CN117531548B - Regeneration technology of waste SCR denitration catalyst - Google Patents
Regeneration technology of waste SCR denitration catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 195
- 239000002699 waste material Substances 0.000 title claims abstract description 93
- 230000008929 regeneration Effects 0.000 title claims abstract description 16
- 238000011069 regeneration method Methods 0.000 title claims abstract description 16
- 238000005516 engineering process Methods 0.000 title description 7
- 238000000034 method Methods 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 238000004140 cleaning Methods 0.000 claims abstract description 11
- 239000004480 active ingredient Substances 0.000 claims abstract description 6
- 238000010304 firing Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims description 30
- IMYZYCNQZDBZBQ-UHFFFAOYSA-N 9,10-epoxyoctadecanoic acid Chemical compound CCCCCCCCC1OC1CCCCCCCC(O)=O IMYZYCNQZDBZBQ-UHFFFAOYSA-N 0.000 claims description 28
- 239000003513 alkali Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 16
- 230000000630 rising effect Effects 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 6
- 239000011609 ammonium molybdate Substances 0.000 claims description 6
- 229940010552 ammonium molybdate Drugs 0.000 claims description 6
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000001172 regenerating effect Effects 0.000 claims 5
- 230000000694 effects Effects 0.000 abstract description 18
- 238000010438 heat treatment Methods 0.000 description 48
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 21
- 239000001301 oxygen Substances 0.000 description 21
- 229910052760 oxygen Inorganic materials 0.000 description 21
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- IMYZYCNQZDBZBQ-IAGOWNOFSA-N 8-[(2r,3r)-3-octyloxiran-2-yl]octanoic acid Chemical compound CCCCCCCC[C@H]1O[C@@H]1CCCCCCCC(O)=O IMYZYCNQZDBZBQ-IAGOWNOFSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000003546 flue gas Substances 0.000 description 5
- 235000006408 oxalic acid Nutrition 0.000 description 5
- IMYZYCNQZDBZBQ-SJORKVTESA-N (9S,10R)-epoxyoctadecanoic acid Chemical compound CCCCCCCC[C@H]1O[C@H]1CCCCCCCC(O)=O IMYZYCNQZDBZBQ-SJORKVTESA-N 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 3
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
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- 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
- B01D53/74—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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- 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
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- 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
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
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- 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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- B01J38/485—Impregnating or reimpregnating with, or deposition of metal compounds or catalytically active elements
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Abstract
The invention relates to the technical field of catalyst regeneration, and provides a regeneration process of a waste SCR denitration catalyst, which comprises the following steps: after the waste SCR denitration catalyst is roasted, cleaning, drying, implanting active ingredients, and calcining to obtain a regenerated SCR denitration catalyst; the firing includes: sequentially performing primary roasting at 180-220 ℃, secondary roasting at 240-260 ℃, tertiary roasting at 280-320 ℃, quaternary roasting at 340-360 ℃ and five roasting at 380-420 ℃. Through the technical scheme, the problem of low denitration activity of the regenerated SCR denitration catalyst in the prior art is solved.
Description
Technical Field
The invention relates to the technical field of catalyst regeneration, in particular to a regeneration process of a waste SCR denitration catalyst.
Background
The sintering process is an indispensable process for steel production, about 50% of nitrogen oxides can be generated in the sintering process, and a Selective Catalytic Reduction (SCR) denitration technology is mostly used for denitration treatment of sintering flue gas in the steel industry so as to reach the allowable emission standard of nitrogen oxides in China.
The core of the SCR denitration technology is an SCR denitration catalyst, and with the wide application of the SCR denitration technology in the steel industry, the waste SCR denitration catalyst with the service life being expired is produced in a large amount, so how to regenerate the waste SCR denitration catalyst is a hot spot developed at present and is also required for environmental protection.
At present, the regeneration technology of the waste SCR denitration catalyst is not mature, and the problems of catalyst cracking, active material loss and the like caused by ammonium sulfate deposition and direct cleaning exist, so that the denitration activity of the regenerated SCR denitration catalyst is low.
Disclosure of Invention
The invention provides a regeneration process of a waste SCR denitration catalyst, which solves the problem of low denitration activity of the regenerated SCR denitration catalyst in the related technology.
The technical scheme of the invention is as follows:
a regeneration process of a waste SCR denitration catalyst comprises the following steps: after the waste SCR denitration catalyst is roasted, cleaning, drying, implanting active ingredients, and calcining to obtain a regenerated SCR denitration catalyst;
the firing includes: sequentially performing primary roasting at 180-220 ℃, secondary roasting at 240-260 ℃, tertiary roasting at 280-320 ℃, quaternary roasting at 340-360 ℃ and five roasting at 380-420 ℃.
As a further technical scheme, the temperature rising rate of the primary roasting is below 1.5 ℃/min;
the temperature rising rates of the secondary roasting, the tertiary roasting, the quaternary roasting and the five-time roasting are respectively and independently 1-1.5 ℃/min.
According to the invention, ammonium bisulfate or ammonium bisulfate is slowly decomposed by controlling the temperature rising rate, so that the damage and even cracking of the internal structure of the catalyst caused by rapid decomposition are avoided, and the denitration activity of the regenerated SCR denitration catalyst is further improved.
As a further technical scheme, the temperature rising rate of the primary roasting is below 1 ℃/min;
the temperature rising rates of the secondary roasting, the tertiary roasting, the quaternary roasting and the five roasting are respectively and independently 1 ℃/min.
As a further technical scheme, the time of the primary roasting, the secondary roasting, the tertiary roasting and the quaternary roasting is respectively and independently 50-80 min, and the time of the five times of roasting is 3.5-4.5 h.
As a further technical scheme, oxygen is introduced at a flow rate of 0.1-0.5 m/min in the roasting process.
The invention is baked in oxygen atmosphere, ammonium bisulfate is oxidized into ammonium sulfate, only ammonia is decomposed, sulfate radical is remained in the catalyst, the acid position is improved, part of the activity of the catalyst is recovered, and sulfate is formed by the sulfate radical and part of alkaline oxide, so that the subsequent cleaning is facilitated. In addition, the residual tetravalent vanadium in the waste SCR denitration catalyst can be oxidized into pentavalent vanadium through roasting in an oxygen atmosphere, the pentavalent vanadium is not easy to wash away in the washing process, the loss of the active component vanadium pentoxide can be reduced, the implantation amount of the active component is reduced, and the cost is reduced.
As a further technical scheme, the cleaning comprises water washing, acid washing and alkali washing.
As a further technical scheme, the acid liquor used in the acid washing comprises a mixture of one or more of sulfuric acid, oxalic acid and citric acid, a surfactant and water.
As a further technical scheme, the alkali liquor used in the alkali washing comprises a mixture of one or more of NaOH, ammonia water and EDTA, a surfactant and water.
As a further technical scheme, the implantation active ingredients specifically are: and immersing the dried SCR denitration catalyst in the active liquid at 40-60 ℃ for 5-15 min.
As a further technical scheme, the active liquid comprises a mixture of one or more of ammonium metavanadate, ammonium metatungstate and ammonium molybdate and water.
As a further technical scheme, the surfactant comprises one or two of OP-10 and peregal.
As a further technical scheme, the calcining specifically comprises: calcining at 100-120 ℃ for 2-3 hours, and then calcining at 350-420 ℃ for 4-5 hours.
As a further technical scheme, the method further comprises the step of modifying the calcined catalyst by using 9, 10-epoxy octadecanoic acid.
According to the invention, the catalyst after calcination is modified by the 9, 10-epoxy octadecanoic acid, so that the service life of the regenerated SCR denitration catalyst is prolonged. Alkane carboxyl is introduced into the regenerated SCR denitration catalyst, so that on one hand, the hydrophobicity of the regenerated SCR denitration catalyst is improved, the poisoning effect of water on the catalyst is reduced, and the problems that the service life is greatly reduced due to the fact that water is condensed in capillary holes of the catalyst, vaporization expansion is carried out along with the increase of temperature, the catalyst structure is damaged, and even the catalyst is broken are solved to a great extent; on the other hand, alkane carboxyl in the regenerated SCR denitration catalyst can react with sulfur trioxide when in use, so that the generation of ammonium salt is reduced to a certain extent, the problem of catalyst deactivation caused by covering the active site of the catalyst with ammonium salt is solved, and the service life of the regenerated SCR denitration catalyst is remarkably prolonged.
As a further technical scheme, the mass ratio of the 9, 10-epoxy octadecanoic acid to the calcined catalyst is 0.3-0.8:1.
According to the invention, the mass ratio of the 9, 10-epoxy octadecanoic acid to the calcined catalyst is further controlled within the range of 0.3-0.8:1, so that the service life of the regenerated SCR denitration catalyst is further prolonged.
As a further technical scheme, the modification treatment specifically comprises: and mixing 9, 10-epoxy octadecanoic acid, the calcined catalyst and a solvent for reaction to obtain the regenerated SCR denitration catalyst.
As a further technical scheme, the reaction temperature is 170-180 ℃ and the reaction time is 40-60 min.
The regenerated SCR denitration catalyst obtained by the regeneration process of the waste SCR denitration catalyst provided by the invention can be regenerated by adopting the regeneration process of the invention continuously after being used.
The working principle and the beneficial effects of the invention are as follows:
the invention provides a regeneration process of a waste SCR denitration catalyst, which comprises the steps of roasting the waste SCR denitration catalyst, cleaning, drying, implanting active ingredients and calcining. The structural integrity of the SCR denitration catalyst in the roasting process is ensured by sequentially carrying out primary roasting at 180-220 ℃, secondary roasting at 240-260 ℃, tertiary roasting at 280-320 ℃, quaternary roasting at 340-360 ℃ and five-time roasting at 380-420 ℃ and staged roasting, so that the denitration activity of the regenerated SCR denitration catalyst is improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The waste SCR denitration catalyst in the following examples and comparative examples was an inactivated honeycomb catalyst (V) having a size of 150 mm. Times.150 mm. Times.1100 mm for 1500 days 2 O 5 -WO 3 -MoO 3 /TiO 2 Catalyst, 18-well x 18-well).
Example 1
S1, heating the waste SCR denitration catalyst to 200 ℃ at a speed of 2 ℃/min under an ozone atmosphere, roasting at 200 ℃ for 60min, heating to 250 ℃ at a speed of 2 ℃/min, roasting at 250 ℃ for 60min, heating to 300 ℃ at a speed of 2 ℃/min, roasting at 300 ℃ for 60min, heating to 350 ℃ at a speed of 2 ℃/min, roasting at 350 ℃ for 60min, heating to 400 ℃ at a speed of 2 ℃/min, and roasting at 400 ℃ for 4h to obtain the roasted waste SCR denitration catalyst, wherein the flow rate of ozone is 0.5m/min;
s2, placing the roasted waste SCR denitration catalyst in an ultrasonic tank, and ultrasonically cleaning for 15min under the conditions of 40 ℃ water and bubbling pressure of 0.4MPa to obtain the washed waste SCR denitration catalyst;
s3, placing the washed waste SCR denitration catalyst in alkali liquor, performing alkali washing for 15min to obtain the washed waste SCR denitration catalyst, wherein the mass volume ratio of the washed waste SCR denitration catalyst to the alkali liquor is 1g to 5mL, and the alkali liquor consists of 0.1wt% of NaOH, 1wt% of EDTA, 5wt% of ammonia water, 1.5wt% of OP-10 and the balance of water;
s4, placing the waste SCR denitration catalyst subjected to alkali washing in acid liquor, and carrying out acid washing for 15min to obtain the waste SCR denitration catalyst subjected to acid washing, wherein the mass volume ratio of the waste SCR denitration catalyst subjected to alkali washing to the acid liquor is 1g to 5mL, and the acid liquor consists of 3wt% of oxalic acid, 7wt% of citric acid, 1.5wt% of OP-10 and the balance of water;
s5, placing the waste SCR denitration catalyst after pickling in deionized water at 35 ℃, rinsing, and drying at 110 ℃ for 5 hours to obtain the waste SCR denitration catalyst after drying;
s6, immersing the dried waste SCR denitration catalyst into active liquid at 50 ℃ for 10min, taking out, drying at 110 ℃ for 2.5h, heating to 400 ℃ and calcining for 4.5h to obtain the regenerated SCR denitration catalyst, wherein the mass volume ratio of the dried waste SCR denitration catalyst to the active liquid is 1g to 10mL, and the active liquid consists of 1wt% of ammonium metavanadate, 5wt% of ammonium metatungstate, 3wt% of ammonium molybdate and the balance of water.
Example 2
S1, heating the waste SCR denitration catalyst to 200 ℃ at a speed of 2 ℃/min under an oxygen atmosphere, roasting at 200 ℃ for 60min, heating to 250 ℃ at a speed of 2 ℃/min, roasting at 250 ℃ for 60min, heating to 300 ℃ at a speed of 2 ℃/min, roasting at 300 ℃ for 60min, heating to 350 ℃ at a speed of 2 ℃/min, roasting at 350 ℃ for 60min, heating to 400 ℃ at a speed of 2 ℃/min, and roasting at 400 ℃ for 4h to obtain the roasted waste SCR denitration catalyst, wherein the flow rate of oxygen is 0.5m/min;
s2, placing the roasted waste SCR denitration catalyst in an ultrasonic tank, and ultrasonically cleaning for 15min under the conditions of 40 ℃ water and bubbling pressure of 0.4MPa to obtain the washed waste SCR denitration catalyst;
s3, placing the washed waste SCR denitration catalyst in alkali liquor, performing alkali washing for 15min to obtain the washed waste SCR denitration catalyst, wherein the mass volume ratio of the washed waste SCR denitration catalyst to the alkali liquor is 1g to 5mL, and the alkali liquor consists of 0.1wt% of NaOH, 1wt% of EDTA, 5wt% of ammonia water, 1.5wt% of OP-10 and the balance of water;
s4, placing the waste SCR denitration catalyst subjected to alkali washing in acid liquor, and carrying out acid washing for 15min to obtain the waste SCR denitration catalyst subjected to acid washing, wherein the mass volume ratio of the waste SCR denitration catalyst subjected to alkali washing to the acid liquor is 1g to 5mL, and the acid liquor consists of 3wt% of oxalic acid, 7wt% of citric acid, 1.5wt% of OP-10 and the balance of water;
s5, placing the waste SCR denitration catalyst after pickling in deionized water at 35 ℃, rinsing, and drying at 110 ℃ for 5 hours to obtain the waste SCR denitration catalyst after drying;
s6, immersing the dried waste SCR denitration catalyst into active liquid at 50 ℃ for 10min, taking out, drying at 110 ℃ for 2.5h, heating to 400 ℃ and calcining for 4.5h to obtain the regenerated SCR denitration catalyst, wherein the mass volume ratio of the dried waste SCR denitration catalyst to the active liquid is 1g to 10mL, and the active liquid consists of 1wt% of ammonium metavanadate, 5wt% of ammonium metatungstate, 3wt% of ammonium molybdate and the balance of water.
Example 3
S1, heating the waste SCR denitration catalyst to 180 ℃ at a speed of 2 ℃/min under an oxygen atmosphere, roasting at 180 ℃ for 80min, heating to 240 ℃ at a speed of 2 ℃/min, roasting at 240 ℃ for 80min, heating to 280 ℃ at a speed of 2 ℃/min, roasting at 280 ℃ for 80min, heating to 340 ℃ at 340 ℃ and roasting at 2 ℃/min to 380 ℃ at 380 ℃ for 4.5h, and obtaining the roasted waste SCR denitration catalyst, wherein the flow rate of oxygen is 0.5m/min;
s2, placing the roasted waste SCR denitration catalyst in an ultrasonic tank, and ultrasonically cleaning for 20min under the conditions of water at 30 ℃ and bubbling pressure of 0.4MPa to obtain the washed waste SCR denitration catalyst;
s3, placing the washed waste SCR denitration catalyst in alkali liquor, and performing alkali washing for 10min to obtain the washed waste SCR denitration catalyst, wherein the mass volume ratio of the washed waste SCR denitration catalyst to the alkali liquor is 1g to 5mL, and the alkali liquor consists of 0.3wt% of NaOH, 0.2wt% of EDTA, 5wt% of ammonia water, 20-2 wt% of peregal O and the balance of water;
s4, placing the waste SCR denitration catalyst subjected to alkali washing in acid liquor, and carrying out acid washing for 10min to obtain the waste SCR denitration catalyst subjected to acid washing, wherein the mass volume ratio of the waste SCR denitration catalyst subjected to alkali washing to the acid liquor is 1g to 5mL, and the acid liquor consists of sulfuric acid 0.5wt%, oxalic acid 1wt%, citric acid 2wt%, OP-10.5 wt% and the balance water;
s5, placing the waste SCR denitration catalyst after pickling in deionized water at 30 ℃, rinsing, and drying at 120 ℃ for 4 hours to obtain the waste SCR denitration catalyst after drying;
s6, immersing the dried waste SCR denitration catalyst into an active liquid at 40 ℃ for 15min, taking out, drying at 100 ℃ for 3h, heating to 350 ℃ and calcining for 5h to obtain the regenerated SCR denitration catalyst, wherein the mass volume ratio of the dried waste SCR denitration catalyst to the active liquid is 1g to 10mL, and the active liquid consists of 2.5wt% of ammonium metavanadate, 2wt% of ammonium metatungstate, 3.5wt% of ammonium molybdate and the balance of water.
Example 4
S1, heating the waste SCR denitration catalyst to 220 ℃ at a speed of 2 ℃/min under an oxygen atmosphere, heating to 260 ℃ at a speed of 2 ℃/min after roasting for 50min at 220 ℃, heating to 320 ℃ at a speed of 2 ℃/min after roasting for 50min at 260 ℃, roasting for 50min at 320 ℃, heating to 360 ℃ at a speed of 2 ℃/min, roasting for 50min at 360 ℃, heating to 420 ℃ at a speed of 2 ℃/min, and roasting for 3.5h at 420 ℃ to obtain the roasted waste SCR denitration catalyst, wherein the flow rate of oxygen is 0.5m/min;
s2, placing the roasted waste SCR denitration catalyst in an ultrasonic tank, and ultrasonically cleaning for 10min under the conditions of 50 ℃ water and bubbling pressure of 0.3MPa to obtain the washed waste SCR denitration catalyst;
s3, placing the washed waste SCR denitration catalyst in alkali liquor, and performing alkali washing for 20min to obtain the washed waste SCR denitration catalyst, wherein the mass volume ratio of the washed waste SCR denitration catalyst to the alkali liquor is 1g to 5mL, and the alkali liquor consists of 0.15wt% of NaOH, 0.3wt% of EDTA, 4.5wt% of ammonia water, 4.2 wt% of OP-10 and the balance of water;
s4, placing the waste SCR denitration catalyst subjected to alkali washing in acid liquor, and carrying out acid washing for 20min to obtain the waste SCR denitration catalyst subjected to acid washing, wherein the mass volume ratio of the waste SCR denitration catalyst subjected to alkali washing to the acid liquor is 1g:5mL, and the acid liquor consists of 0.2wt% of sulfuric acid, 1.5wt% of oxalic acid, 3wt% of citric acid, 20 wt% of peregal O and the balance of water;
s5, placing the waste SCR denitration catalyst after pickling in deionized water at 40 ℃, rinsing, and drying at 100 ℃ for 6 hours to obtain the waste SCR denitration catalyst after drying;
s6, immersing the dried waste SCR denitration catalyst into an active liquid at 60 ℃ for 5min, taking out, drying at 120 ℃ for 2h, heating to 420 ℃ and calcining for 4h to obtain the regenerated SCR denitration catalyst, wherein the mass volume ratio of the dried waste SCR denitration catalyst to the active liquid is 1g to 10mL, and the active liquid consists of 3wt% of ammonium metavanadate, 2.5wt% of ammonium metatungstate, 3wt% of ammonium molybdate and the balance of water.
Example 5
The only difference from example 2 is that: the flow rate of oxygen in S1 was 0.3m/min.
Example 6
The only difference from example 2 is that: the flow rate of oxygen in S1 was 0.1m/min.
Example 7
The only difference from example 2 is that: s1, heating the waste SCR denitration catalyst to 200 ℃ at a speed of 1.5 ℃/min under an oxygen atmosphere, roasting at 200 ℃ for 60min, heating to 250 ℃ at a speed of 2 ℃/min, roasting at 250 ℃ for 60min, heating to 300 ℃ at a speed of 2 ℃/min, roasting at 300 ℃ for 60min, heating to 350 ℃ at a speed of 2 ℃/min, roasting at 350 ℃ for 60min, heating to 400 ℃ at a speed of 2 ℃/min, and roasting at 400 ℃ for 4h to obtain the roasted waste SCR denitration catalyst, wherein the flow rate of oxygen is 0.3m/min.
Example 8
The only difference from example 2 is that: s1, heating the waste SCR denitration catalyst to 200 ℃ at a speed of 1 ℃/min under an oxygen atmosphere, roasting at 200 ℃ for 60min, heating to 250 ℃ at a speed of 2 ℃/min, roasting at 250 ℃ for 60min, heating to 300 ℃ at a speed of 2 ℃/min, roasting at 300 ℃ for 60min, heating to 350 ℃ at a speed of 2 ℃/min, roasting at 350 ℃ for 60min, heating to 400 ℃ at a speed of 2 ℃/min, and roasting at 400 ℃ for 4h to obtain the roasted waste SCR denitration catalyst, wherein the flow rate of oxygen is 0.3m/min.
Example 9
The only difference from example 8 is that: s1, heating the waste SCR denitration catalyst to 200 ℃ at a speed of 1 ℃/min under an oxygen atmosphere, roasting at 200 ℃ for 60min, heating to 250 ℃ at a speed of 1.5 ℃/min, roasting at 250 ℃ for 60min, heating to 300 ℃ at a speed of 1.5 ℃/min, roasting at 300 ℃ for 60min, heating to 350 ℃ at a speed of 1.5 ℃/min, roasting at 350 ℃ for 60min, heating to 400 ℃ at a speed of 1.5 ℃/min, and roasting at 400 ℃ for 4h to obtain the roasted waste SCR denitration catalyst, wherein the flow rate of oxygen is 0.3m/min.
Example 10
The only difference from example 8 is that: s1, heating the waste SCR denitration catalyst to 200 ℃ at a speed of 1 ℃/min under an oxygen atmosphere, roasting at 200 ℃ for 60min, heating to 250 ℃ at a speed of 1 ℃/min, roasting at 250 ℃ for 60min, heating to 300 ℃ at a speed of 1 ℃/min, roasting at 300 ℃ for 60min, heating to 350 ℃ at a speed of 1 ℃/min, roasting at 350 ℃ for 60min, heating to 400 ℃ at a speed of 1 ℃/min, and roasting at 400 ℃ for 4h to obtain the roasted waste SCR denitration catalyst, wherein the flow rate of oxygen is 0.3m/min.
Example 11
The only difference from example 8 is that: s1, heating the waste SCR denitration catalyst to 200 ℃ at a speed of 1 ℃/min under an oxygen atmosphere, roasting at 200 ℃ for 60min, heating to 250 ℃ at a speed of 0.5 ℃/min, roasting at 250 ℃ for 60min, heating to 300 ℃ at a speed of 0.5 ℃/min, roasting at 300 ℃ for 60min, heating to 350 ℃ at a speed of 0.5 ℃/min, roasting at 350 ℃ for 60min, heating to 400 ℃ at a speed of 0.5 ℃/min, and roasting at 400 ℃ for 4h to obtain the roasted waste SCR denitration catalyst, wherein the flow rate of oxygen is 0.3m/min.
Example 12
The only difference from example 10 is that: and S7, after dissolving the trans-9, 10-epoxy octadecanoic acid in the dimethyl sulfoxide, adding a calcined catalyst, and reacting at 175 ℃ for 50min to obtain the regenerated SCR denitration catalyst, wherein the mass ratio of the trans-9, 10-epoxy octadecanoic acid to the calcined catalyst is 0.1:1, and the mass volume ratio of the calcined catalyst to the dimethyl sulfoxide is 1:20mL.
Example 13
The only difference from example 12 is that: the mass ratio of the trans-9, 10-epoxy octadecanoic acid to the calcined catalyst is 0.3:1.
Example 14
The only difference from example 12 is that: the mass ratio of the trans-9, 10-epoxy octadecanoic acid to the calcined catalyst is 0.5:1.
Example 15
The only difference from example 12 is that: the mass ratio of the trans-9, 10-epoxy octadecanoic acid to the calcined catalyst is 0.8:1.
Example 16
The only difference from example 12 is that: the mass ratio of the trans-9, 10-epoxy octadecanoic acid to the calcined catalyst is 1:1.
Example 17
The only difference from example 12 is that: and S7, after dissolving cis-9, 10-epoxy octadecanoic acid in dimethyl sulfoxide, adding a calcined catalyst, and reacting at 170 ℃ for 60min to obtain the regenerated SCR denitration catalyst, wherein the mass ratio of cis-9, 10-epoxy octadecanoic acid to the calcined catalyst is 0.1:1, and the mass volume ratio of the calcined catalyst to dimethyl sulfoxide is 1:15mL.
Example 18
The only difference from example 12 is that: and S7, after dissolving cis-9, 10-epoxy octadecanoic acid in dimethyl sulfoxide, adding a calcined catalyst, and reacting at 180 ℃ for 40min to obtain the regenerated SCR denitration catalyst, wherein the mass ratio of cis-9, 10-epoxy octadecanoic acid to the calcined catalyst is 0.1:1, and the mass volume ratio of the calcined catalyst to dimethyl sulfoxide is 1:25mL.
Comparative example 1
The difference from example 1 is only S1, the waste SCR denitration catalyst is heated to 400 ℃ at a speed of 2 ℃/min under ozone atmosphere, and the waste SCR denitration catalyst is roasted for 4 hours at 400 ℃, so that the roasted waste SCR denitration catalyst is obtained, and the flow rate of ozone is 0.5m/min.
Performance test:
respectively placing an initial SCR denitration catalyst, a waste SCR denitration catalyst and regenerated SCR denitration catalyst test blocks of examples 1-11 and comparative example 1 in a stainless steel fixed bed reactor, introducing simulated flue gas to complete aging, detecting the concentration of NO in the flue gas by adopting a Siemens Feidel online continuous flue gas analyzer, and calculating the denitration rate and the catalyst activity according to the following formula:
NH 3 mole ratio of/NO: 1.05:1;
NO concentration: 300ppm;
SO 2 concentration: 50ppm;
H 2 O：10wt%；
O 2 ：5wt%；
temperature: 280 ℃;
face speed: 15m/h;
volume space velocity: 10000h -1 ；
Denitration rate (%) = (reactor inlet NO concentration-reactor outlet NO concentration)/(reactor inlet NO concentration×100);
the catalyst activity is calculated as follows:
；
wherein: kappa is catalyst activity (standard condition, wet basis), m/h;
AV is the surface velocity, m/h, the ratio of the flue gas flow through the catalyst to the total surface area of the catalyst;
eta is the denitration rate,%.
The results of the catalyst activity test are recorded in table 1.
TABLE 1 denitration rate and catalytic Activity of regenerated SCR denitration catalyst
As can be seen from Table 1, the denitration rate of the regenerated SCR denitration catalyst obtained by the regeneration process of the waste SCR denitration catalyst provided by the invention is as high as more than 85.1%, the activity of the regenerated catalyst is more than 75% of the original activity, and the activity of the regenerated catalyst obtained in examples 13-15 is more than 95% of the original activity.
Compared with comparative example 1, examples 1-18 are subjected to staged roasting, and in comparative example 1, the temperature is directly raised to 400 ℃ and the temperature is roasted for 4 hours at 400 ℃, and the denitration rate and the catalytic activity of the regenerated SCR denitration catalyst obtained in examples 1-18 are higher than those of comparative example 1, which shows that the denitration rate and the catalytic activity of the regenerated SCR denitration catalyst can be improved by adopting staged roasting, probably because the structure of the SCR denitration catalyst can not be damaged in the roasting process due to staged roasting, thereby improving the denitration activity of the regenerated SCR denitration catalyst.
Compared with example 5, the temperature rising rate of the primary roasting in example 7 is 1.5 ℃/min, the temperature rising rate of the primary roasting in example 8 is 1 ℃/min, the temperature rising rate of the primary roasting in example 5 is 2 ℃/min, and the denitration rate and the catalytic activity of the regenerated SCR denitration catalyst obtained in examples 7-8 are higher than those of example 5, which shows that the temperature rising rate of the primary roasting is less than 1.5 ℃/min, and the denitration activity of the regenerated SCR denitration catalyst can be further improved.
Examples 9 to 10 are compared with examples 8 and 11, the temperature rise rates of the secondary, tertiary, quaternary and penta-roasting in example 9 are 1.5 ℃/min, the temperature rise rates of the secondary, tertiary, quaternary and penta-roasting in example 10 are 1 ℃/min, the temperature rise rates of the secondary, tertiary, quaternary and penta-roasting in example 8 are 2 ℃/min, the temperature rise rates of the secondary, tertiary, quaternary and penta-roasting in example 11 are 0.5 ℃/min, and the denitration rates and catalytic activities of the regenerated SCR denitration catalysts obtained in examples 9 to 10 are higher than those of examples 8 and 11, indicating that the temperature rise rates of the secondary, tertiary, quaternary and penta-roasting are 1 to 1.5 ℃/min, and the denitration activities of the regenerated SCR denitration catalysts can be further improved.
Examples 12 to 18 are compared with example 10, in examples 12 to 18, 9, 10-epoxyoctadecanoic acid is used for modifying the calcined catalyst, in example 10, the calcined catalyst is not modified, and the denitration rate and the catalytic activity of the regenerated SCR denitration catalyst obtained in examples 12 to 18 are higher than those of example 10, which shows that the denitration activity of the regenerated SCR denitration catalyst is further improved by modifying the calcined catalyst by 9, 10-epoxyoctadecanoic acid.
The regenerated SCR denitration catalyst obtained in example 10, examples 12 to 18 and comparative example 1 was used for 1200 days in a steel plant, and then the denitration rate was again tested, and the denitration reduction rate was calculated according to the following formula to evaluate the service life of the regenerated SCR denitration catalyst.
Denitration decrease rate (%) = (denitration rate before use-denitration rate after use for 1200 days)/(denitration rate before use×100)
The test results are recorded in table 2.
TABLE 2 denitration rate and denitration decrease rate
As can be seen from Table 2, the regenerated SCR denitration catalyst obtained by the regeneration process of the waste SCR denitration catalyst provided by the invention has the denitration rate of 68.5% or more after being used for 1200 days, the denitration reduction rate of 24.31% or less, and the service life of the regenerated SCR denitration catalyst is long.
Example 10 compared with comparative example 1, example 10 uses staged calcination, whereas comparative example 1 is directly heated to 400 ℃ and calcined at 400 ℃ for 4 hours, the regenerated SCR denitration catalyst obtained in example 10 has a lower denitration reduction rate than comparative example 1 after 1200 days of use, indicating that the use of staged calcination can prolong the service life of the regenerated SCR denitration catalyst.
Examples 12 to 18 were compared with example 10, in which 9, 10-epoxyoctadecanoic acid was used to modify the calcined catalyst in examples 12 to 18, in which example 10 was not used to modify the calcined catalyst, and in which the reduction in denitration rate of the regenerated SCR denitration catalyst obtained in examples 12 to 18 was lower than in example 10 after 1200 days, indicating that the modification of the calcined catalyst with 9, 10-epoxyoctadecanoic acid can extend the service life of the regenerated SCR denitration catalyst.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (7)
1. The regeneration process of the waste SCR denitration catalyst is characterized by comprising the following steps of: after the waste SCR denitration catalyst is roasted, cleaning, drying, implanting active ingredients, and calcining to obtain a regenerated SCR denitration catalyst;
the firing includes: sequentially performing primary roasting at 180-220 ℃, secondary roasting at 240-260 ℃, tertiary roasting at 280-320 ℃, quaternary roasting at 340-360 ℃ and five-time roasting at 380-420 ℃;
the temperature rising rate of the primary roasting is below 1.5 ℃/min;
the temperature rising rates of the secondary roasting, the tertiary roasting, the quaternary roasting and the five-time roasting are respectively and independently 1-1.5 ℃/min;
the time of the primary roasting, the secondary roasting, the tertiary roasting and the quaternary roasting is respectively and independently 50-80 min, and the time of the five times of roasting is 3.5-4.5 h;
the method further comprises the step of modifying the calcined catalyst by using 9, 10-epoxy octadecanoic acid.
2. A process for regenerating a spent SCR denitration catalyst according to claim 1, wherein the washing comprises water washing, acid washing and alkali washing.
3. The regeneration process of the waste SCR denitration catalyst according to claim 1, wherein the mass ratio of the 9, 10-epoxyoctadecanoic acid to the calcined catalyst is 0.3-0.8:1.
4. The process for regenerating a waste SCR denitration catalyst according to claim 1, wherein the modification treatment specifically comprises: and mixing 9, 10-epoxy octadecanoic acid, the calcined catalyst and a solvent for reaction to obtain the regenerated SCR denitration catalyst.
5. The process for regenerating a waste SCR denitration catalyst according to claim 4, wherein the reaction temperature is 170-180 ℃ and the reaction time is 40-60 min.
6. The process for regenerating a spent SCR denitration catalyst according to claim 1, wherein the implanted active ingredients specifically are: and immersing the dried SCR denitration catalyst in the active liquid at 40-60 ℃ for 5-15 min.
7. The process for regenerating a spent SCR denitration catalyst according to claim 6, wherein the active liquid comprises a mixture of water and one or more of ammonium metavanadate, ammonium metatungstate, and ammonium molybdate.
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