CN104772318B - A kind of method of comprehensive utilization to discarded SCR denitration - Google Patents
A kind of method of comprehensive utilization to discarded SCR denitration Download PDFInfo
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- CN104772318B CN104772318B CN201510070862.6A CN201510070862A CN104772318B CN 104772318 B CN104772318 B CN 104772318B CN 201510070862 A CN201510070862 A CN 201510070862A CN 104772318 B CN104772318 B CN 104772318B
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- scr denitration
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Abstract
The present invention relates to a kind of method of comprehensive utilization to discarded SCR denitration.Comprise to discarded SCR denitration pretreatment, to the pulverizing of discarded SCR denitration, utilize acid solution to leach to extract vanadium to discarded SCR denitration, utilize alkali lye to leach discarded SCR denitration is extracted to tungsten or molybdenum, utilized TiO
2etc. step, realize the recycling to discarded SCR denitration and harmlessness disposing.The present invention is main in a wet process, simple and reliable process, and product utilization is worth large, achieves and fully utilizes discarded SCR catalyst.
Description
Technical field
The present invention relates in waste catalyst recovery and utilization technology field, be specifically related to a kind of method of comprehensive utilization to discarded SCR denitration.
Background technology
China is an energy resource consumption big country based on thermal power generation, has discharged a large amount of nitrogen oxide while fire coal, if do not tightened control, the consequence caused China's air environmental pollution will be more and more serious.According to the data that China Environmental Monitoring General Station provides, within 2011, China's discharged nitrous oxides total amount is 2404.3 ten thousand tons, wherein the discharged nitrous oxides of power industry accounts for more than 45%, account for the over half of various burner total emission volumn, and the nitrogen oxide more than 80% of power industry discharge is by discharged from coal-fired boiler.。
For reducing discharged nitrous oxides, selective catalytic reduction is widely used in home and abroad station, is the main flow of coal unit denitration.In SCR system, most critical parts are SCR catalyst, and SCR denitration is primarily of titanium dioxide (TiO
2, content 80%-90%), vanadic anhydride (V
2o
5, content 0.5%-1%), tungstic acid or molybdenum trioxide (WO
3or MoO
3, content 5%-10%) and composition.Deng metal oxide.In SCR device actual motion, a variety of causes may cause catalyst activity to reduce, the lost of life.Along with the growth of catalyst service time, catalyst generation heat ageing, the part or all of loss of activity because suffering the murder by poisoning of some poisonous substance; After denitrating catalyst inactivation, the integer catalyst of about 70%-80% can regenerate, and 20%-30% is damaged, and catalyst cannot regenerate.In whole life cycle, renewable at most 3 times of denitrating catalyst, recyclable various raw material carries out final disposal afterwards.For the regeneration that the processing mode first considered of catalyst lost efficacy is catalyst, extend its service life, economize on resources.But not every spent catalyst can both pass through regeneration reuse; if spent catalyst adopts regeneration still can not activity recovery, need to carry out waste treatment to it; because containing a certain amount of toxic metals in spent catalyst; belong to hazardous waste; therefore; harmlessness disposing and recycling must be carried out, protection of the environment to it.
Point out according to State Grid Corporation of China's " energy base construction and electric power Long-and Medium-term Development planning in-depth research " report, in " 12 " period, newly-increased installation scale 2.87 hundred million kilowatts, within 2015, thermoelectricity installation total capacity will reach 900,000,000 kilowatts; " 13 " period will increase installation scale 2.34 hundred million kilowatts newly, and to the year two thousand twenty latter stage, thermoelectricity total capacity of installing will reach 1,000,000,000 kilowatts.Because SCR catalyst all will be changed for every 3 years, therefore SCR catalyst needs the amount of disposal huge.On 08 05th, 2014, include SCR catalyst in hazardous waste in Chinese Ministry of Environmental Protection's " notice about strengthening waste flue gas denitration catalyst supervision " to manage, the collection of inactivation SCR catalyst, storage, transport, disposal must strictly perform by the regulation of hazardous waste.Therefore, the meaning that harmlessness disposing and recycling have particular importance is carried out to SCR catalyst.
At present, the domestic recovery technology to discarded SCR catalyst mainly contains sodium (calcium) and changes roasting-water logging, wet method acid immersion and alkali leaching, electrolysis etc., the main V reclaimed wherein
2o
5, WO
3(or MoO
3) and TiO
2.Chinese patent CN102936049A, CN101921916A, CN102936039A, CN10255714A, CN201010254247 etc. describe and utilize highly basic roasting-water soaking method to reclaim V from discarded SCR catalyst
2o
5, WO
3and TiO
2; Chinese patent CN103088217A describes and utilizes roasting-extracting process to reclaim tungsten component from discarded SCR catalyst; Chinese patent CN102732730A describes and utilizes electrolysis to reclaim vanadium component from discarded SCR catalyst; Chinese patent CN102930649B describes a kind of method extracting tungsten, titanium, vanadium from discarded SCR catalyst; Chinese patent CN104118911A describes a kind of method reclaiming tungstic acid in discarded SCR catalyst completely., all there is such or such deficiency in all these methods, for the deficiency that above-mentioned prior art exists, the invention provides a kind of new method fully utilized discarded SCR catalyst.
Summary of the invention
A kind of method of comprehensive utilization to discarded SCR denitration of the present invention, concrete steps are as follows:
1. discarded SCR denitration pretreatment: use high pressure airgun to purge SCR catalyst block surface and duct, then SCR catalyst block duct is swept by Water spray spray, finally the SCR catalyst block after above-mentioned process is put into blowing-type drying box dry, baking temperature is 80 ~ 105 DEG C, and drying time is 2 ~ 4h.
2. pulverize: above-mentioned dried discarded SCR catalyst block is put into disintegrating apparatus, is crushed to 100-300 order.
3. extract vanadium: discarded SCR catalyst powder step 2 processed immerses in oxalic acid solution, and stir, the reaction of generation is: 3H
2c
2o
4+ V
2o
5=2VOC
2o
4+ 3H
2o+2CO
2, at this moment, oxalic acid and vanadic anhydride react oxalic vanadyl, and this walks the vanadic anhydride component eliminated in discarded SCR catalyst powder; Then filter, because the vanadyl oxalate generated is solvable, after filtering, vanadyl oxalate enters in liquid, and all the other metal oxides WO
3(or MoO
3) and TiO
2leach Deng with insoluble slag form; Again vanadyl oxalate solution evaporate to dryness just can be obtained vanadyl oxalate product.
4. extract tungsten or molybdenum: step 3 was processed insoluble slag and immerse in alkali lye, stir, the reaction of generation is: 2OH
-+ WO
3=WO
4 2-+ H
2o, or 2OH
-+ MoO
3=MoO
4 2-+ H
2o, alkali and tungsten oxide or molybdenum oxide react and generate tungstates or molybdate, and this walks the tungsten oxide or molybdenum oxide component that eliminate in discarded SCR catalyst powder; Then filter, due to the tungstates that generates or molybdate solvable, to enter in liquid after filtration, and TiO
2leach Deng with insoluble slag form; Again tungstates or molybdate solution are passed through to regulate pH value, wolframic acid or precipitate molybdic acid can be obtained.
5. utilize TiO
2: insoluble slag step 4 processed is dried, because this insoluble slag is to contain TiO
2be that all oneself removes main, poisonous material, can be used as high-quality building materials raw material.
Beneficial effect of the present invention: 1, the present invention is main in a wet process, and simple and reliable process, shortens conventional process flow, saves the discarded SCR denitration cost of process, reduces energy consumption.2, the vanadyl oxalate product prepared by the present invention, wolframic acid or molybdic acid product purity are high, and value is large.3, the TiO prepared by the present invention
2insoluble slag, nontoxic, can be used as high-quality building materials raw material.4, present invention achieves discarded SCR catalyst is fully utilized, environmental protection.
Detailed description of the invention
Embodiment 1
The honeycomb fashion SCR catalyst that Qu Yigenmou power plant is discarded, use high pressure airgun to purge SCR catalyst block surface and duct, block duct is swept in Water spray spray, put into blowing-type drying box dry, baking temperature is 95 DEG C, and drying time is 3h, is then crushed to 200 orders; To discard SCR catalyst powder immerses in quantitative 3% oxalic acid solution, stirs, and filters, obtain vanadyl oxalate solid after filtrate evaporate to dryness after reaction 5h; Immerse in quantitative 20% sodium hydroxide solution by upper step gained filter residue again, stir, filter after 90 DEG C of reaction 10h, filter residue is with TiO
2be main, as high-quality building materials raw material after oven dry; Filtrate is tungstates or molybdate solution, then the pH value hydrochloric acid of filtrate is transferred to 6, refilters, and sediment is wolframic acid or molybdic acid.Through detecting: vanadyl oxalate purity reaches 98.3%, and wolframic acid purity reaches 97.2%, with TiO in filter residue
2purity reaches 96.0%.
Embodiment 2
The honeycomb fashion SCR catalyst that Qu Yigenmou power plant is discarded, use high pressure airgun to purge SCR catalyst block surface and duct, block duct is swept in Water spray spray, put into blowing-type drying box dry, baking temperature is 95 DEG C, and drying time is 3h, is then crushed to 200 orders; To discard SCR catalyst powder immerses in quantitative 3% oxalic acid+sulfuric acid solution, stirs, and filters, obtain vanadyl oxalate solid after filtrate evaporate to dryness after reaction 3h; Immerse in quantitative 20% NaOH+sodium carbonate liquor by upper step gained filter residue again, stir, filter after 90 DEG C of reaction 8h, filter residue is with TiO
2be main, as high-quality building materials raw material after oven dry; Filtrate is tungstates or molybdate solution, then the pH value sulfuric acid of filtrate is transferred to 6, refilters, and sediment is wolframic acid or molybdic acid.Through detecting: vanadyl oxalate purity reaches 99.1%, and wolframic acid purity reaches 97.3%, with TiO in filter residue
2purity reaches 97.1%.
Claims (4)
1., to a method of comprehensive utilization for discarded SCR denitration, comprise following steps:
Step 1: to discarded SCR denitration pretreatment, high pressure airgun is used to purge SCR catalyst block surface and duct, then sweep SCR catalyst block duct by Water spray spray, finally the SCR catalyst block after above-mentioned process is put into blowing-type drying box dry;
Step 2: pulverize discarded SCR denitration, puts into disintegrating apparatus by above-mentioned dried discarded SCR catalyst block, is crushed to 100-300 order;
Step 3: utilize acid solution to leach and extract vanadium to discarded SCR denitration, discarded SCR catalyst powder step 2 processed immerses in oxalic acid solution, and stir, the reaction of generation is: 3H
2c
2o
4+ V
2o
5=2VOC
2o
4+ 3H
2o+2CO
2, at this moment, oxalic acid and vanadic anhydride react oxalic vanadyl, and this walks the vanadic anhydride component eliminated in discarded SCR catalyst powder; Then filter, because the vanadyl oxalate generated is solvable, after filtering, vanadyl oxalate enters in liquid, and all the other metal oxides WO
3or MoO
3and TiO
2leach with insoluble slag form, then vanadyl oxalate solution evaporate to dryness just can be obtained vanadyl oxalate product;
Step 4: utilize alkali lye to leach and extract tungsten or molybdenum to discarded SCR denitration, step 3 was processed insoluble slag and immerse in alkali lye, stir, the reaction of generation is: 2OH
-+ WO
3=WO
4 2-+ H
2o, or 2OH
-+ MoO
3=MoO
4 2-+ H
2o, alkali and tungsten oxide or molybdenum oxide react and generate tungstates or molybdate, and this walks the tungsten oxide or molybdenum oxide component that eliminate in discarded SCR catalyst powder; Then filter, due to the tungstates that generates or molybdate solvable, to enter in liquid after filtration, and TiO
2leach with insoluble slag form, then tungstates or molybdate solution are obtained wolframic acid or precipitate molybdic acid by regulating pH value;
Step 5: insoluble slag step 4 processed is dried, because this insoluble slag is to contain TiO
2be that main, poisonous material is removed all, can be used as high-quality environment-friendly building materials raw material, realize the recycling to discarded SCR denitration and harmlessness disposing.
2. a kind of method of comprehensive utilization to discarded SCR denitration according to claim 1, it is characterized in that: baking temperature is 80 ~ 105 DEG C, drying time is 2 ~ 4h.。
3. a kind of method of comprehensive utilization to discarded SCR denitration according to claim 1, is characterized in that: leach utilizing acid solution and extract in vanadium process to discarded SCR denitration, the concentration of acid is 1-80%.
4. a kind of method of comprehensive utilization to discarded SCR denitration according to claim 1, it is characterized in that: utilize alkali lye to leach and extract in tungsten or molybdenum process discarded SCR denitration, selected alkali is one or more in NaOH, potassium hydroxide, calcium hydroxide, sodium carbonate, potash, sodium oxide molybdena, potassium oxide, calcium oxide, organic base; Paper mill wastewater is 1-85%.
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| CN104772318B true CN104772318B (en) | 2016-03-02 |
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| CN107416902A (en) * | 2016-05-24 | 2017-12-01 | 北京清树科技发展有限公司 | A kind of method that low cost reclaims waste and old SCR denitration component materials |
| CN107416904A (en) * | 2016-05-24 | 2017-12-01 | 北京清树科技发展有限公司 | A kind of method for reclaiming component materials in waste and old SCR denitration |
| CN106622399B (en) * | 2016-12-16 | 2019-05-17 | 华北电力大学 | A kind of recycling method of discarded SCR denitration |
| CN106866073A (en) * | 2017-02-25 | 2017-06-20 | 山东鸿创催化剂综合利用有限公司 | A kind of useless SCR denitration recovery method |
| CN108126763B (en) * | 2018-02-13 | 2019-03-12 | 宜兴市宜刚环保工程材料有限公司 | A kind of denitrating catalyst and preparation method thereof |
| CN108687105A (en) * | 2018-04-23 | 2018-10-23 | 清华大学 | A kind of method of comprehensive utilization to discarding SCR denitration |
| CN110193364A (en) * | 2019-06-04 | 2019-09-03 | 河北惠尔信新材料有限公司 | A kind of discarded SCR catalyst recycling technique |
| CN110923459B (en) * | 2019-12-29 | 2021-02-05 | 江苏龙清环境技术有限公司 | Method for recovering titanium-tungsten powder from waste SCR catalyst |
| CN111996394A (en) * | 2020-08-20 | 2020-11-27 | 兰立华 | Efficient extraction and separation method for vanadium and tungsten in alkali leaching solution of waste denitration catalyst |
| CN115849418B (en) * | 2023-02-06 | 2023-05-09 | 国能龙源环保有限公司 | Method for preparing aluminum hydroxide by using waste denitration catalyst |
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| KR101199477B1 (en) * | 2010-09-20 | 2012-11-09 | 한국전력공사 | Method of regenerating SCR catalyst |
| CN104118911B (en) * | 2014-07-11 | 2015-09-23 | 沈阳远大科技园有限公司 | A kind of method reclaiming tungstic oxide in discarded SCR catalyst completely |
| CN104195342B (en) * | 2014-09-17 | 2016-06-01 | 华北电力大学 | A kind of method reclaiming Vanadium Pentoxide in FLAKES composition in waste and old SCR denitration |
| CN104261415B (en) * | 2014-09-30 | 2016-01-13 | 沈阳远大科技园有限公司 | A kind of method reclaiming silicon-dioxide in discarded SCR catalyst completely |
| CN104263946B (en) * | 2014-10-10 | 2016-07-27 | 武汉凯迪电力环保有限公司 | A kind of method reclaiming tungsten, vanadium, titanium from SCR denitration dead catalyst |
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