CN104492421B - 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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- CN104492421B CN104492421B CN201410731940.8A CN201410731940A CN104492421B CN 104492421 B CN104492421 B CN 104492421B CN 201410731940 A CN201410731940 A CN 201410731940A CN 104492421 B CN104492421 B CN 104492421B
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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, especially a kind of tungstenic, vanadium, the method for arsenic catalyst dearsenization.
Background technology
Nitrogen oxides (nox) are one of Air Pollutants that countries in the world are generally acknowledged.Thermal power plant is China's nitrogen oxides
Topmost emission source.In order to control the discharge of nox, many thermal power plants, the generating set of combustion of fossil fuels adopt technology relatively
For ripe SCR (scr) gas denitrifying technology, its core is the catalyst being made up of tungsten, vanadium, titanium etc.,
The life-span of general coal-burning power plant catalyst is 3 ~ 5 years, however, due to containing micro arsenic, gas in high-temperature flue gas in coal-burning boiler
State as2o3, it is easily accessible the hole of catalyst, react the stable arsenic acid vfanadium compound of generation with the vanadium in catalyst, vanadium loses work
Property, meanwhile, gaseous state arsenic easy blocking catalyst micropore, stop reactant from reaching active sites, also affect the activity of catalyst.Thus dropping
The low service life of catalyst.
How to remove tungstenic, vanadium, arsenide in arsenic catalyst, effective control tungsten, vanadium loss, extend catalyst and use simultaneously
In the life-span, be problem demanding prompt solution.The arsenic removing method of report includes pyrogenic process and two kinds of wet method at present.Fire arsenic removal effect is poor,
And serious secondary pollution can be caused, and very high to equipment requirements, also do not meet the high temperature of large-scale production at present both at home and abroad
Stove.Wet method dearsenication document report is more, how to soak dearsenization using alkali, that is, be directly added into sodium hydroxide concentrated alkali solution and leach dearsenization, but
For indissoluble arsenate in catalyst, dearsenization effect is less desirable, and tungsten, vanadium together can lose with the removing of arsenic.Therefore,
It is necessary to explore one kind and can remove tungstenic, vanadium, arsenide in arsenic catalyst, tungsten, the method for vanadium loss can be controlled simultaneously again.
Content of the invention
Present invention aims to above-mentioned the deficiencies in the prior art, contain arsenic in particular for catalyst and lead
Cause problem that its activity reduces it is proposed that a kind of tungstenic, vanadium, the method for arsenic catalyst dearsenization, this method can not only meet efficiently,
Safe and environment-friendly dearsenization requirement moreover it is possible to effective control catalyst key component tungsten, the loss of vanadium, thus extending making of catalyst
With the life-span, reduce Financial cost.This method of the present invention is stripped of the arsenide in catalyst effectively, can reduce simultaneously again
Tungsten, vanadium loss are so that as2o3Content ＜ 0.15%, separating by extraction is up to 95%, and wo therein3、v2o5The equal ＜ of loss rate 30%.
The present invention is achieved through the following technical solutions: a kind of tungstenic, vanadium, the method for arsenic catalyst dearsenization, and step is as follows:
(1), by tungstenic, vanadium, arsenic catalyst, the sodium hydroxide solution being 3～12g/l with concentration, it is placed in ultrasound reactor
In carry out the leaching dearsenization reaction of alkali, 30～80 DEG C of controlling reaction temperature, response time 0.5～3h, ventilation 0.8～2.0m3/
H, ultrasonic power 300～900w；In course of reaction, add inhibitor edta and the ammonium hydrogen carbonate of 3～5g/l, after reaction terminates
Carry out solid-liquor separation, the catalyst of solid phase is treated to process further；Liquid phase is through ca (oh)2After dearsenization is processed, resulting solution returns one
In secondary alkali leaching operation, it is back to whole system, and gained solid phase is cawo4, ca(vo3)2、ca3(aso4)2Directly bank up；
(2) the catalyst that (1) step obtains is carried out secondary alkali leaching, during fill into the sodium hydroxide solution and 1 of 1～3g/l
The inhibitor edta of～3g/l and ammonium hydrogen carbonate, are carried out equally in ultrasound reactor, 30～80 DEG C of controlling reaction temperature, instead
0.5～3h, ventilation 0.8～2.0m between seasonable3/ h, ultrasonic power 300～900w；After reaction terminates, the liquid phase obtaining is returned
Return in an alkali leaching operation, for the leaching of raw catelyst；The catalyst obtaining carries out next step carrying out washing treatment；
By step (2) in soak the catalyst after dearsenization is processed through secondary alkali and be placed in ultrasound reactor and washed,
25～70 DEG C of controlling reaction temperature, response time 0.5～1.5h, ventilation 0.8～2.0m3/ h, ultrasonic power 100～
600w；After reaction terminates, resulting solution returns in secondary alkali leaching operation, and gained catalyst dried, after the dearsenization of acquisition
As in catalyst2o3Content ＜ 0.15%, separating by extraction is up to 95%, and wo therein3、v2o5The equal ＜ of loss rate 30%.
As the preferred technical solution of the present invention:
In described ultrasound reactor, alkali leaching reaction temperature is 50～70 DEG C, response time 1～2h, ventilation 1.2m3/
H, ultrasonic power 500～700w.
Described ultrasonic wave water washing, temperature is 25～35 DEG C, response time 0.5～1h, ventilation 1.2～1.5m3/ h, ultrasonic
Wave power 300～500w.
The invention has the benefit that this procedure is simple, reliable easy, alkali is adopted to soak dearsenization in ultrasound wave
Method, in catalyst, arsenide removal efficiency is higher, and add inhibitor, can effective control tungsten, the loss of vanadium, during produce
Waste water, can be through ca (oh)2After process, it is back to system, technical process does not pollute ring for closed system it is achieved that recycling
Border, reduces cost again.
Brief description:
Fig. 1 is the process chart of the present invention.
Specific embodiment
As in embodiment 1, catalyst containing arsenic2o3Content is 3～4%.First by tungstenic, vanadium, arsenic catalyst, with concentration it is
The sodium hydroxide solution of 3g/l, is placed in ultrasound reactor and carries out alkali leaching dearsenization reaction, 30～40 DEG C of controlling reaction temperature, instead
2h, ventilation 1.2m between seasonable3/ h, ultrasonic power 500w.In course of reaction, the inhibitor edta of addition and ammonium hydrogen carbonate are equal
For 3g/l.Reaction carries out solid-liquor separation after terminating, and liquid phase is through ca (oh)2After dearsenization is processed, resulting solution can be back to whole body
System, and gained slag is cawo4, ca(vo3)2、ca3(aso4)2Can directly bank up.
Catalyst after the leaching of alkali carries out secondary alkali leaching, during fill into sodium hydroxide solution and the suppression of 1g/l
Edta the and 1g/l ammonium hydrogen carbonate of agent 1g/l, is carried out equally in ultrasound reactor, 30～40 DEG C of controlling reaction temperature, reaction
Time 2h, ventilation 1.2m3/ h, ultrasonic power 500w.After reaction terminates, liquid phase can return to, in an alkali leaching operation, use
Leaching in raw catelyst.The catalyst obtaining carries out next step washing again.
Again the catalyst after the leaching dearsenization of secondary alkali is processed is placed in ultrasound reactor and is washed, control reaction
25～35 DEG C of temperature, response time 0.5h, ventilation 1.2m3/ h, ultrasonic power 300w.After reaction terminates, solution returns body
System, catalyst dried, as in the dearsenization rear catalyst of acquisition2o3Content is 0.12%, and separating by extraction reaches 95.2%, wo3Loss
Rate is 28%, v2o5Loss rate is 22.5%.
As in embodiment 2, catalyst containing arsenic2o3Content is 3～4%.First by tungstenic, vanadium, arsenic catalyst, with concentration it is
The sodium hydroxide solution of 5g/l, is placed in ultrasound reactor and carries out alkali leaching dearsenization reaction, 50～60 DEG C of controlling reaction temperature, instead
1.5h, ventilation 1.2m between seasonable3/ h, ultrasonic power 500w.In course of reaction, add inhibitor edta3g/l, bicarbonate
Ammonium 4g/l.Reaction carries out solid-liquor separation after terminating, and liquid phase is through ca (oh)2After dearsenization is processed, resulting solution can be back to whole body
System, and gained slag is cawo4, ca(vo3)2、ca3(aso4)2Can directly bank up.
Catalyst after the leaching of alkali carries out secondary alkali leaching, during fill into sodium hydroxide solution and the suppression of 2g/l
Edta the and 1g/l ammonium hydrogen carbonate of agent 1g/l, is carried out equally in ultrasound reactor, 50～60 DEG C of controlling reaction temperature, reaction
Time 1.5h, ventilation 1.2m3/ h, ultrasonic power 500w.After reaction terminates, liquid phase can return in an alkali leaching operation,
Leaching for raw catelyst.The catalyst obtaining carries out next step washing again.
Again the catalyst after the leaching dearsenization of secondary alkali is processed is placed in ultrasound reactor and is washed, control reaction
25～35 DEG C of temperature, response time 0.5h, ventilation 1.2m3/ h, ultrasonic power 300w.After reaction terminates, solution returns body
System, catalyst dried, as in the dearsenization rear catalyst of acquisition2o3Content is 0.10%, and separating by extraction reaches 95.6%, wo3Loss
Rate is 27.4%, v2o5Loss rate is 23.6%.
As in embodiment 3, catalyst containing arsenic2o3Content is 3～4%.First by tungstenic, vanadium, arsenic catalyst, with concentration it is
The sodium hydroxide solution of 7g/l, is placed in ultrasound reactor and carries out alkali leaching dearsenization reaction, 60～70 DEG C of controlling reaction temperature, instead
1.0h, ventilation 1.2m between seasonable3/ h, ultrasonic power 700w.In course of reaction, add inhibitor edta4g/l, bicarbonate
Ammonium 4g/l.Reaction carries out solid-liquor separation after terminating, and liquid phase is through ca (oh)2After dearsenization is processed, resulting solution can be back to whole body
System, and gained slag is cawo4, ca(vo3)2、ca3(aso4)2Can directly bank up.
Catalyst after the leaching of alkali carries out secondary alkali leaching, during fill into sodium hydroxide solution and the suppression of 2g/l
Edta the and 2g/l ammonium hydrogen carbonate of agent 2g/l, is carried out equally in ultrasound reactor, 60～70 DEG C of controlling reaction temperature, reaction
Time 1.0h, ventilation 1.2m3/ h, ultrasonic power 700w.After reaction terminates, liquid phase can return in an alkali leaching operation,
Leaching for raw catelyst.The catalyst obtaining carries out next step washing again.
Again the catalyst after the leaching dearsenization of secondary alkali is processed is placed in ultrasound reactor and is washed, control reaction
25～35 DEG C of temperature, response time 0.5h, ventilation 1.2m3/ h, ultrasonic power 500w.After reaction terminates, solution returns body
System, catalyst dried, as in the dearsenization rear catalyst of acquisition2o3Content is 0.11%, and separating by extraction reaches 95.3%, wo3Loss
Rate is 26.5%, v2o5Loss rate is 22.8%.
As in embodiment 4, catalyst containing arsenic2o3Content is 3～4%.First by tungstenic, vanadium, arsenic catalyst, with concentration it is
The sodium hydroxide solution of 10g/l, is placed in ultrasound reactor and carries out alkali leaching dearsenization reaction, 60～70 DEG C of controlling reaction temperature,
Response time 1.0h, ventilation 1.2m3/ h, ultrasonic power 700w.In course of reaction, add inhibitor edta3g/l, carbonic acid
Hydrogen ammonium 5g/l.Reaction carries out solid-liquor separation after terminating, and liquid phase is through ca (oh)2After dearsenization is processed, resulting solution can be back to entirely
System, and gained slag is cawo4, ca(vo3)2、ca3(aso4)2Can directly bank up.
Catalyst after the leaching of alkali carries out secondary alkali leaching, during fill into sodium hydroxide solution and the suppression of 3g/l
Edta the and 3g/l ammonium hydrogen carbonate of agent 1g/l, is carried out equally in ultrasound reactor, 60～70 DEG C of controlling reaction temperature, reaction
Time 1.0h, ventilation 1.2m3/ h, ultrasonic power 700w.After reaction terminates, liquid phase can return in an alkali leaching operation,
Leaching for raw catelyst.The catalyst obtaining carries out next step washing again.
Again the catalyst after the leaching dearsenization of secondary alkali is processed is placed in ultrasound reactor and is washed, control reaction
50～60 DEG C of temperature, response time 1.0h, ventilation 1.8m3/ h, ultrasonic power 600w.After reaction terminates, solution returns body
System, catalyst dried, as in the dearsenization rear catalyst of acquisition2o3Content is 0.10%, and separating by extraction reaches 95.6%, wo3Loss
Rate is 27.3%, v2o5Loss rate is 25.2%.
Claims (3)
1. a kind of tungstenic, vanadium, the method for arsenic catalyst dearsenization are it is characterised in that step is as follows:
(1), by tungstenic, vanadium, arsenic catalyst, the sodium hydroxide solution being 3～12g/l with concentration, it is placed in ultrasound reactor
Alkali leaching dearsenization reaction of row, 30～80 DEG C of controlling reaction temperature, response time 0.5～3h, ventilation 0.8～2.0m3/ h, surpasses
Acoustic power 300～900w；In course of reaction, add the inhibitor edta of 3～5g/l and the ammonium hydrogen carbonate of 3～5g/l, reaction
Carry out solid-liquor separation, the catalyst of solid phase is treated to process further, liquid phase is through ca (oh) after end2After dearsenization is processed, resulting solution
It is back to an alkali leaching operation, gained solid phase is cawo4, ca(vo3)2、ca3(aso4)2Directly bank up；
(2), the catalyst that (1) step obtains is carried out secondary alkali leaching, during fill into the sodium hydroxide solution of 1～3g/l and 1～
The inhibitor edta of 3g/l and the ammonium hydrogen carbonate of 1～3g/l, are carried out equally in ultrasound reactor, and controlling reaction temperature 30～
80 DEG C, response time 0.5～3h, ventilation 0.8～2.0m3/ h, ultrasonic power 300～900w；After reaction terminates, obtain
Liquid phase returns in an alkali leaching operation, for the leaching of raw catelyst；The catalyst obtaining carries out next step carrying out washing treatment；
(3), by step (2) in soak the catalyst after dearsenization is processed through secondary alkali and be placed in ultrasound reactor and washed, control
25～70 DEG C of reaction temperature processed, response time 0.5～1.5h, ventilation 0.8～2.0m3/ h, ultrasonic power 100～600w；
After reaction terminates, resulting solution returns in secondary alkali leaching operation, gained catalyst dried, the dearsenization rear catalyst of acquisition
Middle as2o3Content ＜ 0.15%, separating by extraction reaches more than 95%, wo3、v2o5The equal ＜ of loss rate 30%.
2. tungstenic according to claim 1, vanadium, arsenic catalyst dearsenization method it is characterised in that: described ultrasonic response
In device, alkali leaching reaction temperature is 50～70 DEG C, response time 1～2h, ventilation 1.2m3/ h, ultrasonic power 500～700w.
3. tungstenic according to claim 1, vanadium, arsenic catalyst dearsenization method it is characterised in that: described ultrasound wave water
Wash, temperature is 25～35 DEG C, response time 0.5～1h, ventilation 1.2～1.5m3/ h, ultrasonic power 300～500w.
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