CN111715210A - Regeneration method of cement kiln thallium poisoning SCR denitration catalyst - Google Patents
Regeneration method of cement kiln thallium poisoning SCR denitration catalyst Download PDFInfo
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- 238000011069 regeneration method Methods 0.000 title claims abstract description 30
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- 208000026015 thallium poisoning Diseases 0.000 title abstract description 14
- 238000004140 cleaning Methods 0.000 claims abstract description 35
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 24
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 21
- 239000010936 titanium Substances 0.000 claims abstract description 21
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- 239000010937 tungsten Substances 0.000 claims abstract description 18
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- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000002791 soaking Methods 0.000 claims abstract description 9
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical compound [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 claims abstract description 6
- NWJUARNXABNMDW-UHFFFAOYSA-N tungsten vanadium Chemical compound [W]=[V] NWJUARNXABNMDW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000013543 active substance Substances 0.000 claims abstract description 5
- 229910001868 water Inorganic materials 0.000 claims abstract description 5
- 239000000428 dust Substances 0.000 claims description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 5
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 claims description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 3
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 3
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 3
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 3
- 229910052716 thallium Inorganic materials 0.000 abstract description 22
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 5
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- 102100021587 Embryonic testis differentiation protein homolog A Human genes 0.000 abstract description 2
- 101000898120 Homo sapiens Embryonic testis differentiation protein homolog A Proteins 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 230000005587 bubbling Effects 0.000 description 12
- 230000008929 regeneration Effects 0.000 description 11
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 238000002513 implantation Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 238000009423 ventilation Methods 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- 208000005374 Poisoning Diseases 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000003245 coal Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- -1 AV 8.04m/h Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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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
- B01J23/16—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
- 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
-
- B01J35/61—
-
- 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
-
- 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
Abstract
The invention discloses a regeneration method of a thallium poisoning SCR denitration catalyst of a cement kiln, which comprises the following steps: (1) dedusting; (2) soaking with cleaning solution; (3) rinsing; (4) drying; (5) implanting titanium, vanadium and tungsten soluble active substances; (6) calcining; the cleaning solution in the step (2) comprises EDTA, dilute sulfuric acid and water. In the regeneration method of the cement kiln thallium poisoning SCR denitration catalyst, the cleaning solution is weakly acidic, thallium metal adhered to the surface and pore canals of the catalyst can be effectively removed,the active sites of the catalyst are recovered, the original active components of the catalyst are not reduced, and the removal efficiency of thallium metal by ETDA in the cleaning solution is high. The titanium vanadium tungsten soluble active substance is implanted on the catalyst, SO that the lost vanadium tungsten active component is effectively supplemented, the activity of the catalyst is effectively recovered, and the SO is low2And (4) conversion rate.
Description
Technical Field
The invention belongs to the technical field of denitration catalysts, and relates to a regeneration method of a cement kiln thallium-poisoned SCR denitration catalyst.
Background
The nitrogen oxides are important pollutants of air pollution, and the nitrogen oxide treatment of the coal power plant is mature, so that the requirement of ultralow emission is met. The cement kiln smoke nitrogen oxides are the third pollution source after the tail gas of fire power and automobiles. At present, the SCR denitration technology is one of the most widely applied and mature and effective flue gas denitration technologies. The SCR denitration device of the coal-fired power plant is mainly arranged between the economizer and the air preheater and contains a large amount of fly ash and high-concentration SO2After 24000h of gas operation, the SCR catalyst can be deactivated and replaced to be abandoned due to problems of poisoning, ash blockage, abrasion and the like. The catalyst poisoning problem is common, and the main substances causing the poisoning are as follows: alkali metals, heavy metals, H2O and SO2And the like. Most coal species in China contain thallium, and thallium in flue gas is deposited on the surface of a catalyst during flue gas denitration, so that the catalyst is poisoned, and the activity is reduced.
The deactivation mechanism and regeneration method of thallium-poisoned denitration catalysts are currently under little study. The influence of thallium contained in cement dust on the performance of a denitration catalyst has been studied by the wainscot et al, and particularly, the influence is more serious for a medium-low dust (cement 2015). The research on the thallium-poisoned catalyst regeneration method can prolong the service life of the catalyst and recycle the regenerated substances of the deactivated catalyst. The invention aims at the SCR denitration catalyst inactivated by thallium poisoning of heavy metal in the smoke of the cement kiln, and obtains an effective thallium poisoning catalyst regeneration technical scheme according to the chemical properties and characteristics of thallium.
Disclosure of Invention
The invention aims to provide a regeneration method of a cement kiln thallium-poisoned SCR denitration catalyst, which is simple to operate, economic and effective, and can simply and efficiently remove thallium metal on the surface of the catalyst and restore the activity of the catalyst.
The invention provides a regeneration method of cement kiln thallium poisoning SCR denitration catalyst, which comprises the following steps:
(1) dust removal, preferably negative pressure dust collection;
(2) soaking with cleaning solution;
(3) rinsing;
(4) drying;
(5) implanting titanium, vanadium and tungsten soluble active substances;
(6) calcining;
the cleaning solution in the step (2) comprises EDTA, dilute sulfuric acid and water.
The regeneration method removes dust on the surface through negative pressure dust absorption, and facilitates the overall contact of cleaning liquid and thallium in the subsequent steps. The weak acid cleaning solution of EDTA and dilute sulfuric acid can effectively remove thallium metal adhered to the surface and the pore channels of the catalyst, remove substances blocking the inner and outer pore channels and occupying the active sites of the catalyst, increase the specific surface area of the catalyst, recover the active sites of the catalyst and not reduce the original active components of the catalyst. The implantation of the vanadium-tungsten active component is matched with the subsequent calcination step, SO that the catalyst activity and low SO can be effectively recovered2And (4) conversion rate.
In some embodiments of the invention, in step (1), the negative pressure is from-0.098 to-0.090 MPa.
In some embodiments of the invention, in the step (2), the concentration of EDTA in the cleaning solution is 0.1-0.4mol/l, and the concentration of dilute sulfuric acid is 0.05-0.2 mol/l.
In some embodiments of the present invention, in the step (2), the cleaning solution is soaked for 20min to 40 min.
In some embodiments of the invention, in the solution 2, in the step (3), the deionized water is used for washing for 5min to 10 min.
In some embodiments of the invention, the drying is carried out for 3-5 hours in a ventilated environment at a temperature of 80-140 ℃.
In some embodiments of the invention, the titanium in the titanium-vanadium-tungsten solution is from one or more of titanium dioxide sol, titanium sulfate, metatitanic acid, vanadium is from one or more of vanadyl oxalate, vanadyl acetylacetonate, vanadyl sulfate, ammonium metavanadate, and tungsten is from one or more of ammonium paratungstate, ammonium metatungstate.
In some embodiments of the invention, the concentration of titanium in the titanium vanadium tungsten solution is 100-200g/l, the concentration of vanadium is 0.05-0.3g/l, and the concentration of tungsten is 55-85 g/l.
In some embodiments of the invention, in the step (5), the titanium-containing vanadium-tungsten solution is soaked for 10-30 min.
In some embodiments of the invention, in step (6), the treatment is carried out for 2 to 4 hours in a ventilated environment at a temperature of 380 ℃ to 450 ℃.
During the treatment in the above-mentioned temperature and ventilation environment, drying and calcination are carried out together.
The beneficial technical effects of the invention are as follows:
according to the regeneration method of the cement kiln thallium-poisoned SCR denitration catalyst, the cleaning solution is weakly acidic, thallium metal adhered to the surface and pore channels of the catalyst can be effectively removed, the specific surface area of the catalyst is increased, the active site of the catalyst is recovered, the original active components of the catalyst cannot be reduced, and the thallium metal removal efficiency of ETDA in the cleaning solution is high. The titanium vanadium tungsten soluble active substance is implanted on the catalyst, SO that the lost vanadium tungsten active component is effectively supplemented, the activity of the catalyst is effectively recovered, and the SO is low2And (4) conversion rate. The activity of the regenerated catalyst is recovered by more than 99.5 percent, the service life of the regenerated catalyst is prolonged, and the method has good popularization prospect.
Drawings
FIG. 1 shows the denitration efficiency test results of the catalyst before and after regeneration;
FIG. 2 shows the catalyst SO before and after regeneration according to the invention2And (5) detecting the conversion rate.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The inactivated SCR denitration catalyst of the cement kiln is the same batch of catalyst from a certain cement plant.
Example 1
A regeneration method of cement kiln thallium poisoning SCR denitration catalyst specifically comprises the following steps:
(1) negative pressure dust collection: absorbing the inactivated denitration catalyst by using a negative pressure dust collector under-0.090 MPa until the surface dust is removed;
(2) cleaning: soaking the catalyst treated in the step (1) in a cleaning solution for 40min under the bubbling auxiliary condition, and cleaning thallium metal poisoned by the catalyst; the concentration of EDTA is 0.4mol/l, and the concentration of dilute sulfuric acid is 0.05 mol/l;
(3) rinsing: washing the catalyst treated in the step (2) for 10min by using deionized water;
(4) drying: drying the catalyst treated in the step (3) for 5 hours in a ventilation environment at the temperature of 80 ℃;
(5) active implantation: under the bubbling auxiliary condition, the catalyst in the step (4) is put in a solution containing titanium, vanadium and tungsten for 10min, and active components are supplemented; wherein the titanium is titanium dioxide sol with the concentration of 200g/l, the vanadium is vanadyl oxalate with the concentration of 0.05g/l, and the tungsten is ammonium paratungstate with the concentration of 55 g/l;
(6) and (3) calcining: drying the catalyst treated in the step (5) in a ventilated environment at the temperature of 380 ℃ for 4 hours; and finishing the regeneration.
Example 2
A regeneration method of cement kiln thallium poisoning SCR denitration catalyst specifically comprises the following steps:
(1) negative pressure dust collection: absorbing the inactivated denitration catalyst by a negative pressure dust collector under-0.098 MPa until the surface dust is removed;
(2) cleaning: soaking the catalyst treated in the step (1) in a cleaning solution for 40min under the bubbling auxiliary condition, and cleaning thallium metal poisoned by the catalyst; the concentration of EDTA is 0.1mol/l, and the concentration of dilute sulfuric acid is 0.2 mol/l;
(3) rinsing: washing the catalyst treated in the step (2) for 5min by using deionized water;
(4) drying: drying the catalyst treated in the step (3) in a ventilating environment at the temperature of 140 ℃;
(5) active implantation: under the bubbling auxiliary condition, the catalyst in the step (4) is put in a solution containing titanium, vanadium and tungsten for 30min, and active components are supplemented; wherein the titanium is titanium sulfate with the concentration of 100g/l, the vanadium is vanadyl acetylacetonate with the concentration of 0.3g/l, the tungsten is ammonium metatungstate with the concentration of 85 g/l;
(6) and (3) calcining: drying the catalyst treated in the step (5) in a ventilated environment at the temperature of 400 ℃ for 2 h; and finishing the regeneration.
Example 3
A regeneration method of cement kiln thallium poisoning SCR denitration catalyst specifically comprises the following steps:
(1) negative pressure dust collection: absorbing the inactivated denitration catalyst by a negative pressure dust collector under-0.095 MPa until the surface dust is removed;
(2) cleaning: soaking the catalyst treated in the step (1) in a cleaning solution for 30min under the bubbling auxiliary condition, and cleaning thallium metal poisoned by the catalyst; the concentration of EDTA is 0.2mol/l, and the concentration of dilute sulfuric acid is 0.1 mol/l;
(3) rinsing: washing the catalyst treated in the step (2) with deionized water for 30 min;
(4) drying: drying the catalyst treated in the step (3) for 5 hours in a ventilation environment at the temperature of 120 ℃;
(5) active implantation: under the bubbling auxiliary condition, the catalyst in the step (4) is put in a solution containing titanium, vanadium and tungsten for 20min, and active components are supplemented; wherein the titanium is metatitanic acid with the concentration of 150g/l, the vanadium is vanadyl sulfate with the concentration of 0.2g/l, and the tungsten is ammonium metatungstate with the concentration of 75 g/l;
(6) and (3) calcining: drying the catalyst treated in the step (5) in a ventilated environment at the temperature of 400 ℃ for 4 hours; and finishing the regeneration.
Example 4
A regeneration method of cement kiln thallium poisoning SCR denitration catalyst specifically comprises the following steps:
(1) negative pressure dust collection: absorbing the inactivated denitration catalyst by a negative pressure dust collector under-0.098 MPa until the surface dust is removed;
(2) cleaning: soaking the catalyst treated in the step (1) in a cleaning solution for 40min under the bubbling auxiliary condition, and cleaning thallium metal poisoned by the catalyst; the concentration of EDTA is 0.3mol/l, and the concentration of dilute sulfuric acid is 0.15 mol/l;
(3) rinsing: washing the catalyst treated in the step (2) for 10min by using deionized water;
(4) drying: drying the catalyst treated in the step (3) for 5 hours in a ventilation environment at the temperature of 130 ℃;
(5) active implantation: under the bubbling auxiliary condition, putting the catalyst in the step (4) in a titanium-containing vanadium-tungsten solution for 8min, and supplementing active components; wherein titanium is titanium dioxide sol with the concentration of 100g/l, vanadium is ammonium metavanadate with the concentration of 0.1g/l, tungsten is ammonium metatungstate with the concentration of 65 g/l;
(6) and (3) calcining: drying the catalyst treated in the step (5) in a ventilated environment at the temperature of 400 ℃ for 5 hours; and finishing the regeneration.
Comparative example 1
A regeneration method of cement kiln thallium poisoning SCR denitration catalyst specifically comprises the following steps:
(1) negative pressure dust collection: absorbing the inactivated denitration catalyst by using a negative pressure dust collector under-0.090 MPa until the surface dust is removed;
(2) cleaning: soaking the catalyst treated in the step (1) in a cleaning solution for 40min under the bubbling auxiliary condition, and cleaning thallium metal poisoned by the catalyst; the concentration of EDTA is 0.4 mol/l;
(3) rinsing: washing the catalyst treated in the step (2) for 10min by using deionized water;
(4) drying: drying the catalyst treated in the step (3) for 5 hours in a ventilation environment at the temperature of 80 ℃;
(5) active implantation: under the bubbling auxiliary condition, the catalyst in the step (4) is put in a solution containing titanium, vanadium and tungsten for 10min, and active components are supplemented; wherein the titanium is titanium dioxide sol with the concentration of 200g/l, the vanadium is vanadyl oxalate with the concentration of 0.05g/l, and the tungsten is ammonium paratungstate with the concentration of 55 g/l;
(6) and (3) calcining: drying the catalyst treated in the step (5) in a ventilated environment at the temperature of 380 ℃ for 4 hours; and finishing the regeneration.
Comparative example 2
A regeneration method of cement kiln thallium poisoning SCR denitration catalyst specifically comprises the following steps:
(1) negative pressure dust collection: absorbing the inactivated denitration catalyst by using a negative pressure dust collector under-0.090 MPa until the surface dust is removed;
(2) cleaning: soaking the catalyst treated in the step (1) in a cleaning solution for 40min under the bubbling auxiliary condition, and cleaning thallium metal poisoned by the catalyst; the concentration of the dilute sulfuric acid is 0.05 mol/l;
(3) rinsing: washing the catalyst treated in the step (2) for 10min by using deionized water;
(4) drying: drying the catalyst treated in the step (3) for 5 hours in a ventilation environment at the temperature of 80 ℃;
(5) active implantation: under the bubbling auxiliary condition, the catalyst in the step (4) is put in a solution containing titanium, vanadium and tungsten for 10min, and active components are supplemented; wherein the titanium is titanium dioxide sol with the concentration of 200g/l, the vanadium is vanadyl oxalate with the concentration of 0.05g/l, and the tungsten is ammonium paratungstate with the concentration of 55 g/l;
(6) and (3) calcining: drying the catalyst treated in the step (5) in a ventilated environment at the temperature of 380 ℃ for 4 hours; and finishing the regeneration.
Examples of the experiments
Taking examples 1-4 and comparative examples 1 and 2 and thallium poisoning inactivated SCR denitration catalysts (catalysts before regeneration), carrying out chemical component detection on a Japanese ZSXII fluorescence analyzer, detecting the specific surface area (BET) of the catalyst by American Beckmann specific surface area analysis, detecting denitration performance tests in a fixed bed reactor,
the test conditions were: NO 400mg/Nm3，NH3400Nm3，O22.6％，SO21000mg/Nm3，5％H2O，N2For the balance gas, AV 8.04m/h, catalyst 13 × 13 pores, length 810mm, the temperature is 290 ℃, and an MRU flue gas analyzer is adopted for detection (the denitration efficiency is required to be 87.5%).
TABLE 1 chemical composition and BET test results for different catalysts
As can be seen from table 1 and fig. 1 and 2: the regeneration method can effectively remove thallium poisoned by the deactivated catalyst, and the original active component V2O5And WO3No loss, and the specific surface area, denitration activity and low SO of the catalyst are recovered2The conversion rate and the activity of the regenerated catalyst can be recovered to more than 99.5 percent of that of the fresh catalyst.
It was found that the cleaning solution of the combination of EDTA and dilute sulfuric acid was effective in removing thallium from the deactivated catalyst, and that EDTA and dilute sulfuric acid have a synergistic effect on thallium cleaning. In Table 2, the thallium content in examples 1-4 was much less than the deactivated catalyst before regeneration. Moreover, comparative examples 1 and 2 had much higher thallium content than examples 1 to 4.
While the preferred embodiments and examples of the present invention have been described in detail, the present invention is not limited to the embodiments and examples, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (10)
1. A regeneration method of cement kiln thallium-poisoned SCR denitration catalyst comprises the following steps:
(1) dust removal, preferably negative pressure dust collection;
(2) soaking with cleaning solution;
(3) rinsing;
(4) drying;
(5) implanting titanium, vanadium and tungsten soluble active substances;
(6) calcining;
the cleaning solution in the step (2) comprises EDTA, dilute sulfuric acid and water.
2. The method of claim 1, wherein in step (1), the negative pressure is from-0.098 to-0.090 MPa.
3. The method according to claim 1 or 2, wherein in the step (2), the concentration of EDTA in the cleaning solution is 0.1-0.4mol/l, and the concentration of dilute sulfuric acid is 0.05-0.2 mol/l.
4. The method according to any one of claims 1 to 3, wherein in the step (2), the washing solution is soaked for 20min to 40 min.
5. The method according to any one of claims 1 to 4, wherein in step (3), the deionized water is used to rinse for 5min to 10 min.
6. The method according to any one of claims 1 to 5, wherein in the step (4), the drying is carried out for 3 to 5 hours in a ventilated environment at a temperature of 80 ℃ to 140 ℃.
7. The method according to any one of claims 1 to 6, wherein in the step (5), the titanium in the titanium-vanadium-tungsten solution is one or more selected from titanium dioxide sol, titanium sulfate and metatitanic acid, the vanadium is one or more selected from vanadyl oxalate, vanadyl acetylacetonate, vanadyl sulfate and ammonium metavanadate, and the tungsten is one or more selected from ammonium paratungstate and ammonium metatungstate.
8. The method as claimed in any one of claims 1 to 7, wherein in step (5), the concentration of titanium in the titanium vanadium tungsten solution is 100-200g/l, the concentration of vanadium is 0.05-0.3g/l, and the concentration of tungsten is 55-85 g/l.
9. The method according to any one of claims 1 to 8, wherein in the step (5), the titanium-containing vanadium-tungsten solution is soaked for 10 to 30 min.
10. The method according to any one of claims 1 to 9, wherein in step (6), the treatment is carried out for 2 to 4 hours in a ventilated environment at a temperature of 380 ℃ to 450 ℃.
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| PCT/CN2021/085754 WO2022007450A1 (en) | 2020-07-09 | 2021-04-07 | Method for regenerating thallium poisoning scr denitration catalyst of cement kiln |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112827354A (en) * | 2020-12-28 | 2021-05-25 | 安徽元琛环保科技股份有限公司 | Regeneration method of thallium-poisoned denitration catalyst |
| CN113533245A (en) * | 2021-06-29 | 2021-10-22 | 苏州西热节能环保技术有限公司 | Diagnosis method for thallium poisoning of SCR denitration catalyst |
| CN113600248A (en) * | 2021-08-19 | 2021-11-05 | 苏州西热节能环保技术有限公司 | Thallium-poisoned denitration catalyst regeneration method |
| WO2022007450A1 (en) * | 2020-07-09 | 2022-01-13 | 江苏龙净科杰环保技术有限公司 | Method for regenerating thallium poisoning scr denitration catalyst of cement kiln |
| CN114558625A (en) * | 2022-03-14 | 2022-05-31 | 龙净科杰环保技术（上海）有限公司 | SCR denitration catalyst regeneration process in steel industry |
| CN115212893A (en) * | 2022-08-04 | 2022-10-21 | 苏州西热节能环保技术有限公司 | Regenerated catalyst capable of realizing synchronous denitration and dealcoholization and preparation method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5658545A (en) * | 1995-03-29 | 1997-08-19 | The Regents Of California | Metal regeneration of iron chelates in nitric oxide scrubbing |
| JP2008119695A (en) * | 1996-07-12 | 2008-05-29 | Energie-Versorgung Schwaben Ag | Method of cleaning and/or regenerating wholly or partially deactivated catalyst of stack-gas nitrogen scrubbing |
| CN103350004A (en) * | 2013-08-02 | 2013-10-16 | 张权 | SCR denitrification catalyst regeneration method and mixture for SCR denitrification catalyst regeneration liquid |
| CN103736527A (en) * | 2014-01-12 | 2014-04-23 | 高同柱 | Manufacturing method and process device of reactivated cleaning agent for regeneration of honeycomb SCR (selective catalytic reduction) denitration catalyst |
| CN106947864A (en) * | 2016-01-07 | 2017-07-14 | 中国科学院过程工程研究所 | A kind of system and its processing method that heavy metal is reclaimed from discarded SCR catalyst |
| CN110354915A (en) * | 2019-08-09 | 2019-10-22 | 华北电力大学 | A kind of alkali metal poisoning SCR denitration recycling and reusing method |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102764675A (en) * | 2011-05-05 | 2012-11-07 | 中国科学院城市环境研究所 | Formula for coal-fired flue gas denitrification catalyst activity regeneration |
| CN105709861B (en) * | 2014-12-05 | 2018-07-03 | 中国石油化工股份有限公司 | A kind of regeneration method of SCR denitration |
| CN106807401B (en) * | 2015-11-30 | 2018-04-13 | 神华集团有限责任公司 | A kind of renovation process of denitrating catalyst and a kind of regeneration denitrating catalyst and its application |
| CN105797789A (en) * | 2016-03-22 | 2016-07-27 | 浙江海亮环境材料有限公司 | Regeneration method of denitration catalyst |
| CN111715210A (en) * | 2020-07-09 | 2020-09-29 | 江苏龙净科杰环保技术有限公司 | Regeneration method of cement kiln thallium poisoning SCR denitration catalyst |
-
2020
- 2020-07-09 CN CN202010654293.0A patent/CN111715210A/en active Pending
-
2021
- 2021-04-07 WO PCT/CN2021/085754 patent/WO2022007450A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5658545A (en) * | 1995-03-29 | 1997-08-19 | The Regents Of California | Metal regeneration of iron chelates in nitric oxide scrubbing |
| JP2008119695A (en) * | 1996-07-12 | 2008-05-29 | Energie-Versorgung Schwaben Ag | Method of cleaning and/or regenerating wholly or partially deactivated catalyst of stack-gas nitrogen scrubbing |
| CN103350004A (en) * | 2013-08-02 | 2013-10-16 | 张权 | SCR denitrification catalyst regeneration method and mixture for SCR denitrification catalyst regeneration liquid |
| CN103736527A (en) * | 2014-01-12 | 2014-04-23 | 高同柱 | Manufacturing method and process device of reactivated cleaning agent for regeneration of honeycomb SCR (selective catalytic reduction) denitration catalyst |
| CN106947864A (en) * | 2016-01-07 | 2017-07-14 | 中国科学院过程工程研究所 | A kind of system and its processing method that heavy metal is reclaimed from discarded SCR catalyst |
| CN110354915A (en) * | 2019-08-09 | 2019-10-22 | 华北电力大学 | A kind of alkali metal poisoning SCR denitration recycling and reusing method |
Non-Patent Citations (1)
| Title |
|---|
| XU HUANG等: "Severe deactivation and artificial enrichment of thallium on commercial SCR catalysts installed in cement kiln", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022007450A1 (en) * | 2020-07-09 | 2022-01-13 | 江苏龙净科杰环保技术有限公司 | Method for regenerating thallium poisoning scr denitration catalyst of cement kiln |
| CN112827354A (en) * | 2020-12-28 | 2021-05-25 | 安徽元琛环保科技股份有限公司 | Regeneration method of thallium-poisoned denitration catalyst |
| CN113533245A (en) * | 2021-06-29 | 2021-10-22 | 苏州西热节能环保技术有限公司 | Diagnosis method for thallium poisoning of SCR denitration catalyst |
| CN113600248A (en) * | 2021-08-19 | 2021-11-05 | 苏州西热节能环保技术有限公司 | Thallium-poisoned denitration catalyst regeneration method |
| CN114558625A (en) * | 2022-03-14 | 2022-05-31 | 龙净科杰环保技术（上海）有限公司 | SCR denitration catalyst regeneration process in steel industry |
| CN115212893A (en) * | 2022-08-04 | 2022-10-21 | 苏州西热节能环保技术有限公司 | Regenerated catalyst capable of realizing synchronous denitration and dealcoholization and preparation method thereof |
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| WO2022007450A1 (en) | 2022-01-13 |
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