layers of filter.
During hydrolysis, cross sphenocephaly separates with pivot protrusion, the filter bores sealing of two layers of filter；It is described to stir during filtering Axle to be mixed to move down so that cross sphenocephaly coordinates with cross recess, is rotated by agitating shaft and drives upper level filter plate to rotate, so that The filter bores alignment of upper and lower two layers of filter, forms filtration condition, and so hydrolytic reaction pot can complete hydrolysis and mistake simultaneously Filter.
Specifically, during hydrolysis, cross sphenocephaly separates with pivot protrusion, the filter bores sealing of upper and lower two layers of filter, Alkali is added from filling opening and adjusts material in reactor to hydrolysis pH, is stirred under being incubated, is then stopped stirring insulation standing；Hydrolyze Into during rear filtering, agitating shaft moves down, and cross sphenocephaly coordinates with cross recess, rotates agitating shaft and drives upper level filter plate to rotate, Make the filter bores of upper and lower two layers of filter corresponding, form filtration condition, so the hydrolytic reaction pot can complete simultaneously hydrolysis with Filtering.
Wherein, the material of the filter cloth is selected from polytetrafluoroethylene (PTFE) (being resistant to strong acid, be also resistant to 200 DEG C of high temperature above).
Wherein, hydrolytic reaction pot lower area is additionally provided with vacuum port, can speed up filtering.
Wherein, the hydrolytic reaction pot also includes chuck and overfall.
Wherein, the hydrolytic reaction pot also includes bearing.
Wherein, the hydrolytic reaction pot also includes interior cooling coil.
Beneficial effects of the present invention are as follows：
1. cost is low：The present invention realizes the separation of vanadium using acidleach oxidation, avoids high energy consumption caused by high-temperature roasting Cost；
2. technique is simple：Tetravalence vanadium present in discarded SCR denitration is direct oxidation into pentavalent vanadium by the present invention, is kept away Exempt from the reciprocal process of reduction-oxidation of vanadium, and with sulfuric acid dissolution vanadium and titanium, realize the separation of tungsten and other compositions；
3. spent acid reusable edible：The sulfuric acid that the present invention reclaims after desalination concentrates can realize circulation in step of acid dipping Utilize, not only handled waste water caused by technique, saved resource again；
4. recovery obtains Detitanium-ore-type TiO2, the preparation of SCR denitration can be directly used in.
Brief description of the drawings
Fig. 1 is discarded SCR denitration comprehensive recycling process flow chart.
Fig. 2 is the schematic diagram of discarded SCR denitration comprehensive recovery system.
Fig. 3 is the structure chart of acidleach oxidizing reactor.
Fig. 4 is the structure chart of hydrolytic reaction pot.
Fig. 5 is the structure chart of the filter in hydrolytic reaction pot.
Wherein, 1 charge door, 2 blow vents, 3 chucks, 4 bearings, 5 agitators, 6 discharge ports, 7 filling openings, 8 overfalls, 9 masters Body；10 agitating shafts, 11 charge doors, cooling coil in 12,13 chucks, 14 bearings, 15 pivot protrusions, 16 vacuum ports, 17 filling openings, 18 overfalls, 19 agitators, 20 cross sphenocephalies, 21 filters, 22 discharge ports；23 filters, 24 filter clothes, 25 filter bores, 26 Cross recess
Embodiment
Below by way of embodiment, the present invention is described in further detail, but this should not be interpreted as to the present invention Scope be only limitted to following example.In the case where not departing from above method thought of the present invention, according to ordinary skill The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Heretofore described discarded SCR denitration refer to due to long-lasting catalytic operation cause sintering of catalyst, The non-renewable inactivation SCR denitration catalyst for the formation such as mechanical performance reduces, structure is imperfect, also including can not be again after regenerating The raw out of stock catalyst of the SCR of inactivation again." inactivation SCR denitration catalyst " refers to：SCR denitration in the process of running, Because reason, the catalyst activities such as catalyst dust stratification, active component passage and active sites poisoning gradually reduce, when its activity reduces During to the needs that can not meet the out of stock systems of SCR, just it is referred to as " inactivation SCR denitration catalyst ".The SCR denitration is Refer to and the nitrogen oxides catalysis reduction in pending flue gas is converted into N using selective catalytic reduction2With the innocuous substance such as water Medium (catalyst).Preferably, the SCR denitration is vanadium tungsten titanium-type SCR denitration, and main composition is V2O5- WO3/TiO2, wherein V2O5For active component, WO3For auxiliary agent, TiO2For carrier.
As described above, the invention discloses a kind of method of discarded SCR denitration comprehensive reutilization, using brand-new Acidleach oxidation technology, by the vanadium in discarded SCR denitration, titanium be converted into solubility pentavalent vanadium and sulfuric acid oxygen Titanium, and reclaim WO3It is rough；Pentavalent vanadium hydrolyzes to obtain vanadium crude product, realizes the initial gross separation of vanadium and titanium；Titanyl sulfate hydrolysis produces inclined Metatitanic acid is precipitated, and TiO is completed by filter washing drying and roasting2Recovery, the sulfuric acid of filtrate desalination concentration and recovery can be in step of acid dipping Recycle.Present invention recovery is efficiently, technique is simple, cost is low, and recycling not only for spent acid solves waste water handling problem but also saved About resource.
The acidleach oxidizing reactor of the present invention is described in detail below, as shown in figure 3, the acidleach oxidation of the present invention is anti- Kettle is answered to include charge door 1, blow vent 2, chuck 3, bearing 4, agitator 5, discharge port 6, filling opening 7, overfall 8 and main body 9.Its In, chuck wraps up the middle and lower part of main body 9, plays heating and thermal insulation effect；Charge door 1 and filling opening 7 are located at the top position of main body 9 Put；Overfall 8 is located at the upper area of main body 9；Blow vent is arranged on the top of main body 9, and gas transmission is sealedly connected with blow vent Pipe, is introduced directly into the lower section of agitator by oxidant (such as oxygen or ozone), passes through this setup, it is ensured that folder Set wraps up main body middle and lower part to greatest extent, and so as to improve the heating and thermal insulation effect of acidleach oxidizing reactor, also, oxidant is borrowed Help appendix to be delivered directly to the lower section of agitator, can oxidant is quick, evenly spread in reactor material, effectively improve The reaction effect of acidleach oxidizing reactor；Agitator is located at body interior；Discharge port is arranged on the bottom of main body；Bearing 4 is located at The medium position of acidleach oxidizing reactor, it is preferably placed on the outside of chuck, for supporting acidleach oxidizing reactor.
The pre- place such as the compressed air soot blowing of described discarded SCR denitration and ultrasonic cleaning arsenic removal, mercury, alkali metal salt After reason, 100~200 mesh are crushed to through reducing mechanism, communicated band and charge door 1 are sent into the acidleach oxidizing reactor, the kettle In through filling opening 7 add 1~3 times of volume (relative to the volume of the catalyst added) sulfuric acid, reactor through folder Set 3 heat simultaneously be incubated it is lower stir and lead to oxidant through the blow vent 2, make vanadium in discarded SCR denitration and titanium gradual Water miscible salt is converted into, reaction is drained into the first described lautertuns after completing through discharge port 6.
As shown in figure 4, the hydrolytic reaction pot of the present invention includes charge door 11, chuck 13, bearing 14, pivot protrusion 15, add Liquid mouth 17, overfall 18, agitating device, filter 21 and discharge port 22, the agitating device include agitating shaft 10, agitator 19 With cross sphenocephaly 20, cross sphenocephaly 20 is located at the bottom of agitator 19, and the agitating shaft 10 can drive agitator to rotate, Agitator can be driven to move up and down.The first foregoing hydrolytic reaction pot and the second hydrolytic reaction pot can use this hydrolysis Reactor, one of it can also use this hydrolytic reaction pot.
Only for ease of description, hydrolytic reaction pot main body is divided into three regions of upper, middle and lower, the top of hydrolytic reaction pot main body Region is provided with charge door 11, filling opening 17, overfall 18, and charge door 11 and filling opening 17 are generally located on tip position；Folder The central region of the covering hydrolytic reaction pot main body of set 13, is hydrolytic reaction pot main body heating and thermal insulation in hydrolysis；Bearing 14 The outside of chuck 13 is arranged on, to support whole hydrolytic reaction pot；Agitating device is located at the central region of reactor main body, along anti- The axis of kettle main body is answered to set；The lower area of hydrolytic reaction pot main body is provided with discharge port 22.
Hydrolytic reaction pot lower area is additionally provided with vacuum port 16, for accelerated filtration.
As shown in figure 5, the material of the filter 21 is 304 steel, it is divided into two layers up and down, lower floor's filter is fixed on master Internal side, upper level filter plate is rotatable, and filter bores 25 are equipped with every layer of filter, are connected on the center of upper level filter plate 23 Described pivot protrusion 15 is connect, has cross recess 26 in the pivot protrusion, can coordinate with described cross sphenocephaly 20, on There is one layer of filter cloth 24 between lower two layers of filter.
During hydrolysis, cross sphenocephaly 20 separates with pivot protrusion 15, the filter bores sealing of upper and lower two layers of filter, from liquid feeding Mouth adds alkali and adjusts material in reactor to pH is hydrolyzed, and is incubated lower stirring, then stops stirring insulation and stands；Mistake after the completion of hydrolysis During filter, agitating shaft 10 moves down, and cross sphenocephaly 20 coordinates with cross recess 26, rotates agitating shaft 10 and drives 23 turns of upper level filter plate It is dynamic, make the correspondence of filter bores 25 of upper and lower two layers of filter, then taking out air from vacuum port 16 makes reactor lower space be formed very Sky, accelerated filtration, the material after the completion of filtering enter next device through discharge port.
Second hydrolytic reaction pot also includes interior cooling coil 12, and interior cooling coil 12 is circumferentially positioned at the inner side table of the main body Face, central region is extended to from the upper area of hydrolytic reaction pot main body；For realizing the quick cooling of the reactor.
As shown in Fig. 2 the system of the discarded SCR denitration comprehensive reutilization of the present invention includes pretreatment unit, Reducing mechanism, above-mentioned acidleach oxidizing reactor, the first lautertuns, the first above-mentioned hydrolytic reaction pot, the above-mentioned second hydrolysis Reactor and vacuum evaporation groove；Wherein, the pretreatment of preprocessed device (including compressed air purging and ultrasonic cleaning, wherein, Purging removes surface dust, and cleaning removes surface adsorbate such as arsenic, mercury, alkali metal salt) after discarded SCR denitration warp After the reducing mechanism crushes, the acidleach oxidizing reactor is transported to by conveyer belt；At the acidleach oxidizing reactor Treatment fluid A after reason enters first lautertuns by pipeline；The filtrate of first lautertuns is pipelined to institute State the first hydrolytic reaction pot；After first hydrolytic reaction pot processing, filtrate enters second hydrolysis by pipeline Kettle；After second hydrolytic reaction pot processing, filtrate enters the vacuum evaporation groove by pipeline；Through the vacuum evaporation groove After processing, obtained sulfuric acid enters the acidleach oxidizing reactor by pipeline, is recycled.
Wherein, the course of work of the system is as follows：Preprocessed (including the compressed air purging of discarded SCR denitration And ultrasonic cleaning, wherein, purging removes surface dust, and cleaning removes surface adsorbate such as arsenic, mercury, alkali metal salt) after in powder Crushed in crushing device, communicated band is sent into acidleach oxidizing reactor, reactor heating and thermal insulation, stirs and leads to oxidant, makes to discard Vanadium and titanium in SCR denitration are gradated as water miscible salt, are then fed into the first lautertuns (such as suction filtration tank), must be contained The filtrate I and WO of vanadium, titanium3Rough filter cake.Filtrate I is sent to the first hydrolytic reaction pot, and adding alkali from filling opening makes reactor pH For 1~2, insulation, stirring, then stop stirring insulation and stand, filter, obtaining crude product containing vanadium, (predominantly vanadium crude product precipitates, simultaneously Also it is mixed with a small amount of metatitanic acid precipitation) and filtrate II.Filtrate II is sent to the second hydrolytic reaction pot, adds alkali to adjust pH to 6~8, And a small amount of crystal seed is put into, stir, heating stops agitating and heating after boiling to graying point and stood, and boils again, quick cooling, takes out Filter, metatitanic acid precipitation and filtrate II I are obtained, metatitanic acid precipitation is scrubbed, dry roasting obtains TiO2.Filtrate II I is sent into true Sulfate and sulfuric acid are successively reclaimed in empty evaporator tank desalination concentration, and sulfuric acid returns to be recycled in acidleach oxidizing reactor.Recovery WO3Completed in rough and vanadium crude product most Zhongdao smelter refined.
Embodiment 1
As Figure 1-5, present embodiment discloses a kind of method and dress of discarded SCR denitration comprehensive reutilization Put, carry out according to the following steps.
Will after the pretreatment such as the discarded compressed air soot blowing of SCR denitration and ultrasonic cleaning arsenic removal, mercury, alkali metal salt It is crushed to 120 mesh, and communicated band, which is sent into, 1.5 times of volumes (relative to catalyst volume), the acidleach that concentration is 40g/L sulfuric acid Oxidizing reactor, reactor keeps stirring at 80 DEG C and logical O2, make the vanadium in discarded SCR denitration and titanium gradate for Water miscible salt, suction filtration tank is sent into after 0.5 hour and is filtered, obtains filtrate I and WO containing vanadium, titanium3Rough filter cake.Filtrate I is sent to First hydrolytic reaction pot, adding appropriate 20%NaOH from filling opening makes reactor pH be 1.2, with 100r/ at 50 DEG C of keeping temperature Min speed stirring 1h, then stops stirring insulation and stands 30min, filter, obtain crude product containing vanadium and filtrate II.Filtrate II passes The second hydrolytic reaction pot is delivered to, adds 20%NaOH to adjust pH to 6, and put into a small amount of crystal seed (Detitanium-ore-type TiO2, its addition is 0.8%wt), speed 200r/min is kept stirring for, heating stops agitating and heating after boiling to graying point and stands 30min, boils again Boil 2h, be quickly cooled to 40 DEG C, filter, obtain metatitanic acid precipitation and filtrate III, metatitanic acid precipitation is scrubbed, dry after 600 3h is calcined at DEG C to reclaim to obtain TiO2.Filtrate III, which is sent into, is evaporated in vacuo groove desalination concentration successively recovery Na2SO4And sulfuric acid, sulfuric acid is again Return in acidleach oxidizing reactor and recycle.The WO of recovery3Completed in rough and vanadium crude product most Zhongdao smelter refined.
This technique has quickly and efficiently reclaimed V in discarded SCR denitration2O5、TiO2And WO3, the rate of recovery is respectively 90.63%th, 93.74%, 99.58%, wherein TiO2Purity is 99.51%.
Embodiment 2
As Figure 1-5, present embodiment discloses a kind of method and dress of discarded SCR denitration comprehensive reutilization Put, carry out according to the following steps.
Will after the pretreatment such as the discarded compressed air soot blowing of SCR denitration and ultrasonic cleaning arsenic removal, mercury, alkali metal salt It is crushed to 150 mesh, and communicated band, which is sent into, 1.5 times of volumes (relative to catalyst volume), the acidleach that concentration is 50g/L sulfuric acid Oxidizing reactor, reactor keeps stirring at 90 DEG C and logical O2, make the vanadium in discarded SCR denitration and titanium gradate for Water miscible salt, suction filtration tank is sent into after 1h and is filtered, obtains filtrate I and WO containing vanadium, titanium3Rough filter cake.Filtrate I is sent to the first water Solution reaction kettle, adding appropriate 20%NaOH from filling opening makes reactor pH be 1.5, with 150r/min speed at 60 DEG C of keeping temperature Degree stirring 1.5h, then stop stirring insulation and stand 60min, filter, obtain crude product containing vanadium and filtrate II.Filtrate II is sent to Two hydrolytic reaction pots, add alkali to adjust pH to 7, and put into a small amount of crystal seed (Detitanium-ore-type TiO2, its addition is 0.5%wt), protect Mixing speed 300r/min is held, heating stops agitating and heating after boiling to graying point and stands 60min, boils 3h, fast quickly cooling again But to 50 DEG C, filter, obtain metatitanic acid precipitation and filtrate III, metatitanic acid precipitation it is scrubbed, dry after at 550 DEG C be calcined 2h return Receipts obtain TiO2.Filtrate III, which is sent into, is evaporated in vacuo groove desalination concentration successively recovery Na2SO4And sulfuric acid, sulfuric acid return acidleach oxidation Recycled in reactor.The WO of recovery3Completed in rough and vanadium crude product most Zhongdao smelter refined.
This technique has quickly and efficiently reclaimed V in discarded SCR denitration2O5、TiO2And WO3, the rate of recovery is respectively 93.49%th, 94.72%, 99.26%, wherein TiO2Purity is 99.18%.
Embodiment 3
As Figure 1-5, present embodiment discloses a kind of method and dress of discarded SCR denitration comprehensive reutilization Put, carry out according to the following steps.
Will after the pretreatment such as the discarded compressed air soot blowing of SCR denitration and ultrasonic cleaning arsenic removal, mercury, alkali metal salt It is crushed to 180 mesh, and communicated band, which is sent into, 2 times of volumes (relative to catalyst volume), the acidleach oxygen that concentration is 60g/L sulfuric acid Change reactor, reactor keeps stirring at 85 DEG C and logical O2, the vanadium in discarded SCR denitration and titanium is gradated as water The salt of dissolubility, suction filtration tank is sent into after 1.5h and is filtered, obtains filtrate I and WO containing vanadium, titanium3Rough filter cake.Filtrate I is sent to the first water Solution reaction kettle, adding appropriate 20%NaOH from filling opening makes reactor pH be 1.8, with 200r/min speed at 70 DEG C of keeping temperature Degree stirring 2h, then stop stirring insulation and stand 90min, filter, obtain crude product containing vanadium and filtrate II.Filtrate II is sent to second Hydrolytic reaction pot, add 20%NaOH to adjust pH to 8, and put into a small amount of crystal seed (Detitanium-ore-type TiO2, its addition is 1%wt), Speed 350r/min is kept stirring for, heating stops agitating and heating after boiling to graying point and stands 90min, boils 4h again, quickly Be cooled to 60 DEG C, filter, obtain metatitanic acid precipitation and filtrate III, metatitanic acid precipitation is scrubbed, dry after be calcined 3h at 500 DEG C Recovery obtains TiO2.Filtrate III, which is sent into, is evaporated in vacuo groove desalination concentration successively recovery Na2SO4And sulfuric acid, sulfuric acid return acidleach oxygen Change and recycled in reactor.The WO of recovery3Completed in rough and vanadium crude product most Zhongdao smelter refined.
This technique has quickly and efficiently reclaimed V in discarded SCR denitration2O5、TiO2And WO3, the rate of recovery is respectively 92.58%th, 93.86%, 99.37%, wherein TiO2Purity is 99.27%.

Claims (27)

  1. A kind of 1. method of discarded SCR denitration comprehensive reutilization, it is characterised in that methods described includes following step Suddenly：
    (1) described discarded SCR denitration is crushed, adds in sulfuric acid and lead to oxidant, heating stirring, filtering to contain The filtrate I and WO of vanadium, titanium3Rough filter cake I；
    (2) alkali regulation pH to 1~2, heating stirring are added in the filtrate I obtained to step (1), insulation is stood, and is filtrated to get filter Cake II and filtrate II；It is mainly vanadium crude product precipitation in the filter cake II, while is also mixed with a small amount of metatitanic acid precipitation；The filtrate II includes non-hydrolysing titanyl sulfate；
    (3) add alkali to adjust pH to 6~8 in the filtrate II obtained to step (2), and add a small amount of crystal seed, heating stirring, be incubated quiet Put, boil again, quick cooling, be filtrated to get metatitanic acid precipitation and filtrate II I；
    (4) sulfate and sulfuric acid that the filtrate II I in step (3) is successively recycled through desalination concentration, the sulfuric acid return step Suddenly recycled in (1)；
    (5) metatitanic acid in step (3) precipitates scrubbed, dry roasting and obtains TiO2。
  2. 2. according to the method for claim 1, it is characterised in that also include pre-treatment step before step (1), be specially：With Compressed air purging SCR denitration removes surface dust, then removes surface adsorbate, drying for standby by being cleaned by ultrasonic.
  3. 3. according to the method for claim 1, it is characterised in that the discarded SCR denitration in step (1) is crushed to 100~200 mesh.
  4. 4. according to the method for claim 2, it is characterised in that the discarded SCR denitration by pretreatment in step (1) is urged Agent is crushed to 100~200 mesh.
  5. 5. according to the method for claim 1, it is characterised in that the concentration of the sulfuric acid in step (1) is 30~70g/L, is added Enter 1~3 times of volume that amount is discarded SCR denitration volume.
  6. 6. according to the method for claim 1, it is characterised in that temperature during stirring in step (1) is 80~100 DEG C, Mixing time is 0.5~2h.
  7. 7. according to the method for claim 1, it is characterised in that the oxidant described in step (1) is oxygen, in ozone It is a kind of.
  8. 8. according to the method for claim 1, it is characterised in that alkali described in step (2) is NaOH or KOH.
  9. 9. according to the method for claim 8, it is characterised in that the mass percent concentration of the alkali is 20%.
  10. 10. according to the method for claim 1, it is characterised in that the mixing speed in step (2) is 100~300r/min, Mixing time is 1~2h, and temperature is 50~70 DEG C during stirring.
  11. 11. according to the method for claim 1, it is characterised in that the insulation time of repose in step (2) is 10~90min.
  12. 12. according to the method for claim 1, it is characterised in that alkali described in step (3) is NaOH or KOH.
  13. 13. according to the method for claim 12, it is characterised in that the mass percent concentration of the alkali is 20%.
  14. 14. according to the method for claim 1, it is characterised in that the step added in step (3) after a small amount of crystal seed is specific For：200~400r/min of speed is kept stirring for, heating stops stirring after boiling to graying point, insulation stands 10~90min, then It is secondary to boil 2~4h, 30~60 DEG C are quickly cooled to, is filtrated to get metatitanic acid precipitation and filtrate II I.
  15. 15. according to the method for claim 1, it is characterised in that the crystal seed described in step (3) is Detitanium-ore-type TiO2, its Addition is with TiO in filtrate II2Count 0.5~1wt% of titanium quality.
  16. 16. according to the method for claim 1, it is characterised in that the sintering temperature in step (5) is 500~800 DEG C, roasting The burning time is 1~4h.
  17. 17. a kind of discarded SCR denitration comprehensive reutilization for realizing any one of claim 1-16 methods described is System, it is characterised in that the system include reducing mechanism, acidleach oxidizing reactor, the first lautertuns, the first hydrolytic reaction pot, Second hydrolytic reaction pot and vacuum evaporation groove；
    The discarded SCR denitration is transported to the acidleach after reducing mechanism crushing, by conveyer belt and aoxidized instead Answer kettle；
    Treatment fluid A after acidleach oxidizing reactor processing enters first lautertuns by pipeline；
    The filtrate of first lautertuns is pipelined to first hydrolytic reaction pot；
    Treatment fluid B after first hydrolytic reaction pot processing enters second hydrolytic reaction pot by pipeline；
    Treatment fluid C after second hydrolytic reaction pot processing enters the vacuum evaporation groove by pipeline；
    After the vacuum evaporation groove processing, obtained sulfuric acid enters the acidleach oxidizing reactor by pipeline, is circulated Use.
  18. 18. system according to claim 17, it is characterised in that also include pretreatment unit before reducing mechanism, be used for Pre-processed before the discarded SCR denitration enters reducing mechanism；It is described pretreatment include compressed air purging with It is cleaned by ultrasonic.
  19. 19. the system according to claim 17 or 18, it is characterised in that the acidleach oxidizing reactor include charge door, Blow vent, agitator, filling opening, discharge port and main body；Wherein, charge door and filling opening are located at the tip position of main body, are used for The blow vent for leading to the oxidant is arranged on the top of main body, and agitator is located at body interior, and discharge port is arranged under main body Portion, appendix is sealedly connected with blow vent, oxidant is introduced directly into the lower section of the agitator.
  20. 20. system according to claim 19, it is characterised in that the acidleach oxidizing reactor also includes chuck and overflow Mouthful；The middle and lower part of the chuck parcel main body, plays heating and thermal insulation effect；The overfall is located at the upper area of main body.
  21. 21. system according to claim 20, it is characterised in that the reactor also includes bearing.
  22. 22. the system according to claim 17 or 18, it is characterised in that the described first or second hydrolytic reaction pot includes adding Material mouth, filling opening, discharge port, agitating device and main body；Wherein, charge door and filling opening are located at the tip position of main body, stirring Device is located at body interior, and discharge port is arranged on the bottom of main body.
  23. 23. system according to claim 22, it is characterised in that also include folder in the described first or second hydrolytic reaction pot Set and overfall.
  24. 24. system according to claim 22, it is characterised in that also include interior cooler pan in second hydrolytic reaction pot Pipe.
  25. 25. system according to claim 22, it is characterised in that the agitating device of the described first or second hydrolytic reaction pot Including agitating shaft, agitator and cross sphenocephaly, cross sphenocephaly is located at stirrer bottom, and the agitating shaft can drive stirring Device rotates, and can also drive agitator to move up and down, is provided with the described first or second hydrolytic reaction pot positioned at the hydrolysis The filter of the lower area of reactor main body.
  26. 26. system according to claim 25, it is characterised in that the filter is divided into two layers up and down, lower floor's filter It is fixed on the inside of main body, upper level filter plate is rotatable, and filter bores, the center of upper level filter plate are equipped with every layer of filter It is upper to connect a pivot protrusion, there is cross recess in the pivot protrusion, can coordinate with described cross sphenocephaly, upper and lower two layers One layer of filter cloth is provided between filter；During hydrolysis, cross sphenocephaly separates with pivot protrusion, and the filter bores of two layers of filter are close Envelope；When being filtered after hydrolysis, the agitating shaft moves down so that cross sphenocephaly coordinates with cross recess, is turned by agitating shaft It is dynamic to drive upper level filter plate to rotate, so that the filter bores alignment of upper and lower two layers of filter, forms filtration condition, the so hydrolysis Reactor can be completed to hydrolyze and filtered simultaneously.
  27. 27. system according to claim 22, it is characterised in that hydrolytic reaction pot lower area is additionally provided with vacuum port, It can speed up filtering.
CN201510943530.4A 2015-09-11 2015-12-16 A kind of method and system of discarded SCR denitration comprehensive reutilization Expired - Fee Related CN105536817B (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0211443A1 (en) * 1985-08-19 1987-02-25 Siemens Aktiengesellschaft A process for preparing a catalyst for the selective reduction of nitrogen oxides from exhaust gases
CN102936049A (en) * 2012-11-26 2013-02-20 西南民族大学 Method for extracting tungsten, titanium and vanadium from waste SCR (selective catalytic reduction) catalyst
CN102962079A (en) * 2012-11-27 2013-03-13 南京工业大学 Regeneration method for waste vanadium-titanium-based SCR (Selective Catalytic Reduction) flue gas denitrification catalyst
CN103508491A (en) * 2013-09-23 2014-01-15 宜兴市宜刚环保工程材料有限公司 Method for regeneration and resource utilization of waste honeycombed denitrification catalyst
CN104195342A (en) * 2014-09-17 2014-12-10 华北电力大学 Method for recycling vanadium pentoxide in waste SCR (Selective Catalytic Reduction) denitration catalyst
CN104549380A (en) * 2015-01-22 2015-04-29 龙岩紫荆创新研究院 Method for phosphoric acidification modification of TiO2 carrier for preparing V2O5-WO3/TiO2 based SCR (selective catalytic reduction) denitration catalyst

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0211443A1 (en) * 1985-08-19 1987-02-25 Siemens Aktiengesellschaft A process for preparing a catalyst for the selective reduction of nitrogen oxides from exhaust gases
CN102936049A (en) * 2012-11-26 2013-02-20 西南民族大学 Method for extracting tungsten, titanium and vanadium from waste SCR (selective catalytic reduction) catalyst
CN102962079A (en) * 2012-11-27 2013-03-13 南京工业大学 Regeneration method for waste vanadium-titanium-based SCR (Selective Catalytic Reduction) flue gas denitrification catalyst
CN103508491A (en) * 2013-09-23 2014-01-15 宜兴市宜刚环保工程材料有限公司 Method for regeneration and resource utilization of waste honeycombed denitrification catalyst
CN104195342A (en) * 2014-09-17 2014-12-10 华北电力大学 Method for recycling vanadium pentoxide in waste SCR (Selective Catalytic Reduction) denitration catalyst
CN104549380A (en) * 2015-01-22 2015-04-29 龙岩紫荆创新研究院 Method for phosphoric acidification modification of TiO2 carrier for preparing V2O5-WO3/TiO2 based SCR (selective catalytic reduction) denitration catalyst

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