CN104609753A - Innocuous treatment process of waste flue gas denitration catalyst - Google Patents
Innocuous treatment process of waste flue gas denitration catalyst Download PDFInfo
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- CN104609753A CN104609753A CN201510060312.6A CN201510060312A CN104609753A CN 104609753 A CN104609753 A CN 104609753A CN 201510060312 A CN201510060312 A CN 201510060312A CN 104609753 A CN104609753 A CN 104609753A
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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Abstract
The invention relates to an innocuous treatment process of waste flue gas denitration catalyst. The process comprises a main process flow, wastewater treatment flow and sludge treatment flow. According to the process, by the process steps such as decomposing, rinsing and separating, crushing and grinding, mixing and shaping, deep treatment and recycling of wastewater, as well as stabilization and solidification of sludge cakes obtained after rinsing, the waste flue gas denitration catalyst which is a dangerous solid waste is treated into a comprehensively used product harmless to the environment. A brand-new and complete comprehensive utilization process of waste glue gas denitration catalyst treatment, which has a relatively simple process system, is provided.
Description
Technical field
The present invention relates to a kind of waste flue gas denitration catalyst harmless treatment process.
Background technology
China adopts the coal steam-electric plant smoke denitration of SCR technology to transform on a large scale and starts from 2010, and flue gas denitrification system the earliest can pursue to 2008.The chemical lifetime of the vanadium Titanium series catalyst that SCR denitrating flue gas uses is 20000-24000 hour, and mechanical life is 10 years.But due to quality product in practical application, running environment affects, and the catalyzer that can reach the theoretical life-span is less, generally namely occurs after 3 years that activity decrease needs cleaning and regeneration in use, 6-7 just needs to update afterwards, therefore will produce a large amount of useless denitrating catalysts in 2-3 from now on.Because useless denitrating catalyst treatment and use is still in the starting stage, domestic also do not have an enterprise can carry out this work completely.In general office of national environmental protection portion [2014] No. 990 letters that on August 5th, 2014 puts into effect, vanadium Titanium series catalyst being scrapped rank rear is hazardous solid waste, is numbered HW49.Common useless denitrating catalyst disposal options mainly contains high-temperature calcination process (day the manner) and solidify & bury process (American Way) in the world.No matter which kind of mode is hazardous solid waste method for innocent treatment.High-temperature calcination process and solidify & bury process are not all inconsistent with China's national situation, and the base material (titanium dioxide) of useless denitrating catalyst is a kind of intermediate materials with extensive use, but not hazardous solid waste.Why useless denitrating catalyst has leachability toxicity, mainly because denitrating catalyst in use can adsorb some objectionable impuritiess in flyash and flue gas, as arsenic, selenium, mercury etc.The harmless treatment of useless denitrating catalyst is exactly remove the hazardous and noxious substances in useless denitrating catalyst, and to part can be utilized to recycle.The method removing the objectionable impurities in useless denitrating catalyst has multiple, but a kind of method is not the scheme adopting the present invention to adopt.The present invention intends the hazardous and noxious substances leached by physics, chemical process in useless denitrating catalyst, to being carried out landfill after innoxious solidification treatment by the hazardous and noxious substances leached, and to not having the catalyst substrate of Leaching to recycle and making new product.
Summary of the invention
For problems of the prior art, the object of the present invention is to provide a kind of technical scheme of waste flue gas denitration catalyst harmless treatment process.
Described waste flue gas denitration catalyst harmless treatment process, is characterized in that comprising main technical process, wastewater treatment process and sludge treatment flow process;
A, main technical process:
A. mechanically useless denitrification catalyst module is separated into base material and steel plate;
B. base material isolated from useless denitrification catalyst module is put into the ultrasonic just wash pool of HY-9180 type and carry out ultrasonic cleaning, scavenging period controls at 10-30 minute, removes the particulate matter in base material micropore;
C. put into HY-9185 type matting pond through the base material of ultrasonic previous cleaning and carry out matting: base material is put into HY-9185 type matting pond, and regulate liquid level, add HY-1 clean-out system, scavenging period controls at 20-40 minute, scavenging solution pH value, between 2-5, is cleaned out the hazardous and noxious substances of base material by matting;
D. put into HY-9182 type ultrasonic fine purifiation pond through the base material of matting and carry out ultrasonic fine purifiation: base material is put into ultrasonic fine purifiation pond, and regulate liquid level, add HY-2 clean-out system, fine purifiation time controling, at 10-30 minute, is cleaned out hazardous and noxious substances in the substrate residual after matting by ultrasonic fine purifiation;
E. put into clear water rinsing bath through the base material of ultrasonic fine purifiation and carry out clear water rinsing, rinsing time controls at 10-40 minute, is washed away the cleaning raffinate in base material by clear water rinsing;
F. carry out sampling chemical examination to the base material through clear water rinsing, the base material without leachability toxicity enters next process, and defective base material repeats above-mentioned steps b-e;
G. HY-9175 type dryer is utilized to carry out drying treatment to qualified base material;
H. utilize thunder to cover 5R4121 type medium speed mill to grind dry base material, to make fineness be 300-400 mesh sieve percent of pass is the fines of 90%;
I. the base material and cement, sandstone, water of wearing into fines are mixed in proportion stirring;
J. the subparticle base material be uniformly mixed and cement, sandstone, water miscellany are put into plan nit 1500 type cement brick shaping machine shaping;
K. shaping cement brick is by forming product after seasoning;
B, wastewater treatment process:
1) waste water that in main technical process, ultrasonic previous cleaning, matting, ultrasonic fine purifiation, clear water rinsing produce is undertaken collecting and pre-treatment by the former pond of waste water;
2) carry out deionization process to through the pretreated waste water in the former pond of waste water, the heavy metal in waste water and hazardous and noxious substances are concentrated, precipitate;
3) clear water produced after waste water deionization treatment system enters process water pond reuse;
4) concentrated solution produced after waste water deionization treatment system enters pressure filter and suppresses mud cake;
5) filtrate water that pressure filter extrudes enters waste water former pond circulation;
C, sludge treatment flow process:
1. pressure filter extrude mud cake and stablizer, cement, sandstone be mixed in proportion stirring;
2. by cement brick shaping machine, the mixture of mud cake and stablizer, cement, sandstone is pressed into cured block;
3. the mud cake being pressed into cured block is put into HY-9175 type dryer, under the environment of 400-500 degree Celsius, dry calcining;
4. becoming after having calcined can the cured block of landfill.
Described waste flue gas denitration catalyst harmless treatment process, is characterized in that in described step a, mechanical system is electric wheel cutting or autogenous fusing.
Described waste flue gas denitration catalyst harmless treatment process, is characterized in that base material in described step I, cement, sandstone, water mix in the ratio of 4:1:4:1.
Described waste flue gas denitration catalyst harmless treatment process, is characterized in that the described step mud cake that 1. pressure filter extrudes mixes in the ratio of 5:1:1:3 with stablizer, cement, sandstone.
Beneficial effect of the present invention is mainly manifested in:
1. make useless denitrating catalyst nontoxicization by physics, chemical process;
2. pair cleaned spent catalyst base material grinds;
3. the granularity control of spent catalyst base material grinding is at 400 order percent of pass 90%;
4. fine powdery spent catalyst base material and flyash, cement make cement brick in proportion;
5. the poisonous and harmful mud cleaning spent catalyst generation is uniformly mixed into cured block by adding stablizer with cement, sandstone;
6. dry through calcining with the cured block of stablizer, cement, sandstone mixing moulding.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Below in conjunction with Figure of description, the invention will be further described:
The present invention includes main technical process, wastewater treatment process and sludge treatment flow process;
Main technical process: utilize mechanical system to be separated spent catalyst module, steel substrate or steel shell are separated with the base material that titanium dioxide is made, the steel substrate be separated or steel shell are sold as waste and old steel, titanium dioxide base material is put into mechanical cleaning pond and is carried out ultrasonic cleaning, then put into matting pond and carry out matting, put into clean water basin again and carry out rinsing, and base material is sampled, finally the chemical examination of leachability toxicity is carried out to sample, defective, repeat said process, nontoxic, enter next process and carry out drying treatment, crushed after being dried is ground, with flyash, cement is mixed in proportion makes cement brick,
Wastewater treatment process: the waste water produced in main technical process, enters wastewater collection pond, carries out flocculation precipitation pre-treatment, is then processed by embrane method waste water deionization treatment system, and the clear water obtained is recycled, and mud then enters sludge treatment flow process;
Sludge treatment flow process: the mud that waste water deionization treatment system produces enters batch mixing pond, interpolation stablizer, cement, sandstone are uniformly mixed, and forming and hardening becomes block, adopt and dry calcining case calcining oven dry, make transportable landfill finished product, be transported to landfill yard landfill.
Particularly:
A, main technical process: mechanical separation-ultrasonic previous cleaning-matting-ultrasonic fine purifiation-clear water rinsing-sampling chemical examination-drying treatment-milled processed-mix and blend-cement brick is shaping-product.
B, wastewater treatment process: process water pond-ultrasonic previous cleaning, matting, ultrasonic fine purifiation, clear water rinsing-waste water former pond-Sewage advanced treatment-process water pond (clear water) (the former pond of filtrate water-waste water).
C, sludge treatment flow process: pressure filter-mud cake mix and blend (adding stablizer, cement, sandstone)-mud cake curing molding-mud cake oven dry calcining-can landfill cured block.
The present invention is by disassembling, cleaning separation, pulverize grinding, mixing moulding, Sewage advanced treatment (deionization process) and reuse, the mud cake cleaned out carries out the processing steps such as stable curing and useless denitrating catalyst is not had influential comprehensive utilization product from the paired environment of dangerous solid wastes disposing, provide a kind of completely newly, complete, the relatively simply useless denitrating catalyst of process system disposes comprehensive utilization process.
Technical process of the present invention is described in detail in detail below:
A, main technical process:
A. mechanically useless denitrification catalyst module is separated into base material and steel plate, electric wheel can be adopted to cut for this mechanical system or autogenous fusing mode is carried out;
B. base material isolated from useless denitrification catalyst module is put into the ultrasonic just wash pool of HY-9180 type to clean, scavenging period controls at 10-30 minute, the main particulate matter removed in base material micropore;
C. put into HY-9185 type matting pond through the base material of ultrasonic previous cleaning and carry out matting: base material is put into HY-9185 type matting pond, and regulate liquid level to suitable, add HY-1 clean-out system, scavenging period controls at 20-40 minute, scavenging solution pH value, between 2-5, is cleaned out the hazardous and noxious substances of base material by matting;
D. put into HY-9182 type ultrasonic fine purifiation pond through the base material of matting and carry out ultrasonic fine purifiation: base material is put into ultrasonic fine purifiation pond, and regulate liquid level to suitable, add HY-2 clean-out system, fine purifiation time controling, at 10-30 minute, is cleaned out hazardous and noxious substances in the substrate residual after matting by ultrasonic fine purifiation;
E. clear water rinsing bath put into by the base material through ultrasonic fine purifiation, and rinsing time controls at 10-40 minute, washed away the cleaning raffinate in base material by clear water rinsing;
F. carry out sampling chemical examination to the base material through clear water rinsing, the base material without leachability toxicity enters next process, and defective base material repeats above-mentioned steps 2-5;
G. HY-9175 type dryer is utilized to carry out drying treatment to qualified base material;
H. utilize thunder to cover 5R4121 type medium speed mill to grind dry base material, to make fineness be 300-400 mesh sieve percent of pass is the fines of 90%;
I. the base material of fines and cement, sandstone, water will be worn in the ratio mix and blend of 4:1:4:1;
J. the subparticle base material be uniformly mixed and cement, sandstone, water miscellany are put into the plan nit 1500 type cement brick shaping machine that Fujian Quan'gong Machinery Co., Ltd. produces shaping;
K. shaping cement brick is by forming product after seasoning.
B, wastewater treatment process:
1) waste water that in main technical process, ultrasonic previous cleaning, matting, ultrasonic fine purifiation, clear water rinsing produce is undertaken collecting and pre-treatment by the former pond of waste water;
2) carry out deionization process to through the pretreated waste water in the former pond of waste water, the heavy metal in waste water and hazardous and noxious substances are concentrated, precipitate;
3) clear water produced after waste water deionization treatment system enters process water pond reuse;
4) concentrated solution produced after waste water deionization treatment system enters pressure filter and suppresses mud cake;
5) filtrate water that pressure filter extrudes enters waste water former pond circulation.
C, sludge treatment flow process:
1. the mud cake that extrudes of pressure filter and stablizer (epoxy resin), cement sandstone are in the ratio mix and blend of 5:1:1:3;
2. by plan nit 1500 type cement brick shaping machine, the mixture of mud cake and stablizer, cement, sandstone is pressed into cured block;
3. the mud cake being pressed into cured block is put into HY-9175 type dryer, under the environment of 400-500 degree Celsius, dry calcining;
4. becoming after having calcined can the cured block of landfill.
The ultrasonic just wash pool of HY-9180 type of the present invention is purchased from Hangzhou Hai Yun Ingegneria Ambientale SRL;
HY-9185 type matting pond of the present invention is purchased from Hangzhou Hai Yun Ingegneria Ambientale SRL;
HY-1 clean-out system of the present invention is purchased from Hangzhou Hai Yun Ingegneria Ambientale SRL, and main component is dilute sulphuric acid;
The ultrasonic fine purifiation pond of HY-9182 type of the present invention is purchased from Hangzhou Hai Yun Ingegneria Ambientale SRL;
HY-2 clean-out system of the present invention is purchased from Hangzhou Hai Yun Ingegneria Ambientale SRL, and main component is dilute sulphuric acid;
HY-9175 type dryer of the present invention is purchased from Hangzhou Hai Yun Ingegneria Ambientale SRL;
Thunder of the present invention covers 5R4121 type medium speed mill and wears fertile mechanical Science and Technology Ltd. purchased from Shanghai;
Plan nit 1500 type cement brick shaping machine of the present invention is purchased from Fujian Quan'gong Machinery Co., Ltd..
The present invention utilizes the subitem technology of current domestic maturation, by scientific and reasonable combination, poisonous and hazardous spent catalyst is carried out harmlessness disposing and fully recycles it utilizing part.Process system is simple, and it is convenient to implement, and comprehensive utilization end-use is extensive, is a kind of very effective useless denitrating catalyst treatment and use technique.Advantage of the present invention is:
1. propose a kind of new departure fully utilizing spent catalyst, solve spent catalyst harmlessness disposing problem;
2. present system is simple, and energy consumption is very low;
3. technical scheme environmental friendliness of the present invention is pollution-free;
4. byproduct of the present invention is of many uses;
5. the subitem technology maturation of technical solution of the present invention is reliable.
Claims (4)
1. waste flue gas denitration catalyst harmless treatment process, is characterized in that comprising main technical process, wastewater treatment process and sludge treatment flow process;
A, main technical process:
A. mechanically useless denitrification catalyst module is separated into base material and steel plate;
B. base material isolated from useless denitrification catalyst module is put into the ultrasonic just wash pool of HY-9180 type and carry out ultrasonic cleaning, scavenging period controls at 10-30 minute, removes the particulate matter in base material micropore;
C. put into HY-9185 type matting pond through the base material of ultrasonic previous cleaning and carry out matting: base material is put into HY-9185 type matting pond, and regulate liquid level, add HY-1 clean-out system, scavenging period controls at 20-40 minute, scavenging solution pH value, between 2-5, is cleaned out the hazardous and noxious substances of base material by matting;
D. put into HY-9182 type ultrasonic fine purifiation pond through the base material of matting and carry out ultrasonic fine purifiation: base material is put into ultrasonic fine purifiation pond, and regulate liquid level, add HY-2 clean-out system, fine purifiation time controling, at 10-30 minute, is cleaned out hazardous and noxious substances in the substrate residual after matting by ultrasonic fine purifiation;
E. put into clear water rinsing bath through the base material of ultrasonic fine purifiation and carry out clear water rinsing, rinsing time controls at 10-40 minute, is washed away the cleaning raffinate in base material by clear water rinsing;
F. carry out sampling chemical examination to the base material through clear water rinsing, the base material without leachability toxicity enters next process, and defective base material repeats above-mentioned steps b-e;
G. HY-9175 type dryer is utilized to carry out drying treatment to qualified base material;
H. utilize thunder to cover 5R4121 type medium speed mill to grind dry base material, to make fineness be 300-400 mesh sieve percent of pass is the fines of 90%;
I. the base material and cement, sandstone, water of wearing into fines are mixed in proportion stirring;
J. the subparticle base material be uniformly mixed and cement, sandstone, water miscellany are put into plan nit 1500 type cement brick shaping machine shaping;
K. shaping cement brick is by forming product after seasoning;
B, wastewater treatment process:
1) waste water that in main technical process, ultrasonic previous cleaning, matting, ultrasonic fine purifiation, clear water rinsing produce is undertaken collecting and pre-treatment by the former pond of waste water;
2) carry out deionization process to through the pretreated waste water in the former pond of waste water, the heavy metal in waste water and hazardous and noxious substances are concentrated, precipitate;
3) clear water produced after waste water deionization treatment system enters process water pond reuse;
4) concentrated solution produced after waste water deionization treatment system enters pressure filter and suppresses mud cake;
5) filtrate water that pressure filter extrudes enters waste water former pond circulation;
C, sludge treatment flow process:
1. pressure filter extrude mud cake and stablizer, cement, sandstone be mixed in proportion stirring;
2. by cement brick shaping machine, the mixture of mud cake and stablizer, cement, sandstone is pressed into cured block;
3. the mud cake being pressed into cured block is put into HY-9175 type dryer, under the environment of 400-500 degree Celsius, dry calcining;
4. becoming after having calcined can the cured block of landfill.
2. waste flue gas denitration catalyst harmless treatment process according to claim 1, is characterized in that in described step a, mechanical system is electric wheel cutting or autogenous fusing.
3. waste flue gas denitration catalyst harmless treatment process according to claim 1, is characterized in that base material in described step I, cement, sandstone, water mix in the ratio of 4:1:4:1.
4. waste flue gas denitration catalyst harmless treatment process according to claim 1, is characterized in that the described step mud cake that 1. pressure filter extrudes mixes in the ratio of 5:1:1:3 with stablizer, cement, sandstone.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104926235A (en) * | 2015-06-11 | 2015-09-23 | 陈颖通 | Treating and curing method before scrapped SCR denitration catalyst burying |
| CN105945036A (en) * | 2016-06-22 | 2016-09-21 | 中电恒德（北京）环保投资有限公司 | Pretreatment method for waste smoke selective denitration catalyst |
| 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 |
| CN106966666A (en) * | 2017-04-27 | 2017-07-21 | 华能国际电力股份有限公司 | Mix the method and concrete for preparing concrete again by useless denitrating catalyst and flyash |
| CN111499351A (en) * | 2020-05-06 | 2020-08-07 | 龙净科杰环保技术（上海）有限公司 | Method for preparing porous purification stone by using residual sludge of cleaning waste SCR catalyst |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103962189A (en) * | 2014-05-21 | 2014-08-06 | 成都东方凯特瑞环保催化剂有限责任公司 | Recovery method of waste SCR (Selective Catalytic Reduction) catalyst, recovery cleaning fluid and catalyst prepared from recovered catalyst |
| CN104071832B (en) * | 2014-06-26 | 2016-06-22 | 山东鲁北企业集团总公司 | The method extracting metal-oxide from discarded SCR denitration |
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2015
- 2015-02-05 CN CN201510060312.6A patent/CN104609753B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104926235A (en) * | 2015-06-11 | 2015-09-23 | 陈颖通 | Treating and curing method before scrapped SCR denitration catalyst burying |
| CN104926235B (en) * | 2015-06-11 | 2017-09-08 | 陈小通 | A kind of processing scrapped before SCR denitration landfill and curing |
| CN105945036A (en) * | 2016-06-22 | 2016-09-21 | 中电恒德（北京）环保投资有限公司 | Pretreatment method for waste smoke selective denitration catalyst |
| CN105945036B (en) * | 2016-06-22 | 2017-12-29 | 中电恒德（北京）环保投资有限公司 | A kind of preprocess method to flue gas selective denitrification catalyst |
| 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 |
| CN106966666A (en) * | 2017-04-27 | 2017-07-21 | 华能国际电力股份有限公司 | Mix the method and concrete for preparing concrete again by useless denitrating catalyst and flyash |
| CN111499351A (en) * | 2020-05-06 | 2020-08-07 | 龙净科杰环保技术（上海）有限公司 | Method for preparing porous purification stone by using residual sludge of cleaning waste SCR catalyst |
| CN111499351B (en) * | 2020-05-06 | 2022-05-20 | 龙净科杰环保技术（上海）有限公司 | Method for preparing porous purification stone by using excess sludge of cleaning waste SCR catalyst |
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