CN110152744A - A kind of electrochemical process for treating of arsenic poisoning SCR denitration - Google Patents
A kind of electrochemical process for treating of arsenic poisoning SCR denitration Download PDFInfo
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- CN110152744A CN110152744A CN201910447284.1A CN201910447284A CN110152744A CN 110152744 A CN110152744 A CN 110152744A CN 201910447284 A CN201910447284 A CN 201910447284A CN 110152744 A CN110152744 A CN 110152744A
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- scr denitration
- arsenic
- arsenic poisoning
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- 208000008316 Arsenic Poisoning Diseases 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000008569 process Effects 0.000 title claims abstract description 28
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 73
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 73
- 230000001590 oxidative effect Effects 0.000 claims abstract description 34
- 239000000843 powder Substances 0.000 claims abstract description 33
- 230000005518 electrochemistry Effects 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 26
- 238000001354 calcination Methods 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 238000005554 pickling Methods 0.000 claims abstract description 18
- 239000004071 soot Substances 0.000 claims abstract description 17
- 238000007664 blowing Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 32
- 239000007789 gas Substances 0.000 claims description 32
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910021529 ammonia Inorganic materials 0.000 claims description 16
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 16
- 238000003487 electrochemical reaction Methods 0.000 claims description 11
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 9
- 235000006408 oxalic acid Nutrition 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- XDBSEZHMWGHVIL-UHFFFAOYSA-M hydroxy(dioxo)vanadium Chemical compound O[V](=O)=O XDBSEZHMWGHVIL-UHFFFAOYSA-M 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical compound [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000011282 treatment Methods 0.000 claims description 8
- 230000001413 cellular effect Effects 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 30
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000004604 Blowing Agent Substances 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 230000005428 wave function Effects 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- -1 diethyl-dithio formates Chemical class 0.000 description 1
- WQABCVAJNWAXTE-UHFFFAOYSA-N dimercaprol Chemical compound OCC(S)CS WQABCVAJNWAXTE-UHFFFAOYSA-N 0.000 description 1
- 229960001051 dimercaprol Drugs 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/92—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/12—Treating with free oxygen-containing gas
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/485—Impregnating or reimpregnating with, or deposition of metal compounds or catalytically active elements
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
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Abstract
The invention discloses a kind of electrochemical process for treating of arsenic poisoning SCR denitration, comprising the following steps: 1) carries out mechanical soot blowing processing to arsenic poisoning SCR denitration, then carry out crushing and ball milling；2) the arsenic poisoning SCR denitration powder that step 1) obtains is mixed with aqueous slkali, it is added to mixture as electrolyte in electrochemistry arsenic removing apparatus again, it is passed through oxidizing gas simultaneously, so that mixture is electrochemically reacted under the conditions of oxidizing gas, the SCR denitration after obtaining arsenic removal；3) SCR denitration after arsenic removal is put into acid solution and is cleaned by ultrasonic, the SCR denitration after obtaining pickling；4) SCR denitration after pickling is impregnated into regenerated liquid；5) heating roasting is carried out after microwave calcination, so that the predecessor on SCR denitration surface is converted into active component, this method is high to the arsenic removal rate of arsenic poisoning SCR denitration, and process conditions are mild, and pollution-free.
Description
Technical field
The invention belongs to environmental protection technologies and denitration catalyst field, are related to a kind of electrochemistry of arsenic poisoning SCR denitration
Processing method.
Background technique
China's domestic thermal power plant mostly uses greatly selective catalytic reduction (SCR) technology to carry out denitrating flue gas at this stage, with
The carrying out of denitrating flue gas process will generate the denitrating catalyst largely inactivated.Due to having in decaying catalyst containing toxic to environment
Evil substance, has been cited as hazardous waste, if directly outlet necessarily will cause great environmental pressure, and brings catalysis to power plant
The financial burden of agent renewal cost and dangerous waste disposal costs.Regeneration disposition is carried out to decaying catalyst, it not only can be to avoid discarded
Problem of environmental pollution caused by catalyst can also reduce the input cost of catalyst change.Therefore from economy, environment and society
Angle is set out, and the regeneration of denitrating catalyst is all following development trend.
In areas such as China Inner Mongol, northeast, since coal-fired arsenic content is higher, power plant's denitrating catalyst of most area
There is different degrees of arsenic poisoning problem.Since arsenic species can be combined with catalyst activity component in the form of being chemically bonded, and
And catalytic inner can be penetrated into and form zone of saturation, therefore the efficient removal of harmful arsenic becomes in denitrating catalyst regenerative process
Key link.Arsenic poisoning SCR denitration generally uses wet-cleaning arsenic removal；Oxalic acid, acetic acid, hydrochloric acid, nitric acid and sulfuric acid etc.
Inorganic acid, the alkaline solutions such as sodium carbonate, sodium bicarbonate and sodium hydroxide can be used as cleaning solution.Second two is also utilized in the research of part
The complexing agent of amine tetraacethyl and sodium salt as ion arsenic, the chelating agent as arsenic such as diethyl-dithio formates, dimercaprol,
Arsenic is set to form complex compound and chelate raising removal rate.Although the above method has certain effect, arsenic removal rate to arsenic removal
It is not high, while the significant loss of catalyst activity component can be brought.
Therefore, this field needs to develop a kind of arsenic poisoning SCR denitration processing unit and method, so that in processing arsenic
The arsenic removal rate of malicious catalyst is high, process conditions are mild and pollution-free.
Summary of the invention
It is an object of the invention to overcome the above-mentioned prior art, a kind of arsenic poisoning SCR denitration is provided
Electrochemical process for treating, this method is high to the arsenic removal rate of arsenic poisoning SCR denitration, and process conditions are mild, and without dirt
Dye.
In order to achieve the above objectives, the electrochemical process for treating of arsenic poisoning SCR denitration of the present invention, feature
It is, comprising the following steps:
1) mechanical soot blowing processing is carried out to arsenic poisoning SCR denitration, then urges the arsenic poisoning SCR denitration after soot blowing
Agent carries out crushing and ball milling, obtains arsenic poisoning SCR denitration powder；
2) the arsenic poisoning SCR denitration powder that step 1) obtains is mixed with aqueous slkali, obtains mixture, then will
Mixture is added in electrochemistry arsenic removing apparatus as electrolyte, while being passed through oxidizing gas into electrochemistry arsenic removing apparatus, is made
It obtains mixture to be electrochemically reacted under the conditions of oxidizing gas, the SCR denitration after obtaining arsenic removal；
3) SCR denitration after arsenic removal that step 2) obtains is put into acid solution and is cleaned by ultrasonic, to go
SCR denitration except the alkali metal ion on the SCR denitration surface after arsenic removal, after obtaining pickling；
4) SCR denitration after pickling is impregnated into regenerated liquid, the SCR denitration after must impregnating；
5) SCR denitration after dipping is subjected to microwave calcination, and carries out heating roasting, so that SCR denitration is catalyzed
The predecessor on agent surface is converted into active component, completes the electrochemical treatments of arsenic poisoning SCR denitration.
Arsenic poisoning SCR denitration in step 1) is cellular or flat vanadium tungsten titanium system denitrating catalyst.
The granularity of arsenic poisoning SCR denitration powder is 60~100 mesh in step 1).
Aqueous slkali in step 2) is the sodium hydroxide solution that concentration is 0.01~2.0mol/L, and arsenic poisoning SCR denitration is urged
The solid-to-liquid ratio of agent powder and aqueous slkali is 0.5~50g/L.
In step 2), the anode of electrochemistry arsenic removing apparatus is selected from DSA electrode, and anode current is 5~15A, the rotation of anode plate
Rotational speed rate is 200~1000rpm；
Cathode is graphite electrode or carbon felt electrode, and cathode current is 5~10A；
Electrochemical reaction temperature is 20~60 DEG C, and the time of electrochemical reaction is 2~6h.
In step 2), oxidizing gas is air or oxygen, and the flow of oxidizing gas is 0.1~5L/min.
Acid solution is the sulfuric acid solution that concentration is 0.05~1.0mol/L in step 3), when ultrasonic cleaning, ultrasonic wave function
Rate is 10~50kw, and the time of ultrasonic cleaning is 20~60min.
In step 4) in regenerated liquid metavanadic acid ammonia density be 0.5~2.0wt%, metatungstic acid ammonia density be 1.0~
5.0wt%, concentration of oxalic acid are 0.05~0.2wt%；Dip time is 0.5~4.0h.
In step 5), the power of microwave calcination is 0.1~2.0kw, and temperature is 400~600 DEG C, and calcination time is 2~6h.
The invention has the following advantages:
The electrochemical process for treating of arsenic poisoning SCR denitration of the present invention, using electrochemical oxidation method pair
Arsenic poisoning SCR denitration carries out arsenic removal processing, recycles acid solution to remove the alkali metal ion on its surface, then utilizes
Microwave calcination and heating roasting after regenerated liquid dipping, so that the predecessor on SCR denitration surface is converted into active component.It needs
It is noted that the present invention is reduced reaction temperature and subtracted dense using electrochemical process for treating arsenic removal compared to traditional handicraft
Degree, process conditions are mild, and beneficial to energy-saving, and arsenic removal rate is high, pollution-free.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
The invention will be described in further detail with reference to the accompanying drawing:
With reference to Fig. 1, the electrochemical process for treating of arsenic poisoning SCR denitration of the present invention the following steps are included:
1) mechanical soot blowing processing is carried out to arsenic poisoning SCR denitration, then urges the arsenic poisoning SCR denitration after soot blowing
Agent carries out crushing and ball milling, obtains arsenic poisoning SCR denitration powder；
2) the arsenic poisoning SCR denitration powder that step 1) obtains is mixed with aqueous slkali, obtains mixture, then will
Mixture is added in electrochemistry arsenic removing apparatus as electrolyte, while being passed through oxidizing gas into electrochemistry arsenic removing apparatus, is made
It obtains mixture to be electrochemically reacted under the conditions of oxidizing gas, the SCR denitration after obtaining arsenic removal；
3) SCR denitration after arsenic removal that step 2) obtains is put into acid solution and is cleaned by ultrasonic, to go
SCR denitration except the alkali metal ion on the SCR denitration surface after arsenic removal, after obtaining pickling；
4) SCR denitration after pickling is impregnated into regenerated liquid, the SCR denitration after must impregnating；
5) SCR denitration after dipping is subjected to microwave calcination, and carries out heating roasting, so that SCR denitration is catalyzed
The predecessor on agent surface is converted into active component, completes the electrochemical treatments of arsenic poisoning SCR denitration.
Arsenic poisoning SCR denitration in step 1) is cellular or flat vanadium tungsten titanium system denitrating catalyst.
The granularity of arsenic poisoning SCR denitration powder is 60~100 mesh in step 1).
Aqueous slkali in step 2) is the sodium hydroxide solution that concentration is 0.01~2.0mol/L, and arsenic poisoning SCR denitration is urged
The solid-to-liquid ratio of agent powder and aqueous slkali is 0.5~50g/L.
In step 2), the anode of electrochemistry arsenic removing apparatus is selected from DSA electrode, and anode current is 5~15A, the rotation of anode plate
Rotational speed rate is 200~1000rpm；Cathode is graphite electrode or carbon felt electrode, and cathode current is 5~10A；Electrochemical reaction temperature
It is 20~60 DEG C, the time of electrochemical reaction is 2~6h.
In step 2), oxidizing gas is air or oxygen, and the flow of oxidizing gas is 0.1~5L/min.
Acid solution is the sulfuric acid solution that concentration is 0.05~1.0mol/L in step 3), when ultrasonic cleaning, ultrasonic wave function
Rate is 10~50kw, and the time of ultrasonic cleaning is 20~60min.
In step 4) in regenerated liquid metavanadic acid ammonia density be 0.5~2.0wt%, metatungstic acid ammonia density be 1.0~
5.0wt%, concentration of oxalic acid are 0.05~0.2wt%；Dip time is 0.5~4.0h.
In step 5), the power of microwave calcination is 0.1~2.0kw, and temperature is 400~600 DEG C, and calcination time is 2~6h.
Embodiment one
The electrochemical process for treating of arsenic poisoning SCR denitration of the present invention the following steps are included:
1) mechanical soot blowing processing is carried out to arsenic poisoning SCR denitration, then urges the arsenic poisoning SCR denitration after soot blowing
Agent carries out crushing and ball milling, obtains arsenic poisoning SCR denitration powder；
2) the arsenic poisoning SCR denitration powder that step 1) obtains is mixed with aqueous slkali, obtains mixture, then will
Mixture is added in electrochemistry arsenic removing apparatus as electrolyte, while being passed through oxidizing gas into electrochemistry arsenic removing apparatus, is made
It obtains mixture to be electrochemically reacted under the conditions of oxidizing gas, the SCR denitration after obtaining arsenic removal；
3) SCR denitration after arsenic removal that step 2) obtains is put into acid solution and is cleaned by ultrasonic, to go
SCR denitration except the alkali metal ion on the SCR denitration surface after arsenic removal, after obtaining pickling；
4) SCR denitration after pickling is impregnated into regenerated liquid, the SCR denitration after must impregnating；
5) SCR denitration after dipping is subjected to microwave calcination, and carries out heating roasting, so that SCR denitration is catalyzed
The predecessor on agent surface is converted into active component, completes the electrochemical treatments of arsenic poisoning SCR denitration.
Arsenic poisoning SCR denitration in step 1) is flat vanadium tungsten titanium system (V2O5-WO3/TiO2) denitration
Catalyst, the content of arsenic is 3.0wt% in catalyst.
The granularity of arsenic poisoning SCR denitration powder is 100 mesh in step 1).
Aqueous slkali in step 2) is the sodium hydroxide solution that concentration is 2.0mol/L, arsenic poisoning SCR denitration powder
The solid-to-liquid ratio of end and aqueous slkali is 50g/L.
In step 2), the anode of electrochemistry arsenic removing apparatus is selected from DSA electrode, anode current 15A, the rotation speed of anode plate
Rate is 1000rpm；Cathode is graphite electrode or carbon felt electrode, cathode current 10A；Electrochemical reaction temperature is 60 DEG C, electrification
The time for learning reaction is 6h.
In step 2), oxidizing gas is air or oxygen, and the flow of oxidizing gas is 5L/min.
Acid solution is the sulfuric acid solution that concentration is 1.0mol/L in step 3), and when ultrasonic cleaning, ultrasonic power is
50kw, the time of ultrasonic cleaning are 60min.
Metavanadic acid ammonia density is 2.0wt% in regenerated liquid in step 4), and metatungstic acid ammonia density is 5.0wt%, concentration of oxalic acid
For 0.2wt%；Dip time is 4.0h.
In step 5), the power of microwave calcination is 2.0kw, and temperature is 600 DEG C, calcination time 6h.
To treated, catalyst is detected, it is found that its arsenic removal rate reaches 93%, activation recovering to raw catelyst
95%.
Embodiment two
The electrochemical process for treating of arsenic poisoning SCR denitration of the present invention the following steps are included:
1) mechanical soot blowing processing is carried out to arsenic poisoning SCR denitration, then urges the arsenic poisoning SCR denitration after soot blowing
Agent carries out crushing and ball milling, obtains arsenic poisoning SCR denitration powder；
2) the arsenic poisoning SCR denitration powder that step 1) obtains is mixed with aqueous slkali, obtains mixture, then will
Mixture is added in electrochemistry arsenic removing apparatus as electrolyte, while being passed through oxidizing gas into electrochemistry arsenic removing apparatus, is made
It obtains mixture to be electrochemically reacted under the conditions of oxidizing gas, the SCR denitration after obtaining arsenic removal；
3) SCR denitration after arsenic removal that step 2) obtains is put into acid solution and is cleaned by ultrasonic, to go
SCR denitration except the alkali metal ion on the SCR denitration surface after arsenic removal, after obtaining pickling；
4) SCR denitration after pickling is impregnated into regenerated liquid, the SCR denitration after must impregnating；
5) SCR denitration after dipping is subjected to microwave calcination, and carries out heating roasting, so that SCR denitration is catalyzed
The predecessor on agent surface is converted into active component, completes the electrochemical treatments of arsenic poisoning SCR denitration.
Arsenic poisoning SCR denitration in step 1) is cellular vanadium tungsten titanium system (V2O5-WO3/TiO2) denitration
Catalyst, the content of arsenic is 2.0wt% in catalyst.
The granularity of arsenic poisoning SCR denitration powder is 80 mesh in step 1).
Aqueous slkali in step 2) is the sodium hydroxide solution that concentration is 0.5mol/L, arsenic poisoning SCR denitration powder
The solid-to-liquid ratio of end and aqueous slkali is 5g/L.
In step 2), the anode of electrochemistry arsenic removing apparatus is selected from DSA electrode, anode current 10A, the rotation speed of anode plate
Rate is 500rpm；Cathode is graphite electrode or carbon felt electrode, cathode current 8A；Electrochemical reaction temperature is 40 DEG C, electrochemistry
The time of reaction is 4h.
In step 2), oxidizing gas is air or oxygen, and the flow of oxidizing gas is 1L/min.
Acid solution is the sulfuric acid solution that concentration is 0.5mol/L in step 3), and when ultrasonic cleaning, ultrasonic power is
20kw, the time of ultrasonic cleaning are 40min.
Metavanadic acid ammonia density is 1.0wt% in regenerated liquid in step 4), and metatungstic acid ammonia density is 2.0wt%, concentration of oxalic acid
For 0.1wt%；Dip time is 2.0h.
In step 5), the power of microwave calcination is 1.0kw, and temperature is 500 DEG C, calcination time 4h.
To treated, catalyst is detected, it is found that its arsenic removal rate reaches 92%, activation recovering to raw catelyst
93%.
Embodiment three
The electrochemical process for treating of arsenic poisoning SCR denitration of the present invention the following steps are included:
1) mechanical soot blowing processing is carried out to arsenic poisoning SCR denitration, then urges the arsenic poisoning SCR denitration after soot blowing
Agent carries out crushing and ball milling, obtains arsenic poisoning SCR denitration powder；
2) the arsenic poisoning SCR denitration powder that step 1) obtains is mixed with aqueous slkali, obtains mixture, then will
Mixture is added in electrochemistry arsenic removing apparatus as electrolyte, while being passed through oxidizing gas into electrochemistry arsenic removing apparatus, is made
It obtains mixture to be electrochemically reacted under the conditions of oxidizing gas, the SCR denitration after obtaining arsenic removal；
3) SCR denitration after arsenic removal that step 2) obtains is put into acid solution and is cleaned by ultrasonic, to go
SCR denitration except the alkali metal ion on the SCR denitration surface after arsenic removal, after obtaining pickling；
4) SCR denitration after pickling is impregnated into regenerated liquid, the SCR denitration after must impregnating；
5) SCR denitration after dipping is subjected to microwave calcination, and carries out heating roasting, so that SCR denitration is catalyzed
The predecessor on agent surface is converted into active component, completes the electrochemical treatments of arsenic poisoning SCR denitration.
Arsenic poisoning SCR denitration in step 1) is cellular vanadium tungsten titanium system (V2O5-WO3/TiO2) denitration
Catalyst, wherein the content of arsenic is 2.0wt% in catalyst.
The granularity of arsenic poisoning SCR denitration powder is 60 mesh in step 1).
Aqueous slkali in step 2) is the sodium hydroxide solution that concentration is 0.01mol/L, arsenic poisoning SCR denitration powder
The solid-to-liquid ratio of end and aqueous slkali is 0.5g/L.
In step 2), the anode of electrochemistry arsenic removing apparatus is selected from DSA electrode, anode current 5A, the rotation speed of anode plate
Rate is 200rpm；Cathode is graphite electrode or carbon felt electrode, cathode current 5A；Electrochemical reaction temperature is 20 DEG C, electrochemistry
The time of reaction is 2h.
In step 2), oxidizing gas is air or oxygen, and the flow of oxidizing gas is 0.1L/min.
Acid solution is the sulfuric acid solution that concentration is 0.05mol/L in step 3), and when ultrasonic cleaning, ultrasonic power is
10kw, the time of ultrasonic cleaning are 20min.
Metavanadic acid ammonia density is 0.5wt% in regenerated liquid in step 4), and metatungstic acid ammonia density is 1.0wt%, concentration of oxalic acid
For 0.05wt%；Dip time is 0.5h.
In step 5), the power of microwave calcination is 0.1kw, and temperature is 400 DEG C, calcination time 2h.
To treated, catalyst is detected, it is found that its arsenic removal rate reaches 85%, activation recovering to raw catelyst
91%.
Example IV
The electrochemical process for treating of arsenic poisoning SCR denitration of the present invention the following steps are included:
1) mechanical soot blowing processing is carried out to arsenic poisoning SCR denitration, then urges the arsenic poisoning SCR denitration after soot blowing
Agent carries out crushing and ball milling, obtains arsenic poisoning SCR denitration powder；
2) the arsenic poisoning SCR denitration powder that step 1) obtains is mixed with aqueous slkali, obtains mixture, then will
Mixture is added in electrochemistry arsenic removing apparatus as electrolyte, while being passed through oxidizing gas into electrochemistry arsenic removing apparatus, is made
It obtains mixture to be electrochemically reacted under the conditions of oxidizing gas, the SCR denitration after obtaining arsenic removal；
3) SCR denitration after arsenic removal that step 2) obtains is put into acid solution and is cleaned by ultrasonic, to go
SCR denitration except the alkali metal ion on the SCR denitration surface after arsenic removal, after obtaining pickling；
4) SCR denitration after pickling is impregnated into regenerated liquid, the SCR denitration after must impregnating；
5) SCR denitration after dipping is subjected to microwave calcination, and carries out heating roasting, so that SCR denitration is catalyzed
The predecessor on agent surface is converted into active component, completes the electrochemical treatments of arsenic poisoning SCR denitration.
Arsenic poisoning SCR denitration in step 1) is cellular vanadium tungsten titanium system denitrating catalyst.
The granularity of arsenic poisoning SCR denitration powder is 100 mesh in step 1).
Aqueous slkali in step 2) is the sodium hydroxide solution that concentration is 1.5mol/L, arsenic poisoning SCR denitration powder
The solid-to-liquid ratio of end and aqueous slkali is 20g/L.
In step 2), the anode of electrochemistry arsenic removing apparatus is selected from DSA electrode, anode current 10A, the rotation speed of anode plate
Rate is 300rpm；Cathode is graphite electrode or carbon felt electrode, cathode current 6A；Electrochemical reaction temperature is 30 DEG C, electrochemistry
The time of reaction is 3h.
In step 2), oxidizing gas is air or oxygen, and the flow of oxidizing gas is 1L/min.
Acid solution is the sulfuric acid solution that concentration is 1.2mol/L in step 3), and when ultrasonic cleaning, ultrasonic power is
20kw, the time of ultrasonic cleaning are 30min.
Metavanadic acid ammonia density is 0.8wt% in regenerated liquid in step 4), and metatungstic acid ammonia density is 1.5wt%, concentration of oxalic acid
For 0.1wt%；Dip time is 2.0h.
In step 5), the power of microwave calcination is 0.5kw, and temperature is 450 DEG C, calcination time 3h.
Embodiment five
The electrochemical process for treating of arsenic poisoning SCR denitration of the present invention the following steps are included:
1) mechanical soot blowing processing is carried out to arsenic poisoning SCR denitration, then urges the arsenic poisoning SCR denitration after soot blowing
Agent carries out crushing and ball milling, obtains arsenic poisoning SCR denitration powder；
2) the arsenic poisoning SCR denitration powder that step 1) obtains is mixed with aqueous slkali, obtains mixture, then will
Mixture is added in electrochemistry arsenic removing apparatus as electrolyte, while being passed through oxidizing gas into electrochemistry arsenic removing apparatus, is made
It obtains mixture to be electrochemically reacted under the conditions of oxidizing gas, the SCR denitration after obtaining arsenic removal；
3) SCR denitration after arsenic removal that step 2) obtains is put into acid solution and is cleaned by ultrasonic, to go
SCR denitration except the alkali metal ion on the SCR denitration surface after arsenic removal, after obtaining pickling；
4) SCR denitration after pickling is impregnated into regenerated liquid, the SCR denitration after must impregnating；
5) SCR denitration after dipping is subjected to microwave calcination, and carries out heating roasting, so that SCR denitration is catalyzed
The predecessor on agent surface is converted into active component, completes the electrochemical treatments of arsenic poisoning SCR denitration.
Arsenic poisoning SCR denitration in step 1) is cellular vanadium tungsten titanium system denitrating catalyst.
The granularity of arsenic poisoning SCR denitration powder is 90 mesh in step 1).
Aqueous slkali in step 2) is the sodium hydroxide solution that concentration is 1.8mol/L, arsenic poisoning SCR denitration powder
The solid-to-liquid ratio of end and aqueous slkali is 40g/L.
In step 2), the anode of electrochemistry arsenic removing apparatus is selected from DSA electrode, anode current 12A, the rotation speed of anode plate
Rate is 800rpm；Cathode is graphite electrode or carbon felt electrode, cathode current 9A；Electrochemical reaction temperature is 50 DEG C, electrochemistry
The time of reaction is 5h.
In step 2), oxidizing gas is air or oxygen, and the flow of oxidizing gas is 4L/min.
Acid solution is the sulfuric acid solution that concentration is 0.8mol/L in step 3), and when ultrasonic cleaning, ultrasonic power is
40kw, the time of ultrasonic cleaning are 50min.
Metavanadic acid ammonia density is 1.6wt% in regenerated liquid in step 4), and metatungstic acid ammonia density is 4.0wt%, concentration of oxalic acid
For 0.15wt%；Dip time is 3.0h.
In step 5), the power of microwave calcination is 1.0kw, and temperature is 500 DEG C, calcination time 5h.
Claims (9)
1. a kind of electrochemical process for treating of arsenic poisoning SCR denitration, which comprises the following steps:
1) mechanical soot blowing processing is carried out to arsenic poisoning SCR denitration, then by the arsenic poisoning SCR denitration after soot blowing
Crushing and ball milling are carried out, arsenic poisoning SCR denitration powder is obtained；
2) the arsenic poisoning SCR denitration powder that step 1) obtains is mixed with aqueous slkali, obtains mixture, then will mixing
Object is added in electrochemistry arsenic removing apparatus as electrolyte, while being passed through oxidizing gas into electrochemistry arsenic removing apparatus, so that mixed
It closes object to be electrochemically reacted under the conditions of oxidizing gas, the SCR denitration after obtaining arsenic removal；
3) SCR denitration after arsenic removal that step 2) obtains is put into acid solution and is cleaned by ultrasonic, to remove
The alkali metal ion on the SCR denitration surface after arsenic, the SCR denitration after obtaining pickling；
4) SCR denitration after pickling is impregnated into regenerated liquid, the SCR denitration after must impregnating；
5) SCR denitration after dipping is subjected to microwave calcination, and carries out heating roasting, so that SCR denitration table
The predecessor in face is converted into active component, completes the electrochemical treatments of arsenic poisoning SCR denitration.
2. the electrochemical process for treating of arsenic poisoning SCR denitration according to claim 1, which is characterized in that step
1) the arsenic poisoning SCR denitration in is cellular or flat vanadium tungsten titanium system denitrating catalyst.
3. the electrochemical process for treating of arsenic poisoning SCR denitration according to claim 1, which is characterized in that step
1) granularity of arsenic poisoning SCR denitration powder is 60~100 mesh in.
4. the electrochemical process for treating of arsenic poisoning SCR denitration according to claim 1, which is characterized in that step
2) aqueous slkali in is the sodium hydroxide solution that concentration is 0.01~2.0mol/L, arsenic poisoning SCR denitration powder and alkali
The solid-to-liquid ratio of solution is 0.5~50g/L.
5. the electrochemical process for treating of arsenic poisoning SCR denitration according to claim 1, which is characterized in that step
2) in, the anode of electrochemistry arsenic removing apparatus is selected from DSA electrode, and anode current is 5~15A, and the speed of rotation of anode plate is 200~
1000rpm；
Cathode is graphite electrode or carbon felt electrode, and cathode current is 5~10A；
Electrochemical reaction temperature is 20~60 DEG C, and the time of electrochemical reaction is 2~6h.
6. the electrochemical process for treating of arsenic poisoning SCR denitration according to claim 1, which is characterized in that step
2) in, oxidizing gas is air or oxygen, and the flow of oxidizing gas is 0.1~5L/min.
7. the electrochemical process for treating of arsenic poisoning SCR denitration according to claim 1, which is characterized in that step
3) acid solution is the sulfuric acid solution that concentration is 0.05~1.0mol/L in, and when ultrasonic cleaning, ultrasonic power is 10~50kw,
The time of ultrasonic cleaning is 20~60min.
8. the electrochemical process for treating of arsenic poisoning SCR denitration according to claim 1, which is characterized in that step
4) metavanadic acid ammonia density is 0.5~2.0wt% in regenerated liquid in, and metatungstic acid ammonia density is 1.0~5.0wt%, and concentration of oxalic acid is
0.05~0.2wt%；Dip time is 0.5~4.0h.
9. the electrochemical process for treating of arsenic poisoning SCR denitration according to claim 1, which is characterized in that step
5) in, the power of microwave calcination is 0.1~2.0kw, and temperature is 400~600 DEG C, and calcination time is 2~6h.
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