CN104492421A - Dearsenification method for tungsten, vanadium and arsenic-containing catalyst - Google Patents
Dearsenification method for tungsten, vanadium and arsenic-containing catalyst Download PDFInfo
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- CN104492421A CN104492421A CN201410731940.8A CN201410731940A CN104492421A CN 104492421 A CN104492421 A CN 104492421A CN 201410731940 A CN201410731940 A CN 201410731940A CN 104492421 A CN104492421 A CN 104492421A
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- dearsenification
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Abstract
The invention discloses a dearsenification method for a tungsten, vanadium and arsenic-containing catalyst. The method can be used for effectively removing arsenide in the catalyst and further reducing loss of tungsten and vanadium, so that the As2O3 content is less than 0.15%, the dearsenification rate can reach 95% and the WO3 and V2O5 loss rate are less than 30%. The method is simple in process and reliable and feasible. By adopting a method of alkaline leaching to dearsenificate in ultrasonic waves, the arsenide removal rate in the catalyst is relatively high, and an inhibiting agent is added, so that the loss of tungsten and vanadium can be effectively controlled. The wastewater generated in the process can be treated by Ca(OH)2 and is reused in the system. The technical process is a closed system which can be used for realizing cyclic utilization, is free of environmental pollution and further can be used for lowering the cost.
Description
Technical field
The present invention relates to catalyst dearsenic technique field, the method for especially a kind of tungstenic, vanadium, the dearsenification of arsenic catalyst.
Background technology
Nitrogen oxide (NOx) is one of the Air Pollutants that countries in the world are generally acknowledged.Thermal power plant is the topmost emission source of China's nitrogen oxide.In order to the discharge of control NOx, the generating set of many thermal power plants, combustion of fossil fuels adopts SCR (SCR) gas denitrifying technology that technology is comparatively ripe, its core is the catalyst be made up of tungsten, vanadium, titanium etc., the life-span of general coal-burning power plant catalyst is 3 ~ 5 years, but, owing to containing the arsenic of trace in coal-burning boiler, gaseous state As in high-temperature flue gas
2o
3, easily enter the hole of catalyst, react with the vanadium in catalyst and generate stable arsenic acid vfanadium compound, vanadium loses activity, and meanwhile, the easy blocking catalyst micropore of gaseous state arsenic, stops reactant to arrive active sites, also affect the activity of catalyst.Thus reduce the service life of catalyst.
How removing arsenide in tungstenic, vanadium, arsenic catalyst, effectively control tungsten, vanadium loss simultaneously, extending catalyst service life, is problem demanding prompt solution.The arsenic removing method of current report comprises pyrogenic process and wet method two kinds.Fire arsenic removal effect is poor, and can cause serious secondary pollution, and very high to equipment requirement, does not also meet the high temperature furnace of large-scale production at present both at home and abroad.Wet method dearsenication bibliographical information is more, and the alkali that adopts soaks dearsenification more, namely directly add NaOH concentrated alkali solution and leach dearsenification, but for indissoluble arsenate in catalyst, dearsenification effect is not very desirable, and tungsten, vanadium together can lose along with removing of arsenic.Therefore, be necessary that exploring one can remove arsenide in tungstenic, vanadium, arsenic catalyst, the method for tungsten, vanadium loss can be controlled again simultaneously.
Summary of the invention
The object of the invention is to for above-mentioned the deficiencies in the prior art, especially its active problem reduced is caused for catalyst containing arsenic, propose a kind of method of tungstenic, vanadium, the dearsenification of arsenic catalyst, this method can not only meet efficiently, safety, environmental protection dearsenification requirement, effectively can also control the loss of catalyst key component tungsten, vanadium, thus the service life of extending catalyst, reduce financial cost.This method of the present invention is stripped of the arsenide in catalyst effectively, can reduce again tungsten, vanadium loss simultaneously, make As
2o
3content < 0.15%, separating by extraction can reach 95%, and WO wherein
3, V
2o
5the equal < 30% of loss late.
The present invention is achieved through the following technical solutions: a kind of method of tungstenic, vanadium, the dearsenification of arsenic catalyst, and step is as follows:
(1) by tungstenic, vanadium, arsenic catalyst, be the sodium hydroxide solution of 3 ~ 12g/l with concentration, be placed in ultrasound reactor and carry out an alkali leaching dearsenification reaction, control reaction temperature 30 ~ 80 DEG C, reaction time 0.5 ~ 3h, throughput 0.8 ~ 2.0m
3/ h, ultrasonic power 300 ~ 900w; In course of reaction, add inhibitor EDTA and the carbonic hydroammonium of 3 ~ 5g/l, carry out solid-liquor separation after reaction terminates, further process treated by the catalyst of solid phase; Liquid phase is through Ca (OH)
2after dearsenification process, gained solution returns in an alkali leaching operation, be back to whole system, and gained solid phase is CaWO
4, Ca(VO
3)
2, Ca
3(AsO
4)
2directly bank up;
(2) catalyst step (1) obtained carries out the leaching of secondary alkali, fill into the sodium hydroxide solution of 1 ~ 3g/l and the inhibitor EDTA of 1 ~ 3g/l and carbonic hydroammonium in process, carry out in ultrasound reactor equally, control reaction temperature 30 ~ 80 DEG C, reaction time 0.5 ~ 3h, throughput 0.8 ~ 2.0m
3/ h, ultrasonic power 300 ~ 900w; After reaction terminates, the liquid phase obtained turns back in an alkali leaching operation, for the leaching of raw catelyst; The catalyst obtained carries out next step carrying out washing treatment;
By step (2) in catalyst after secondary alkali leaching dearsenification process be placed in ultrasound reactor and wash, control reaction temperature 25 ~ 70 DEG C, reaction time 0.5 ~ 1.5h, throughput 0.8 ~ 2.0m
3/ h, ultrasonic power 100 ~ 600w; After reaction terminates, gained solution turns back in secondary alkali leaching operation, gained catalyst drying process, As in the dearsenification rear catalyst of acquisition
2o
3content < 0.15%, separating by extraction can reach 95%, and WO wherein
3, V
2o
5the equal < 30% of loss late.
As the preferred technical solution of the present invention:
In described ultrasound reactor, alkali leaching reaction temperature is 50 ~ 70 DEG C, reaction time 1 ~ 2h, throughput 1.2m
3/ h, ultrasonic power 500 ~ 700w.
Described ultrasonic wave water washing, temperature is 25 ~ 35 DEG C, reaction time 0.5 ~ 1h, throughput 1.2 ~ 1.5m
3/ h, ultrasonic power 300 ~ 500w.
Beneficial effect of the present invention is: this procedure simply, reliably easy, in ultrasonic wave, adopt alkali to soak the method for dearsenification, in catalyst, arsenide removal efficiency is higher, and add inhibitor, effectively can control the loss of tungsten, vanadium, the waste water produced in process, can through Ca (OH)
2after process, be back to system, technical process is closed system, achieves and recycles, free from environmental pollution, again reduces cost.
accompanying drawing explanation:
Fig. 1 is process chart of the present invention.
Detailed description of the invention
embodiment 1, containing As in arsenic catalyst
2o
3content is 3 ~ 4%.First by tungstenic, vanadium, arsenic catalyst, be the sodium hydroxide solution of 3g/l with concentration, be placed in ultrasound reactor and carry out alkali leaching dearsenification reaction, control reaction temperature 30 ~ 40 DEG C, reaction time 2h, throughput 1.2m
3/ h, ultrasonic power 500w.In course of reaction, the inhibitor EDTA added and carbonic hydroammonium are 3g/l.Carry out solid-liquor separation after reaction terminates, liquid phase is through Ca (OH)
2after dearsenification process, gained solution can be back to whole system, and gained slag is CaWO
4, Ca(VO
3)
2, Ca
3(AsO
4)
2can directly bank up.
Catalyst after an alkali leaching carries out the leaching of secondary alkali, fill into the sodium hydroxide solution of 1g/l and EDTA and the 1g/l carbonic hydroammonium of inhibitor 1g/l in process, carry out in ultrasound reactor equally, control reaction temperature 30 ~ 40 DEG C, reaction time 2h, throughput 1.2m
3/ h, ultrasonic power 500w.After reaction terminates, liquid phase can turn back in an alkali leaching operation, for the leaching of raw catelyst.The catalyst obtained carries out next step washing again.
Again the catalyst after secondary alkali leaching dearsenification process is placed in ultrasound reactor to wash, controls reaction temperature 25 ~ 35 DEG C, reaction time 0.5h, throughput 1.2m
3/ h, ultrasonic power 300w.After reaction terminates, solution returns system, catalyst drying process, As in the dearsenification rear catalyst of acquisition
2o
3content is 0.12%, and separating by extraction reaches 95.2%, WO
3loss late is 28%, V
2o
5loss late is 22.5%.
embodiment 2, containing As in arsenic catalyst
2o
3content is 3 ~ 4%.First by tungstenic, vanadium, arsenic catalyst, be the sodium hydroxide solution of 5g/l with concentration, be placed in ultrasound reactor and carry out alkali leaching dearsenification reaction, control reaction temperature 50 ~ 60 DEG C, reaction time 1.5h, throughput 1.2m
3/ h, ultrasonic power 500w.In course of reaction, add inhibitor EDTA3g/l, carbonic hydroammonium 4g/l.Carry out solid-liquor separation after reaction terminates, liquid phase is through Ca (OH)
2after dearsenification process, gained solution can be back to whole system, and gained slag is CaWO
4, Ca(VO
3)
2, Ca
3(AsO
4)
2can directly bank up.
Catalyst after an alkali leaching carries out the leaching of secondary alkali, fill into the sodium hydroxide solution of 2g/l and EDTA and the 1g/l carbonic hydroammonium of inhibitor 1g/l in process, carry out in ultrasound reactor equally, control reaction temperature 50 ~ 60 DEG C, reaction time 1.5h, throughput 1.2m
3/ h, ultrasonic power 500w.After reaction terminates, liquid phase can turn back in an alkali leaching operation, for the leaching of raw catelyst.The catalyst obtained carries out next step washing again.
Again the catalyst after secondary alkali leaching dearsenification process is placed in ultrasound reactor to wash, controls reaction temperature 25 ~ 35 DEG C, reaction time 0.5h, throughput 1.2m
3/ h, ultrasonic power 300w.After reaction terminates, solution returns system, catalyst drying process, As in the dearsenification rear catalyst of acquisition
2o
3content is 0.10%, and separating by extraction reaches 95.6%, WO
3loss late is 27.4%, V
2o
5loss late is 23.6%.
embodiment 3, containing As in arsenic catalyst
2o
3content is 3 ~ 4%.First by tungstenic, vanadium, arsenic catalyst, be the sodium hydroxide solution of 7g/l with concentration, be placed in ultrasound reactor and carry out alkali leaching dearsenification reaction, control reaction temperature 60 ~ 70 DEG C, reaction time 1.0h, throughput 1.2m
3/ h, ultrasonic power 700w.In course of reaction, add inhibitor EDTA4g/l, carbonic hydroammonium 4g/l.Carry out solid-liquor separation after reaction terminates, liquid phase is through Ca (OH)
2after dearsenification process, gained solution can be back to whole system, and gained slag is CaWO
4, Ca(VO
3)
2, Ca
3(AsO
4)
2can directly bank up.
Catalyst after an alkali leaching carries out the leaching of secondary alkali, fill into the sodium hydroxide solution of 2g/l and EDTA and the 2g/l carbonic hydroammonium of inhibitor 2g/l in process, carry out in ultrasound reactor equally, control reaction temperature 60 ~ 70 DEG C, reaction time 1.0h, throughput 1.2m
3/ h, ultrasonic power 700w.After reaction terminates, liquid phase can turn back in an alkali leaching operation, for the leaching of raw catelyst.The catalyst obtained carries out next step washing again.
Again the catalyst after secondary alkali leaching dearsenification process is placed in ultrasound reactor to wash, controls reaction temperature 25 ~ 35 DEG C, reaction time 0.5h, throughput 1.2m
3/ h, ultrasonic power 500w.After reaction terminates, solution returns system, catalyst drying process, As in the dearsenification rear catalyst of acquisition
2o
3content is 0.11%, and separating by extraction reaches 95.3%, WO
3loss late is 26.5%, V
2o
5loss late is 22.8%.
embodiment 4, containing As in arsenic catalyst
2o
3content is 3 ~ 4%.First by tungstenic, vanadium, arsenic catalyst, be the sodium hydroxide solution of 10g/l with concentration, be placed in ultrasound reactor and carry out alkali leaching dearsenification reaction, control reaction temperature 60 ~ 70 DEG C, reaction time 1.0h, throughput 1.2m
3/ h, ultrasonic power 700w.In course of reaction, add inhibitor EDTA3g/l, carbonic hydroammonium 5g/l.Carry out solid-liquor separation after reaction terminates, liquid phase is through Ca (OH)
2after dearsenification process, gained solution can be back to whole system, and gained slag is CaWO
4, Ca(VO
3)
2, Ca
3(AsO
4)
2can directly bank up.
Catalyst after an alkali leaching carries out the leaching of secondary alkali, fill into the sodium hydroxide solution of 3g/l and EDTA and the 3g/l carbonic hydroammonium of inhibitor 1g/l in process, carry out in ultrasound reactor equally, control reaction temperature 60 ~ 70 DEG C, reaction time 1.0h, throughput 1.2m
3/ h, ultrasonic power 700w.After reaction terminates, liquid phase can turn back in an alkali leaching operation, for the leaching of raw catelyst.The catalyst obtained carries out next step washing again.
Again the catalyst after secondary alkali leaching dearsenification process is placed in ultrasound reactor to wash, controls reaction temperature 50 ~ 60 DEG C, reaction time 1.0h, throughput 1.8m
3/ h, ultrasonic power 600w.After reaction terminates, solution returns system, catalyst drying process, As in the dearsenification rear catalyst of acquisition
2o
3content is 0.10%, and separating by extraction reaches 95.6%, WO
3loss late is 27.3%, V
2o
5loss late is 25.2%.
Claims (4)
1. a method for tungstenic, vanadium, the dearsenification of arsenic catalyst, it is characterized in that, step is as follows:
(1), by tungstenic, vanadium, arsenic catalyst, be the sodium hydroxide solution of 3 ~ 12g/l with concentration, be placed in ultrasound reactor and carry out an alkali leaching dearsenification reaction, control reaction temperature 30 ~ 80 DEG C, reaction time 0.5 ~ 3h, throughput 0.8 ~ 2.0m
3/ h, ultrasonic power 300 ~ 900w; In course of reaction, add the inhibitor EDTA of 3 ~ 5g/l and the carbonic hydroammonium of 3 ~ 5g/l, carry out solid-liquor separation after reaction terminates, further process treated by the catalyst of solid phase, and liquid phase is through Ca (OH)
2after dearsenification process, gained solution is back to an alkali leaching operation, and gained solid phase is CaWO
4, Ca(VO
3)
2, Ca
3(AsO
4)
2directly bank up;
(2) the catalyst, step (1) obtained carries out the leaching of secondary alkali, the carbonic hydroammonium of the sodium hydroxide solution of 1 ~ 3g/l and the inhibitor EDTA of 1 ~ 3g/l and 1 ~ 3g/l is filled in process, carry out in ultrasound reactor equally, control reaction temperature 30 ~ 80 DEG C, reaction time 0.5 ~ 3h, throughput 0.8 ~ 2.0m
3/ h, ultrasonic power 300 ~ 900w; After reaction terminates, the liquid phase obtained turns back in an alkali leaching operation, for the leaching of raw catelyst; The catalyst obtained carries out next step carrying out washing treatment;
, by step (2) in catalyst after secondary alkali leaching dearsenification process be placed in ultrasound reactor and wash, control reaction temperature 25 ~ 70 DEG C, reaction time 0.5 ~ 1.5h, throughput 0.8 ~ 2.0m
3/ h, ultrasonic power 100 ~ 600w; After reaction terminates, gained solution turns back in secondary alkali leaching operation, gained catalyst drying process, As in the dearsenification rear catalyst of acquisition
2o
3content < 0.15%, separating by extraction reaches more than 95%, WO
3, V
2o
5the equal < 30% of loss late.
2. the method for tungstenic according to claim 1, vanadium, the dearsenification of arsenic catalyst, is characterized in that: in described ultrasound reactor, and alkali leaching reaction temperature is 50 ~ 70 DEG C, reaction time 1 ~ 2h, throughput 1.2m
3/ h, ultrasonic power 500 ~ 700w.
3. the method for tungstenic according to claim 1, vanadium, the dearsenification of arsenic catalyst, is characterized in that: described ultrasonic wave water washing, and temperature is 25 ~ 35 DEG C, reaction time 0.5 ~ 1h, throughput 1.2 ~ 1.5m
3/ h, ultrasonic power 300 ~ 500w.
4. the method for tungstenic according to claim 1, vanadium, the dearsenification of arsenic catalyst, is characterized in that: the inhibitor EDTA added and carbonic hydroammonium are respectively 3g/l, 4g/l.
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| CN104492421B CN104492421B (en) | 2017-01-25 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105668897A (en) * | 2016-03-18 | 2016-06-15 | 昆明冶金研究院 | Method for dearsenization of arsenic containing waste water generated in regeneration process of vanadium, tungsten and titanium denitration catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030108462A1 (en) * | 2001-12-06 | 2003-06-12 | Oskoui Kazem Eradat | Method of extracting contaminants from solid matter |
| CN101016582A (en) * | 2007-02-15 | 2007-08-15 | 郴州市金贵有色金属有限公司 | Method of removing arsenic for anode mud with high arsenic and lead content |
| CN101194683A (en) * | 2008-01-09 | 2008-06-11 | 北京市科威华食品工程技术有限公司 | Novel arsenic removing technique for sargassum fusiforme |
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2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030108462A1 (en) * | 2001-12-06 | 2003-06-12 | Oskoui Kazem Eradat | Method of extracting contaminants from solid matter |
| CN101016582A (en) * | 2007-02-15 | 2007-08-15 | 郴州市金贵有色金属有限公司 | Method of removing arsenic for anode mud with high arsenic and lead content |
| CN101194683A (en) * | 2008-01-09 | 2008-06-11 | 北京市科威华食品工程技术有限公司 | Novel arsenic removing technique for sargassum fusiforme |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105668897A (en) * | 2016-03-18 | 2016-06-15 | 昆明冶金研究院 | Method for dearsenization of arsenic containing waste water generated in regeneration process of vanadium, tungsten and titanium denitration catalyst |
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Address after: 650031 No. 86 Yuantong North Road, Yunnan, Kunming Patentee after: Kunming Metallurgical Research Institute Co.,Ltd. Address before: 650031 No. 86 Yuantong North Road, Yunnan, Kunming Patentee before: KUNMING METALLURGICAL Research Institute |