CN107442135B - Regeneration method of arsenic poisoning SCR denitration catalyst - Google Patents
Regeneration method of arsenic poisoning SCR denitration catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 195
- 238000011069 regeneration method Methods 0.000 title claims abstract description 21
- 208000008316 Arsenic Poisoning Diseases 0.000 title abstract description 14
- 238000004140 cleaning Methods 0.000 claims abstract description 46
- 239000007789 gas Substances 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000008367 deionised water Substances 0.000 claims abstract description 24
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 24
- 230000009467 reduction Effects 0.000 claims abstract description 22
- 238000002791 soaking Methods 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 16
- 238000007664 blowing Methods 0.000 claims abstract description 11
- 239000012670 alkaline solution Substances 0.000 claims abstract description 8
- 239000004071 soot Substances 0.000 claims abstract description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 24
- 230000001172 regenerating effect Effects 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 13
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- DLCOPLYGCSRNAY-UHFFFAOYSA-N molybdenum titanium vanadium Chemical compound [Ti][Mo][V] DLCOPLYGCSRNAY-UHFFFAOYSA-N 0.000 claims description 5
- 239000001294 propane Substances 0.000 claims description 5
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical compound [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 claims description 5
- 239000012159 carrier gas Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 abstract description 26
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 26
- 238000010438 heat treatment Methods 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 238000004506 ultrasonic cleaning Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000003546 flue gas Substances 0.000 description 18
- 239000002956 ash Substances 0.000 description 16
- 238000006722 reduction reaction Methods 0.000 description 15
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 9
- 230000008929 regeneration Effects 0.000 description 9
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229910001868 water Inorganic materials 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000003245 coal Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 5
- IKIWQIUJLIJZJB-UHFFFAOYSA-N [N].O=[C] Chemical compound [N].O=[C] IKIWQIUJLIJZJB-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- 208000005374 Poisoning Diseases 0.000 description 3
- 231100000631 Secondary poisoning Toxicity 0.000 description 3
- SAIFTDNQIARTIU-UHFFFAOYSA-N [N].CCC Chemical compound [N].CCC SAIFTDNQIARTIU-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- COHDHYZHOPQOFD-UHFFFAOYSA-N arsenic pentoxide Inorganic materials O=[As](=O)O[As](=O)=O COHDHYZHOPQOFD-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 229910017251 AsO4 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DUHOAUWIKMJUNR-UHFFFAOYSA-N [Ti+5].[W+4].[V+5] Chemical group [Ti+5].[W+4].[V+5] DUHOAUWIKMJUNR-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910000413 arsenic oxide Inorganic materials 0.000 description 1
- 229960002594 arsenic trioxide Drugs 0.000 description 1
- MJLGNAGLHAQFHV-UHFFFAOYSA-N arsenopyrite Chemical compound [S-2].[Fe+3].[As-] MJLGNAGLHAQFHV-UHFFFAOYSA-N 0.000 description 1
- 229910052964 arsenopyrite Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- KTTMEOWBIWLMSE-UHFFFAOYSA-N diarsenic trioxide Chemical compound O1[As](O2)O[As]3O[As]1O[As]2O3 KTTMEOWBIWLMSE-UHFFFAOYSA-N 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- -1 vanadium molybdenum titanium (V) Chemical compound 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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- 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
- B01J23/90—Regeneration or reactivation
- B01J23/92—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
- B01D53/565—Nitrogen oxides by treating the gases with solids
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/88—Handling or mounting catalysts
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- 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
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- 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
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
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- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
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Abstract
The invention belongs to the fields of environmental protection technology and catalytic denitration, and particularly relates to a regeneration method of an arsenic poisoning SCR denitration catalyst. The method comprises the steps of firstly carrying out soot blowing and impurity removal on the arsenic poisoning SCR denitration catalyst, then carrying out ultrasonic cleaning by using deionized water under the condition of introducing ozone-air mixed gas, then carrying out soaking and cleaning by using weak alkaline solution, then carrying out two-stage gradient reduction by using different reducing gases at different temperatures, and finally carrying out rapid heating and roasting in the air to obtain the regenerated catalyst. After the method is adopted to regenerate the SCR denitration catalyst poisoned by arsenic, the denitration efficiency is recovered to the level of a fresh catalyst, the arsenic removal rate reaches more than 99 percent, and the arsenic poisoning resistance of the regenerated catalyst is greatly improved. In addition, the method has simple process and stronger operability, and is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the fields of environmental protection technology and denitration catalysis, and particularly relates to a regeneration method of an arsenic poisoning SCR denitration catalyst.
Background
The Selective Catalytic Reduction (SCR) denitration method has the advantages of high denitration efficiency, good selectivity, perfect technology and the like, and is the most widely applied smoke at presentGas denitration technology. The catalyst is the core of the SCR denitration technology, and the performance of the catalyst directly influences the integral denitration effect of the SCR system. However, in the actual use process, because the working environment is very harsh, the catalyst is deactivated due to abrasion, blockage, poisoning or sintering, and the denitration efficiency is obviously reduced, and when the catalyst cannot meet the overall denitration performance requirement of the SCR system, the catalyst needs to be replaced in time. The deactivated catalyst contains heavy metals and V2O5And the like, which are harmful solid wastes rich in various highly toxic elements, if the harmful solid wastes are not properly disposed, the sustainable development of technology, economy and environment is not facilitated. In order to standardize the disposal method of the deactivated catalyst, the technical policy for preventing and controlling nitrogen oxides of thermal power plants (issued in 2010 by the ministry of environmental protection) (issued in 2010]10) and the like, the regeneration treatment of the spent catalyst should be performed preferentially, and the development and application of the regeneration of the spent catalyst and the safe disposal technology are encouraged. It can be seen that regeneration has become a necessary option for the disposal of deactivated catalyst.
Arsenic is one of the important poisons causing the deactivation of the catalyst by poisoning. Arsenic species in the boiler tail flue gas are mainly derived from fossil fuel coal. China's coal contains a certain amount of arsenic, and arsenic species in the coal are mainly arsenic pyrite, and a small part is organic arsenic. The content of arsenic species changes with the change of coal types, and the arsenic content in southwest China, especially in coal mined in Guizhou, is very high. During combustion of coal in the furnace, arsenopyrite is oxidized to As at high temperature2O3(g) As produced by oxidation2O3(g) Diffuses into the catalyst by siphoning. On the one hand, As in catalyst micropores2O3(g) When the partial pressure exceeds the equilibrium partial pressure, the gas is condensed and adhered to surface sites to block catalyst channels, so that the reaction gas cannot reach catalytic active sites in the channels, and the catalyst is poisoned and inactivated; on the other hand, due to the catalyst surface sites and As2O3(g) Has very high binding force between them, As2O3(g) Is easy to be adsorbed on the active site and the inactive site of the surface, and then undergoes oxidation reaction to generate As2O5As produced by oxidation2O5Continuously accumulate on the surface of the catalyst to form an arsenic covering layer which blocks NH3Leading to catalyst poisoning and deactivation.
The regeneration process of the arsenic poisoning catalyst is researched by the prior scholars, and certain achievements are obtained. In general, existing regeneration methods are categorized into the following categories: firstly, cleaning and regenerating by adopting a strong oxidant; secondly, cleaning and regenerating by adopting weak base strong acid salt solution and dilute acid solution in sequence; thirdly, cleaning and regenerating by adopting a strong base solution and a strong acid solution in sequence; fourthly, directly regenerating by adopting a reducing organic matter at a high temperature; fifthly, firstly carrying out thermal reduction and then cleaning and regenerating by adopting an organic solution. The existing arsenic poisoning catalyst regeneration method has the advantages that the wet regeneration technology has relatively excellent arsenic removal effect, but is usually accompanied by the phenomena of secondary poisoning of the catalyst and large dissolution and loss of active ingredients; the thermal reduction regeneration can well avoid the defects, but the existing thermal reduction regeneration process needs to be carried out at an extremely high temperature, so that the phenomena of high-temperature sintering, active site damage and the like of the catalyst also exist.
Based on the problems, the invention aims at the arsenic-poisoned SCR denitration catalyst, and searches a regeneration method of the arsenic-poisoned SCR denitration catalyst based on the existing related research around the unique physical and chemical characteristics of the arsenic-poisoned SCR denitration catalyst, and seeks a technical scheme which is reasonable, effective and suitable for large-scale production.
Disclosure of Invention
The invention aims to provide a reasonable and effective regeneration method of an arsenic poisoning SCR denitration catalyst, the denitration efficiency of the catalyst regenerated by the method is recovered to the level of a fresh catalyst, the arsenic removal rate reaches over 99 percent, and the arsenic poisoning resistance of the regenerated catalyst is greatly improved.
According to the present invention there is provided a method comprising the steps of:
(1) firstly, mechanically blowing soot on an arsenic-poisoned SCR denitration catalyst, and then ultrasonically cleaning with deionized water under the condition of introducing ozone-air mixed gas;
(2) placing the catalyst treated in the step (1) in a weak alkaline solution for soaking and cleaning, and stirring discontinuously in the cleaning process;
(3) rinsing the catalyst treated in the step (2) by using deionized water, and then drying;
(4) placing the catalyst treated in the step (3) into a reactor, introducing strong reducing gas which is formed by taking inert gas as carrier gas and one or two of hydrogen or carbon monoxide, and carrying out primary reduction at low temperature, wherein the volume concentration of the gas is 1-30%, the reduction temperature is 250-300 ℃, and the reduction time is 1-6 h; then, introducing weak reducing gas which is formed by taking inert gas as carrier gas and one of ethylene, propane or propylene or any combination of the gases, and carrying out secondary reduction at high temperature, wherein the volume concentration of the gas is 1-30%, the reduction temperature is 350-550 ℃, and the reduction time is 0.5-1.5 h; finally, the regenerated catalyst is obtained after quick temperature rise roasting in the air.
Preferably, in the step (1), the arsenic-poisoned SCR denitration catalyst is vanadium tungsten titanium (V)2O5-WO3/TiO2) System or vanadium molybdenum titanium (V)2O5-MoO3/TiO2) A honeycomb denitration catalyst of the system.
Preferably, in the step (1), the cleaning temperature of the deionized water is 40-60 ℃, and the cleaning time is 5-20 min.
Preferably, in the step (1), the concentration of ozone in the ozone-air mixed gas is 10-250 mg/L.
Preferably, in the step (2), the weak alkaline solution is one or a mixture of two weak alkaline solutions of monoethanolamine or ammonia water, the concentration of the solution is 0.05-1.0 mol/L, and the cleaning time is 10-60 min.
Preferably, in the step (3), the drying temperature is 80-150 ℃ and the drying time is 4-12 h.
Preferably, in the step (4), the roasting temperature is 400-550 ℃, the heating rate is 20-30 ℃/min, and the roasting time is 1-5 h.
The invention has the beneficial effects that:
the method of the invention regenerates the arsenic poisoning catalyst by combining wet cleaning and thermal reduction. Firstly, the method can remove the fly ash deposited on the surface of the catalyst by using deionized water for ultrasonic cleaning, and simultaneously, ozone is introduced in the cleaning process, so that the method has the following beneficial effects: the ozone has strong oxidizing property, and on one hand, can be used for removing most of As on the surface of the catalyst2O3Oxidized to As2O5And is beneficial to the removal of arsenic species. On the other hand, ozone can not only remove V on the surface of the catalyst4+Is oxidized to V in a proper amount5+To adjust the valence state of the active component and optimize the surface V of the catalyst4+/V5+The specific value is used, and carbon deposit on the surface of the catalyst can be oxidized and removed, so that the specific surface area and the pore volume of the catalyst are recovered, and the recovery of the catalytic activity is facilitated. In addition, other types of strong oxidants can have negative effects, for example, treatment with hydrogen peroxide or potassium permanganate can also treat As2O3Oxidized to As2O5But may result in substantial dissolution of the active ingredient or K during processing+The introduction of metal ion impurities causes secondary poisoning. Subsequently, the invention adopts specific alkalescent solution for cleaning, and has a plurality of beneficial effects: first, As hardly soluble under alkaline conditions2O5Will be AsO4 3-The form of the catalyst is transferred into the solution, so that the catalyst can be removed to the maximum extent, and the recovery of the activity of the catalyst is facilitated; secondly, the cleaning by adopting monoethanolamine or ammonia water can avoid Na+Or K+The introduction of plasma metal ion impurities can not generate secondary poisoning phenomenon, and can ensure most V in the catalyst2O5And WO3(or MoO)3) Etc. are preserved, so that the active implantation step of the conventional regeneration technology can be omitted; and thirdly, the damage of the cleaning liquid to the physical structure of the catalyst can be controlled in a minimum range, and the mechanical property of the catalyst is slightly influenced. Then, the invention adopts a unique two-stage heating gradient reduction method to treat the arsenic poisoning catalyst so as to thoroughly remove the surfaceThe residual arsenic species on the surface can be removed by adopting strong reducing gas to carry out primary reduction at low temperature (250-300 ℃), and can be removed by adopting weak reducing gas to carry out secondary reduction at high temperature (350-550 ℃), and the method has the following beneficial effects: firstly, arsenic species remained on the surface of the catalyst can be removed to the maximum extent, and the arsenic removal rate reaches more than 99 percent; secondly, after the treatment of the weakly alkaline solution, the interaction force between the catalyst and the residual arsenic oxide is weakened, so that the reduction temperature is relatively low, and the deterioration of the structural characteristics of the catalyst carrier and the active component, which is possibly caused by long-time high-temperature reduction, is avoided. Finally, the catalyst activity is recovered by rapid heating and roasting in the air, the denitration activity reaches the level of a fresh catalyst, the catalyst void structure is further optimized, and partial mesopores and macropores are added on the basis of keeping a large number of micropores. Even if micropores of the regenerated catalyst are blocked by poisons such as arsenic and the like in the actual flue gas operation process, mesopores and macropores can still be used as pore channels for gas circulation to keep the catalytic activity of the catalyst, so that the arsenic poisoning resistance of the arsenic poisoning catalyst is greatly improved after the regeneration treatment.
Detailed Description
The invention provides a regeneration method of an arsenic-poisoned SCR denitration catalyst, and the invention is further explained by combining a specific embodiment.
Example 1
Example 1 describes a method for regenerating an arsenic-poisoned SCR denitration catalyst, which comprises the following specific steps:
(1) selecting an arsenic-poisoned vanadium-molybdenum-titanium honeycomb SCR denitration catalyst, mechanically removing ash, blowing by using 2Mpa clean and dry compressed air for 1h, removing the ash on the surface and in holes of the catalyst, cutting a 5 multiplied by 5 hole catalyst block with the height of 60mm, soaking the catalyst block in sufficient deionized water, introducing ozone-air mixed gas with the ozone concentration of 80mg/L, and ultrasonically shaking and cleaning for 20min at 40 ℃;
(2) transferring the catalyst treated in the step (1) to a sufficient amount of 0.25mol/L monoethanolamine solution prepared in advance, soaking and cleaning for 40min, and stirring discontinuously in the cleaning process;
(3) repeatedly rinsing the catalyst treated in the step (2) by using deionized water, and then putting the catalyst into an oven to be dried for 8 hours at the temperature of 110 ℃;
(4) and (3) placing the catalyst treated in the step (3) into a reactor, introducing a hydrogen-argon mixed gas with the volume concentration of 6% of hydrogen at the same time, reducing for 3 hours at 280 ℃, then switching to an ethylene-helium mixed gas with the volume concentration of 12% of ethylene, reducing for 1.5 hours at 450 ℃, finally moving the catalyst into a muffle furnace, heating to 500 ℃ at the speed of 25 ℃/min, and roasting for 3 hours at the temperature to obtain the regenerated catalyst.
The performance of the regenerated catalyst is evaluated by adopting simulated flue gas conditions to obtain NH3As a reducing agent, under typical flue gas conditions: NO 300ppm, SO2300ppm, O23 vol%, H2O is 5 vol%, the ammonia-nitrogen ratio is 1: 1, N2The space velocity is 4500h for balancing gas-1The denitration efficiency at a reaction temperature of 350 ℃ was 90.67%. Meanwhile, the regenerated catalyst is subjected to characterization test, and the result shows that the arsenic removal rate reaches over 99 percent.
Example 2
Example 2 also describes a method for regenerating an arsenic-poisoned SCR denitration catalyst, which comprises the following specific steps:
(1) selecting an arsenic-poisoned vanadium-molybdenum-titanium honeycomb SCR denitration catalyst, mechanically removing ash, blowing by using 2Mpa clean and dry compressed air for 1h, removing the ash on the surface and in holes of the catalyst, cutting a 5 multiplied by 5 hole catalyst block with the height of 60mm, soaking the catalyst block in sufficient deionized water, introducing ozone-air mixed gas with the ozone concentration of 80mg/L, and ultrasonically shaking and cleaning for 20min at 40 ℃;
(2) transferring the catalyst treated in the step (1) to a sufficient amount of 0.5mol/L monoethanolamine solution prepared in advance, soaking and cleaning for 30min, and stirring discontinuously in the cleaning process;
(3) repeatedly rinsing the catalyst treated in the step (2) by using deionized water, and then putting the catalyst into an oven to be dried for 8 hours at the temperature of 110 ℃;
(4) and (3) placing the catalyst treated in the step (3) into a reactor, introducing carbon monoxide-nitrogen mixed gas with the carbon monoxide volume concentration of 6% into the reactor, reducing the carbon monoxide-nitrogen mixed gas at 280 ℃ for 3h, switching to ethylene-helium mixed gas with the ethylene volume concentration of 12%, reducing the ethylene-helium mixed gas at 500 ℃ for 1h, finally moving the catalyst into a muffle furnace, heating to 500 ℃ at the speed of 25 ℃/min, and roasting at the temperature for 3h to obtain the regenerated catalyst.
The performance of the regenerated catalyst is evaluated by adopting simulated flue gas conditions to obtain NH3As a reducing agent, under typical flue gas conditions: NO 300ppm, SO2300ppm, O23 vol%, H2O is 5 vol%, the ammonia-nitrogen ratio is 1: 1, N2The space velocity is 4500h for balancing gas-1The denitration efficiency at a reaction temperature of 350 ℃ was 91.00%. Meanwhile, the regenerated catalyst is subjected to characterization test, and the result shows that the arsenic removal rate reaches over 99 percent.
Example 3
Example 3 also describes a method for regenerating an arsenic-poisoned SCR denitration catalyst, which comprises the following specific steps:
(1) selecting an arsenic-poisoned vanadium-molybdenum-titanium honeycomb SCR denitration catalyst, mechanically removing ash, blowing clean and dry compressed air of 2Mpa for 1h, removing the ash on the surface and in holes of the catalyst, cutting a catalyst block body with the height of 60mm and 5 multiplied by 5 holes, soaking the catalyst block body in sufficient deionized water, introducing ozone-air mixed gas with the ozone concentration of 120mg/L, and ultrasonically shaking and cleaning the catalyst block body for 16min at 40 ℃;
(2) transferring the catalyst treated in the step (1) to a sufficient amount of 0.75mol/L monoethanolamine solution prepared in advance, soaking and cleaning for 20min, and stirring discontinuously in the cleaning process;
(3) repeatedly rinsing the catalyst treated in the step (2) by using deionized water, and then putting the catalyst into an oven to be dried for 8 hours at the temperature of 110 ℃;
(4) and (3) placing the catalyst treated in the step (3) into a reactor, introducing a hydrogen-argon mixed gas with the volume concentration of 6% of hydrogen at the same time, reducing for 3 hours at 280 ℃, then switching to an ethylene-helium mixed gas with the volume concentration of 12% of ethylene, reducing for 0.5 hour at 550 ℃, finally moving the catalyst into a muffle furnace, heating to 500 ℃ at the speed of 25 ℃/min, and roasting for 3 hours at the temperature to obtain the regenerated catalyst.
The performance of the regenerated catalyst is evaluated by adopting simulated flue gas conditions to obtain NH3As a reducing agent, under typical flue gas conditions: NO 300ppm, SO2300ppm, O23 vol%, H2O is 5 vol%, the ammonia-nitrogen ratio is 1: 1, N2The space velocity is 4500h for balancing gas-1The denitration efficiency at a reaction temperature of 350 ℃ was 92.00%. Meanwhile, the regenerated catalyst is subjected to characterization test, and the result shows that the arsenic removal rate reaches over 99 percent.
Example 4
Example 4 also describes a method for regenerating an arsenic-poisoned SCR denitration catalyst, which comprises the following specific steps:
(1) selecting an arsenic-poisoned vanadium-molybdenum-titanium honeycomb SCR denitration catalyst, mechanically removing ash, blowing clean and dry compressed air of 2Mpa for 1h, removing the ash on the surface and in holes of the catalyst, cutting a catalyst block body with the height of 60mm and 5 multiplied by 5 holes, soaking the catalyst block body in sufficient deionized water, introducing ozone-air mixed gas with the ozone concentration of 120mg/L, and ultrasonically shaking and cleaning the catalyst block body for 16min at 40 ℃;
(2) transferring the catalyst treated in the step (1) to a sufficient amount of 1.0mol/L monoethanolamine solution prepared in advance, soaking and cleaning for 10min, and stirring discontinuously in the cleaning process;
(3) repeatedly rinsing the catalyst treated in the step (2) by using deionized water, and then putting the catalyst into an oven to be dried for 8 hours at the temperature of 110 ℃;
(4) and (3) placing the catalyst treated in the step (3) into a reactor, introducing carbon monoxide-nitrogen mixed gas with the carbon monoxide volume concentration of 6% at the same time, reducing for 3 hours at 280 ℃, then switching to propane-nitrogen mixed gas with the propane volume concentration of 12%, reducing for 1.5 hours at 450 ℃, finally moving the catalyst into a muffle furnace, heating to 500 ℃ at the speed of 25 ℃/min, and roasting for 3 hours at the temperature to obtain the regenerated catalyst.
The performance of the regenerated catalyst is evaluated by adopting simulated flue gas conditions to obtain NH3As a reducing agent, under typical flue gas conditions: NO 300ppm, SO2300ppm, O23 vol%, H2O is 5 vol%, the ammonia-nitrogen ratio is 1: 1, N2The space velocity is 4500h for balancing gas-1The denitration efficiency at a reaction temperature of 350 ℃ was 91.33%. Meanwhile, the regenerated catalyst is subjected to characterization test, and the result shows that the arsenic removal rate reaches over 99 percent.
Example 5
Example 5 also describes a method for regenerating an arsenic-poisoned SCR denitration catalyst, which comprises the specific steps of:
(1) selecting an arsenic-poisoned vanadium-tungsten-titanium system honeycomb SCR denitration catalyst, mechanically removing ash, blowing the catalyst for 1h by using 2Mpa clean and dry compressed air, removing the ash on the surface and in holes of the catalyst, cutting a 5 multiplied by 5 hole catalyst block with the height of 60mm, soaking the catalyst block in sufficient deionized water, introducing ozone-air mixed gas with the ozone concentration of 160mg/L, and ultrasonically shaking and cleaning the catalyst at 40 ℃ for 12 min;
(2) transferring the catalyst treated in the step (1) to a sufficient amount of 0.25mol/L ammonia water solution prepared in advance, soaking and cleaning for 40min, and stirring discontinuously in the cleaning process;
(3) repeatedly rinsing the catalyst treated in the step (2) by using deionized water, and then putting the catalyst into an oven to be dried for 8 hours at the temperature of 110 ℃;
(4) and (3) placing the catalyst treated in the step (3) into a reactor, introducing a hydrogen-argon mixed gas with 6% of hydrogen volume concentration, reducing for 2.5h at 300 ℃, switching to a propane-nitrogen mixed gas with 12% of propane volume concentration, reducing for 1.0h at 500 ℃, finally, transferring the catalyst into a muffle furnace, heating to 500 ℃ at the speed of 25 ℃/min, and roasting for 3h at the temperature to obtain the regenerated catalyst.
The performance of the regenerated catalyst is evaluated by adopting simulated flue gas conditions to obtain NH3As a reducing agent, under typical flue gas conditions: NO 300ppm, SO2300ppm, O23 vol%, H2O is 5 vol%, the ammonia-nitrogen ratio is 1: 1, N2The space velocity is 4500h for balancing gas-1The denitration efficiency at a reaction temperature of 350 ℃ was 92.00%. Meanwhile, the regenerated catalyst is subjected to characterization test, and the result shows that the arsenic removal rate reaches over 99 percent.
Example 6
Example 6 also describes a method for regenerating an arsenic-poisoned SCR denitration catalyst, which comprises the specific steps of:
(1) selecting an arsenic-poisoned vanadium-tungsten-titanium system honeycomb SCR denitration catalyst, mechanically removing ash, blowing the catalyst for 1h by using 2Mpa clean and dry compressed air, removing the ash on the surface and in holes of the catalyst, cutting a 5 multiplied by 5 hole catalyst block with the height of 60mm, soaking the catalyst block in sufficient deionized water, introducing ozone-air mixed gas with the ozone concentration of 160mg/L, and ultrasonically shaking and cleaning the catalyst at 40 ℃ for 12 min;
(2) transferring the catalyst treated in the step (1) to a sufficient amount of 0.5mol/L ammonia water solution prepared in advance, soaking and cleaning for 30min, and stirring discontinuously in the cleaning process;
(3) repeatedly rinsing the catalyst treated in the step (2) by using deionized water, and then putting the catalyst into an oven to be dried for 8 hours at the temperature of 110 ℃;
(4) and (3) placing the catalyst treated in the step (3) into a reactor, introducing carbon monoxide-nitrogen mixed gas with the carbon monoxide volume concentration of 6% at the same time, reducing for 2.5h at 300 ℃, then switching to propane-nitrogen mixed gas with the propane volume concentration of 12%, reducing for 0.5h at 550 ℃, finally moving the catalyst into a muffle furnace, heating to 500 ℃ at the speed of 25 ℃/min, and roasting for 3h at the temperature to obtain the regenerated catalyst.
The performance of the regenerated catalyst is evaluated by adopting simulated flue gas conditions to obtain NH3As a reducing agent, under typical flue gas conditions: NO 300ppm, SO2300ppm, O23 vol%, H2O is 5 vol%, the ammonia-nitrogen ratio is 1: 1, N2The space velocity is 4500h for balancing gas-1The denitration efficiency at a reaction temperature of 350 ℃ was 92.33%. Simultaneous characterization of regenerated catalystThe test shows that the arsenic removal rate reaches over 99 percent.
Example 7
Example 7 describes a method for regenerating an arsenic-poisoned SCR denitration catalyst, which comprises the following specific steps:
(1) selecting an arsenic-poisoned vanadium-tungsten-titanium system honeycomb SCR denitration catalyst, mechanically removing ash, blowing the catalyst for 1h by using 2Mpa clean and dry compressed air, removing the ash on the surface and in holes of the catalyst, cutting a 5 multiplied by 5 hole catalyst block with the height of 60mm, soaking the catalyst block in sufficient deionized water, introducing ozone-air mixed gas with the ozone concentration of 200mg/L, and ultrasonically shaking and cleaning the catalyst for 8min at 40 ℃;
(2) transferring the catalyst treated in the step (1) to a sufficient amount of 0.75mol/L ammonia water solution prepared in advance, soaking and cleaning for 20min, and stirring discontinuously in the cleaning process;
(3) repeatedly rinsing the catalyst treated in the step (2) by using deionized water, and then putting the catalyst into an oven to be dried for 8 hours at the temperature of 110 ℃;
(4) and (3) placing the catalyst treated in the step (3) into a reactor, introducing a hydrogen-argon mixed gas with 6% of hydrogen volume concentration, reducing for 2.5h at 300 ℃, switching to a propylene-argon mixed gas with 12% of propylene volume concentration, reducing for 1.0h at 500 ℃, finally moving the catalyst into a muffle furnace, heating to 500 ℃ at the speed of 25 ℃/min, and roasting for 3h at the temperature to obtain the regenerated catalyst.
The performance of the regenerated catalyst is evaluated by adopting simulated flue gas conditions to obtain NH3As a reducing agent, under typical flue gas conditions: NO 300ppm, SO2300ppm, O23 vol%, H2O is 5 vol%, the ammonia-nitrogen ratio is 1: 1, N2The space velocity is 4500h for balancing gas-1The denitration efficiency at a reaction temperature of 350 ℃ was 91.66%. Meanwhile, the regenerated catalyst is subjected to characterization test, and the result shows that the arsenic removal rate reaches over 99 percent.
Example 8
Example 8 also describes a method for regenerating an arsenic-poisoned SCR denitration catalyst, which comprises the specific steps of:
(1) selecting an arsenic-poisoned vanadium-tungsten-titanium system honeycomb SCR denitration catalyst, mechanically removing ash, blowing the catalyst for 1h by using 2Mpa clean and dry compressed air, removing the ash on the surface and in holes of the catalyst, cutting a 5 multiplied by 5 hole catalyst block with the height of 60mm, soaking the catalyst block in sufficient deionized water, introducing ozone-air mixed gas with the ozone concentration of 200mg/L, and ultrasonically shaking and cleaning the catalyst for 8min at 40 ℃;
(2) transferring the catalyst treated in the step (1) to a sufficient amount of pre-prepared 1.0mol/L ammonia water solution for soaking and cleaning for 10min, and carrying out intermittent stirring in the cleaning process;
(3) repeatedly rinsing the catalyst treated in the step (2) by using deionized water, and then putting the catalyst into an oven to be dried for 8 hours at the temperature of 110 ℃;
(4) and (3) placing the catalyst treated in the step (3) into a reactor, introducing a carbon monoxide-nitrogen mixed gas with the carbon monoxide volume concentration of 6% at the same time, reducing for 2.5h at 300 ℃, then switching to a propylene-argon mixed gas with the propylene volume concentration of 12%, reducing for 0.5h at 550 ℃, finally moving the catalyst into a muffle furnace, heating to 500 ℃ at the speed of 25 ℃/min, and roasting for 3h at the temperature to obtain the regenerated catalyst.
The performance of the regenerated catalyst is evaluated by adopting simulated flue gas conditions to obtain NH3As a reducing agent, under typical flue gas conditions: NO 300ppm, SO2300ppm, O23 vol%, H2O is 5 vol%, the ammonia-nitrogen ratio is 1: 1, N2The space velocity is 4500h for balancing gas-1The denitration efficiency at a reaction temperature of 350 ℃ was 92.33%. Meanwhile, the regenerated catalyst is subjected to characterization test, and the result shows that the arsenic removal rate reaches over 99 percent.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, but rather as the subject matter of any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention.
Claims (7)
1. A regeneration method of an arsenic-poisoned SCR denitration catalyst is characterized by comprising the following steps:
(1) firstly, mechanically blowing soot on an arsenic-poisoned SCR denitration catalyst, and then ultrasonically cleaning with deionized water under the condition of introducing ozone-air mixed gas;
(2) placing the catalyst treated in the step (1) in a weak alkaline solution for soaking and cleaning, and stirring discontinuously in the cleaning process;
(3) rinsing the catalyst treated in the step (2) by using deionized water, and then drying;
(4) placing the catalyst treated in the step (3) into a reactor, introducing strong reducing gas which is formed by taking inert gas as carrier gas and one or two of hydrogen or carbon monoxide, and carrying out primary reduction at low temperature, wherein the volume concentration of the strong reducing gas is 1-30%, the reduction temperature is 250-300 ℃, and the reduction time is 1-6 h; then, introducing weak reducing gas which is formed by taking inert gas as carrier gas and one or any combination of ethylene, propane or propylene, and carrying out secondary reduction at high temperature, wherein the volume concentration of the weak reducing gas is 1-30%, the reduction temperature is 350-550 ℃, and the reduction time is 0.5-1.5 h; finally, the regenerated catalyst is obtained after quick temperature rise roasting in the air.
2. The method as claimed in claim 1, wherein in the step (1), the arsenic-poisoned SCR denitration catalyst is a honeycomb denitration catalyst of a vanadium-tungsten-titanium system or a vanadium-molybdenum-titanium system.
3. The regeneration method of the arsenic-poisoned SCR denitration catalyst as claimed in claim 1, wherein in the step (1), the cleaning temperature of deionized water is 40-60 ℃ and the cleaning time is 5-20 min.
4. The method for regenerating an arsenic-poisoned SCR denitration catalyst according to claim 1, wherein in the step (1), the concentration of ozone in the ozone-air mixed gas is 10 to 250 mg/L.
5. The method for regenerating an arsenic-poisoned SCR denitration catalyst as claimed in claim 1, wherein in the step (2), the weak alkaline solution is one or a mixture of two weak alkaline solutions of monoethanolamine or ammonia water, the solution concentration is 0.05-1.0 mol/L, and the cleaning time is 10-60 min.
6. The method for regenerating an arsenic-poisoned SCR denitration catalyst as claimed in claim 1, wherein in the step (3), the drying temperature is 80 to 150 ℃ and the drying time is 4 to 12 hours.
7. The regeneration method of the arsenic-poisoned SCR denitration catalyst as claimed in claim 1, wherein in the step (4), the roasting temperature is 400-550 ℃, the temperature rise rate is 20-30 ℃/min, and the roasting time is 1-5 h.
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| CN109999923B (en) * | 2019-04-28 | 2023-01-13 | 上海理工大学 | Method and device for realizing in-situ activation of SCR (selective catalytic reduction) catalyst by utilizing ozone |
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