CN113019353A - Anti-poisoning ion exchange type attapulgite-based denitration catalyst, and preparation method and application thereof - Google Patents
Anti-poisoning ion exchange type attapulgite-based denitration catalyst, and preparation method and application thereof Download PDFInfo
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- CN113019353A CN113019353A CN202110154258.7A CN202110154258A CN113019353A CN 113019353 A CN113019353 A CN 113019353A CN 202110154258 A CN202110154258 A CN 202110154258A CN 113019353 A CN113019353 A CN 113019353A
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- attapulgite
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- 239000003054 catalyst Substances 0.000 title claims abstract description 215
- 229960000892 attapulgite Drugs 0.000 title claims abstract description 122
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 122
- 238000005342 ion exchange Methods 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 33
- 238000005406 washing Methods 0.000 claims abstract description 28
- 238000001354 calcination Methods 0.000 claims abstract description 26
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 8
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract 2
- 238000003756 stirring Methods 0.000 claims description 85
- 239000007787 solid Substances 0.000 claims description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 50
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- 238000000227 grinding Methods 0.000 claims description 28
- 238000010992 reflux Methods 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 26
- 235000019270 ammonium chloride Nutrition 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 13
- 239000006228 supernatant Substances 0.000 claims description 13
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000012876 carrier material Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 229940010698 activated attapulgite Drugs 0.000 claims description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical group [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 238000005119 centrifugation Methods 0.000 claims 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- -1 nonahydrate ferric nitrate Chemical class 0.000 claims 1
- 206010027439 Metal poisoning Diseases 0.000 abstract description 41
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 27
- 208000010501 heavy metal poisoning Diseases 0.000 abstract description 27
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 21
- 239000003546 flue gas Substances 0.000 abstract description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 14
- 239000003513 alkali Substances 0.000 abstract description 13
- 125000005372 silanol group Chemical group 0.000 abstract description 2
- 229910008051 Si-OH Inorganic materials 0.000 abstract 1
- 229910006358 Si—OH Inorganic materials 0.000 abstract 1
- 239000002689 soil Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 51
- 238000005303 weighing Methods 0.000 description 42
- 238000006243 chemical reaction Methods 0.000 description 34
- 208000005374 Poisoning Diseases 0.000 description 27
- 230000000694 effects Effects 0.000 description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 15
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 15
- 150000001342 alkaline earth metals Chemical class 0.000 description 14
- 230000000607 poisoning effect Effects 0.000 description 14
- 239000004927 clay Substances 0.000 description 12
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 12
- 230000009467 reduction Effects 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 11
- 239000003085 diluting agent Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 239000008187 granular material Substances 0.000 description 11
- 238000005470 impregnation Methods 0.000 description 11
- 231100000572 poisoning Toxicity 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 3
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 238000004056 waste incineration Methods 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- SKEYZPJKRDZMJG-UHFFFAOYSA-N cerium copper Chemical compound [Cu].[Ce] SKEYZPJKRDZMJG-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910003439 heavy metal oxide Inorganic materials 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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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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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
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- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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Abstract
本发明公开了一种离子交换型凹凸棒土基脱硝催化剂及其制备方法，本发明催化剂是一种具备很好抗碱/碱土/重金属能力的脱硝催化剂。凹凸棒因其独特的层链状结构形成大量活性硅烷醇基团(Si‑OH)而具备很好的离子交换性能，该催化剂利用这一特性通过两步交换法将不同活性金属离子(Fe、Cu、Mn、Ce、Ni、Co)交换到凹凸棒中，经洗涤、烘干和煅烧形成离子交换型凹凸棒土基催化剂。本发明催化剂中低温脱硝性能优异、N2选择性高、二次污染小、并具有很好的抗碱/碱土/重金属中毒能力、价格低廉等优点，其可适用于含碱/碱土/重金属飞灰的固定源烟气脱硝。
The invention discloses an ion exchange type attapulgite-based denitration catalyst and a preparation method thereof. The catalyst of the invention is a denitration catalyst with good alkali/alkaline earth/heavy metal resistance. Attapulgite has good ion exchange performance due to its unique layered chain structure forming a large number of active silanol groups (Si-OH). The catalyst utilizes this characteristic to convert different active metal ions (Fe, Cu, Mn, Ce, Ni, Co) were exchanged into attapulgite, and ion-exchanged attapulgite soil-based catalyst was formed by washing, drying and calcining. The catalyst of the invention has the advantages of excellent low-temperature denitration performance, high N 2 selectivity, little secondary pollution, good resistance to alkali/alkaline earth/heavy metal poisoning, low price, etc. A fixed source of ash for flue gas denitrification.
Description
Technical Field
The invention relates to a denitration catalyst and a preparation method thereof, in particular to an ion exchange type attapulgite-based denitration catalyst and a preparation method thereof, which are applied to the technical field of nitrogen oxide control and purification in environmental protection.
Background
With the explosive growth of population, the economic society develops continuously, the activities of industrial and agricultural production and living are strengthened continuously, and the problem of environmental pollution is getting worse. Among the numerous pollutants, Nitrogen Oxides (NO)x) Is one of important pollution sources causing air pollution, can cause various serious pollution phenomena such as haze, acid rain, ozone cavities, photochemical smog and the like, and seriously influences the human health and the balance and stability of an ecological system. In order to control the emission of nitrogen oxides, China has come to have a plurality of relevant laws and regulations to restrict in recent years. At present, methods for removing nitrogen oxides mainly include Selective Catalytic Reduction (SCR), selective non-catalytic reduction (SNCR), adsorption, plasma, and the like. Among them, ammonia selective catalytic reduction method (NH)3SCR) is the fixed source flue gas denitration technology which is widely applied and most effective in removing nitrogen oxides at present, commercial NH3SCR catalyst V2O5-WO3(MoO3)/TiO2The conversion rate of nearly 100 percent is kept in the temperature range of 300-400 ℃, but the conversion rate still exists in the actual application of denitrationHigh biological toxicity, serious toxic inactivation and the like.
In industrial boiler flue gases of complex composition, K2O、CaO、Na2O、PdO、CdO、As2O3The presence of large amounts of iso-alkaline/alkaline earth/heavy metal oxides is an important factor in the deactivation of the catalyst. The alkali/alkaline earth/heavy metal can occupy acid sites or active sites of the catalyst, affect the surface acidity and redox cycle of the catalyst, and further cause the deactivation of the catalyst. At present, the acidity of the catalyst is improved mainly by using a strong acid carrier, adding an auxiliary agent, constructing a sacrificial site and the like, and the resistance of the catalyst is improved by separating an active site and a toxic site and the like. Although the methods can relieve the poisoning of the catalyst to a certain extent and improve the resistance of the catalyst, the catalyst itself has the problems of biological toxicity, environmental pollution, complex manufacturing process, high cost, unstable structure, poor thermal stability and the like, so that the development of a denitration catalyst which has low cost, environmental protection, high stability, high denitration activity and good alkali/alkaline earth/heavy metal poisoning resistance is an urgent problem to be solved.
Disclosure of Invention
The invention relates to an anti-poisoning ion exchange type attapulgite-based denitration catalyst, a preparation method and application thereof.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
an anti-poisoning ion exchange type attapulgite-based denitration catalyst is prepared by taking attapulgite raw ore or activated and modified attapulgite as a material for exchanging active metal ions by a two-step exchange method; the active metal exchanged by the catalyst is at least one of metal ions of copper, iron, manganese, cerium, cobalt and nickel.
Preferably, the active metal element for exchange is at least one of copper, iron, manganese, cerium, cobalt, nickel.
The invention discloses a preparation method of an anti-poisoning ion exchange type attapulgite-based denitration catalyst, which comprises the following steps:
a. purifying and activating the attapulgite:
dissolving a dispersing agent in deionized water, adding attapulgite crude ore into water in which the dispersing agent is dissolved while stirring, stirring for 0.5-2 h, performing ultrasonic treatment for 0.5-2 h, repeatedly stirring and performing ultrasonic treatment for 2-4 times, standing for 2-5 h, pouring out an upper suspension, centrifugally washing for 2-5 times by using a dilute acid solution, washing to be neutral by using deionized water, drying at 70-90 ℃, grinding to obtain purified attapulgite, and recording the purified attapulgite with powder A;
b. acid activation of the attapulgite:
placing an acid solution in a rotary steaming bottle, adding magnetons, adding the powder A into the acid solution while stirring to obtain an attapulgite mixed solution, placing the rotary steaming bottle in a constant-temperature oil bath kettle at 60-80 ℃, carrying out condensation reflux stirring for at least 4 hours, carrying out oil bath, carrying out centrifugal washing until the solution is neutral, placing the solution under the condition of 70-90 ℃ for drying, and grinding to obtain acid-activated attapulgite, wherein the powder B is marked;
c. adding deionized water into a rotary evaporation bottle, dissolving ammonium chloride solid into water, adding magnetons, and stirring until the ammonium chloride solid is dissolved to obtain an ammonium chloride solution; adding attapulgite raw ore, powder A or powder B as a carrier material into an ammonium chloride solution while stirring, adjusting the pH value of the ammonium chloride solution to 3-4 by using hydrochloric acid with the mass percentage concentration of not more than 10 wt%, placing a rotary evaporation bottle into a constant-temperature oil bath kettle at 60-80 ℃, condensing, refluxing and stirring for at least 2 hours, centrifugally washing after oil bath until the supernatant is free of chloride ions, drying at 70-90 ℃, and grinding to obtain the product exchanged with NH4 +The attapulgite clay of (1);
d. and (3) putting deionized water into a rotary evaporation bottle, dissolving a metal precursor salt into water, adding magnetons, stirring until the solid is dissolved, adding the solid obtained in the step c into the solution while stirring, putting the rotary evaporation bottle into a constant-temperature oil bath kettle at 80-90 ℃, performing condensation reflux stirring for at least 3 hours, performing centrifugal washing for 2-5 times after oil bath, drying at 70-90 ℃, grinding, and calcining in a muffle furnace at 450-550 ℃, wherein the obtained product is the ion exchange type attapulgite-based denitration catalyst.
Preferably, in step a, the dispersant used is sodium hexametaphosphate.
Preferably, in the step a, the mass ratio of the dispersing agent to the attapulgite to be purified is (0.01-0.1): 1.
Preferably, in the step a, the concentration of the used diluted acid solution is 0.05-0.2 mol/L.
Preferably, in the step b, at least one of hydrochloric acid, sulfuric acid and nitric acid is used as the acid.
Preferably, in the step b, the concentration of the acid solution is 0.2-4 mol/L.
Preferably, in the step b, the pH value of the mixed solution of attapulgite prepared by the acid solution is not higher than 5.
Preferably, in the step c, the concentration of the prepared ammonium chloride solution is 2.5-5 mol/L.
Preferably, in the step c, the mixing mass ratio of the ammonium chloride to the attapulgite raw ore in the step c is (3.4700-4.8141): 1.
preferably, in the step d, the metal precursor salt used is at least one of copper nitrate trihydrate, ferric nitrate nonahydrate, manganese nitrate solution, cerium nitrate hexahydrate, nickel nitrate hexahydrate and cobalt nitrate hexahydrate.
Preferably, in the step d, the concentration of the metal precursor salt solution is 0.02-0.1 mol/L.
Preferably, in said step d, the calcination is carried out for at least 2 h.
Preferably, in said step d, a metal precursor salt and NH4 +The mass percentage of the concave-convex rods after exchange is (1.2080-4.04): 1.
the invention discloses an application of an anti-poisoning ion exchange type attapulgite-based denitration catalyst, which is applied to a denitration technological process.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. the denitration catalyst is an ion exchange type attapulgite-based catalyst prepared by a two-step exchange method by using attapulgite raw ore or activated and modified attapulgite as a material for exchanging active metal ions, and the active components of the catalyst obtained by the exchange method have high dispersion degree, so that the catalyst has good medium-low temperature denitration performance; a large amount of active silanol hydroxyl groups in the attapulgite structure can well combine alkali/alkaline earth/heavy metal ions, and the influence of poisoning metal ions on active components is reduced, so that the catalyst also has good alkali/alkaline earth/heavy metal resistance;
2. the denitration catalyst has low cost, low requirement on synthesis equipment, and good alkali/alkaline earth/heavy metal poisoning resistance, and is suitable for denitration of fixed source flue gas containing alkali/alkaline earth/heavy metal fly ash, such as cement plants, garbage incineration boilers, biomass fuel boilers and glass furnaces.
Description of the drawings:
fig. 1 is a denitration activity graph of an alkali metal poisoning sample of the cerium ion-exchange type attapulgite-based denitration catalyst prepared in example 1 of the present invention.
Fig. 2 is a denitration activity graph of the copper-cerium ion-exchange type attapulgite-based denitration catalyst prepared in example 6 of the present invention.
Detailed Description
The following detailed description of the embodiments of the invention refers to the accompanying drawings.
Example 1
In this embodiment, a preparation method of an anti-poisoning ion exchange type attapulgite-based denitration catalyst includes the following steps:
a. putting 20ml deionized water into a eggplant-shaped bottle, weighing 3.47g of ammonium chloride solid, dissolving in water, adding magnetons, stirring until the solid is dissolved, weighing 1g of attapulgite crude ore, adding into the solution while stirring, adjusting pH to 3 with dilute hydrochloric acid, putting the eggplant-shaped bottle into a constant temperature oil bath kettle at 80 ℃, condensing, refluxing and stirring for 2h, centrifugally washing after oil bath until the supernatant is free of chloride ions, putting the eggplant-shaped bottle into an oven at 80 ℃, drying, grinding to obtain the product exchanged with NH4 +The attapulgite clay of (1);
b. and (2) putting 100ml of deionized water into an eggplant-shaped bottle, weighing 2.1711g of cerous nitrate hexahydrate, dissolving in water, adding magnetons, stirring until the solid is dissolved, weighing 1g of the solid obtained in the step a, adding into the solution while stirring, putting the eggplant-shaped bottle into a constant-temperature oil bath kettle at 90 ℃, condensing, refluxing and stirring for 3 hours, carrying out centrifugal washing for 3 times after oil bath, putting into an oven at 80 ℃ for drying, grinding, putting into a muffle furnace, and calcining at 450 ℃, wherein the obtained product is the ion exchange type attapulgite-based denitration catalyst.
Experimental test analysis:
testing the denitration performance of the catalyst: granulating the prepared catalyst into 20-40 meshes, putting the granules into a reaction furnace for activity and N2Selectivity test is carried out, the reaction temperature is 300-450 ℃, and the space velocity is 50000h-1Under the conditions of (1), the denitration efficiency is stabilized to be more than 80 percent, and the integral N is2The O yield was less than 10 ppm. Simulated flue gas is O25％，NO 500ppm，NH3500 ppm，N2Is diluent gas.
Alkali metal poisoning resistance test: the catalyst is loaded with 1 wt% of K by adopting an impregnation method2And O, calcining the catalyst at the temperature of 450 ℃ for 2 hours to obtain a simulated poisoned catalyst, and testing the denitration performance of the catalyst, wherein the reaction temperature is 340-420 ℃, and the space velocity is 50000h-1Under the conditions of (1), the denitration efficiency is stabilized to be more than 80 percent, and the integral N is2The amount of O produced was less than 10 ppm. Referring to fig. 1, the catalyst of the present embodiment is an ion-exchange type attapulgite-based selective reduction denitration catalyst with good performance, and the catalyst makes full use of the structural characteristics of attapulgite, so that the influence of alkali metal poisoning on the acid content and the redox capability of the catalyst is reduced to a great extent, and the alkali metal poisoning effect of the catalyst is improved. The catalyst of the embodiment can ensure the excellent medium and low temperature activity of the catalyst, and simultaneously enhance the alkali metal resistance of the catalyst.
Example 2
This embodiment is substantially the same as embodiment 1, and is characterized in that:
in this embodiment, a preparation method of an anti-poisoning ion exchange type attapulgite-based denitration catalyst includes the following steps:
a. putting 20ml deionized water into a eggplant-shaped bottle, and weighing3.7443g ammonium chloride solid is dissolved in water, magnetons are added and stirred until the solid is dissolved, 1g attapulgite crude ore is weighed and added into the solution while stirring, dilute hydrochloric acid is used for adjusting the pH value to 3, the eggplant-shaped bottle is placed in a constant temperature oil bath kettle at 70 ℃, the mixture is condensed, refluxed and stirred for 3 hours, centrifugally washed after oil bath until the supernatant is free of chloride ions, placed in a drying oven at 80 ℃ for drying, and ground to obtain the product which is exchanged with NH4 +The attapulgite clay of (1);
b. and (2) putting 100ml of deionized water into an eggplant-shaped bottle, weighing 2.1711g of cerous nitrate hexahydrate, dissolving in water, adding magnetons, stirring until the solid is dissolved, weighing 1g of the solid obtained in the step a, adding into the solution while stirring, putting the eggplant-shaped bottle into a constant-temperature oil bath kettle at 90 ℃, condensing, refluxing and stirring for 3 hours, carrying out centrifugal washing for 3 times after oil bath, putting into an oven at 80 ℃ for drying, grinding, putting into a muffle furnace, and calcining at 450 ℃, wherein the obtained product is the ion exchange type attapulgite-based denitration catalyst.
Experimental test analysis:
testing the denitration performance of the catalyst: granulating the prepared catalyst into 20-40 meshes, putting the granules into a reaction furnace for activity and N2Selectivity test is carried out, the reaction temperature is 290-450 ℃, and the space velocity is 50000h-1Under the conditions of (1), the denitration efficiency is stabilized to be more than 80 percent, and the integral N is2The O yield was less than 10 ppm. Simulated flue gas is O25％，NO 500ppm，NH3500 ppm，N2Is diluent gas.
And (3) testing the heavy metal poisoning resistance: loading 2 wt% of PbO on the catalyst by adopting an impregnation method, calcining the catalyst at 450 ℃ for 2 hours to obtain a simulated poisoned catalyst, and testing the denitration performance of the simulated poisoned catalyst, wherein the reaction temperature is 320-400 ℃, and the space velocity is 50000h-1Under the conditions of (1), the denitration efficiency is stabilized to be more than 80 percent, and the integral N is2The amount of O produced is low. The catalyst of the embodiment is an ion exchange type attapulgite-based selective reduction denitration catalyst with good performance, and the catalyst makes full use of the structural characteristics of attapulgite, separates active metal sites and heavy metal poisoning sites to a great extent, and reduces the influence of heavy metal poisoning on the redox capability of the catalyst, so that the heavy metal poisoning effect of the catalyst is obviously improved. This example catalyst is in the process of ensuring catalystOn the basis of excellent medium and low temperature activity, the heavy metal resistance of the catalyst is enhanced. ,
example 3
This embodiment is substantially the same as embodiment 1, and is characterized in that:
in this embodiment, a preparation method of an anti-poisoning ion exchange type attapulgite-based denitration catalyst includes the following steps:
a. putting 20ml deionized water into a eggplant-shaped bottle, weighing 4.2792g of ammonium chloride solid, dissolving in water, adding magnetons, stirring until the solid is dissolved, weighing 1g of attapulgite crude ore, adding into the solution while stirring, adjusting pH to 4 with dilute hydrochloric acid, putting the eggplant-shaped bottle into a constant temperature oil bath kettle at 80 ℃, condensing, refluxing and stirring for 2.5h, centrifugally washing after oil bath until the supernatant is free of chloride ions, putting the eggplant-shaped bottle into an oven at 80 ℃, drying, and grinding to obtain the product exchanged with NH4 +The attapulgite clay of (1);
b. and (2) putting 100ml of deionized water into an eggplant-shaped bottle, weighing 1.208g of copper nitrate trihydrate to dissolve in water, adding magnetons to stir until the solid is dissolved, weighing 1g of the solid obtained in the step a to add into the solution while stirring, putting the eggplant-shaped bottle into a constant-temperature oil bath kettle at 85 ℃, condensing, refluxing and stirring for 3.5h, centrifugally washing for 3 times after oil bath, putting the eggplant-shaped bottle into an oven at 80 ℃ to dry, grinding the eggplant-shaped bottle, and putting the eggplant-shaped bottle into a muffle furnace to calcine at 450 ℃, wherein the obtained product is the ion exchange type attapulgite-based denitration catalyst.
Experimental test analysis:
testing the denitration performance of the catalyst: granulating the prepared catalyst into 20-40 meshes, putting the granules into a reaction furnace for activity and N2Selectivity test is carried out, the reaction temperature is 250-350 ℃, and the space velocity is 50000h-1The denitration efficiency is stabilized to be more than 80 percent under the condition of (1), N2The O yield was less than 10 ppm. Simulated flue gas is O25％，NO 500ppm，NH3500 ppm，N2Is diluent gas.
Testing the alkaline earth metal poisoning resistance: the denitration performance of the simulated poisoning catalyst obtained by loading 1 wt% of CaO on the catalyst by adopting an impregnation method and calcining the catalyst for 2 hours at 450 ℃ is tested again, wherein the reaction temperature is 340-390 ℃, and the space velocity is 50000h-1Under the condition of (1), denitration efficiencyThe rate is stabilized at more than 70 percent, and the whole N2The amount of O produced is small. The catalyst of the embodiment is an ion exchange type attapulgite-based selective reduction denitration catalyst with good performance, and the catalyst makes full use of the structural characteristics of attapulgite, so that active metal sites and alkaline earth metal poisoning sites are separated to a great extent, the influence of alkaline earth metal poisoning on the redox capability of the catalyst is reduced, and the alkaline earth metal poisoning effect of the catalyst is improved. The catalyst of the embodiment can ensure the excellent medium and low temperature activity of the catalyst, and simultaneously enhance the alkaline earth metal resistance of the catalyst.
Example 4
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a preparation method of an anti-poisoning ion exchange type attapulgite-based denitration catalyst includes the following steps:
a. putting 20ml deionized water into a eggplant-shaped bottle, weighing 3.47g of ammonium chloride solid, dissolving in water, adding magnetons, stirring until the solid is dissolved, weighing 1g of attapulgite crude ore, adding into the solution while stirring, adjusting pH to 4 with dilute hydrochloric acid, putting the eggplant-shaped bottle into a constant temperature oil bath kettle at 80 ℃, condensing, refluxing and stirring for 2h, centrifugally washing after oil bath until the supernatant is free of chloride ions, putting the eggplant-shaped bottle into an oven at 80 ℃, drying, grinding to obtain the product exchanged with NH4 +The attapulgite clay of (1);
b. and (2) putting 100ml of deionized water into an eggplant-shaped bottle, weighing 3.03g of ferric nitrate nonahydrate, dissolving in water, adding magnetons, stirring until the solid is dissolved, weighing 1g of the solid obtained in the step a, adding into the solution while stirring, putting the eggplant-shaped bottle into a constant-temperature oil bath kettle at 90 ℃, condensing, refluxing and stirring for 3 hours, centrifugally washing for 4 times after oil bath, putting into an oven at 80 ℃ for drying, grinding, putting into a muffle furnace, and calcining at 500 ℃ to obtain the product, namely the ion exchange type attapulgite-based denitration catalyst.
Experimental test analysis:
testing the denitration performance of the catalyst: granulating the prepared catalyst into 20-40 meshes, putting the granules into a reaction furnace for activity and N2Selectivity test is carried out, the reaction temperature is 300-370 ℃, and the space velocity is 50000h-1Under the conditions of (a) under (b),the denitration efficiency is stabilized to be more than 80 percent, N2The O yield is low. Simulated flue gas is O25％，NO 500ppm，NH3500 ppm，N2Is diluent gas.
And (3) testing the heavy metal poisoning resistance: loading 3 wt% of CdO on the catalyst by adopting an impregnation method, calcining the catalyst at 450 ℃ for 2 hours to obtain a simulated poisoning catalyst, and testing the denitration performance of the simulated poisoning catalyst, wherein the reaction temperature is 325-360 ℃, and the space velocity is 50000h-1The denitration efficiency is stabilized to be more than 70 percent under the condition of (1), and the integral N is2The amount of O produced is small. The catalyst is an ion exchange type attapulgite-based selective reduction denitration catalyst with good performance, the catalyst makes full use of the structural characteristics of attapulgite, active metal sites and heavy metal poisoning sites are separated to a great extent, and the influence of heavy metal poisoning on the redox capability of the catalyst is reduced, so that the heavy metal poisoning effect of the catalyst is improved. The catalyst of the embodiment enhances the heavy metal resistance of the catalyst on the basis of ensuring the excellent medium and low temperature activity of the catalyst.
Example 5
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a preparation method of an anti-poisoning ion exchange type attapulgite-based denitration catalyst includes the following steps:
a. putting 20ml deionized water into a eggplant-shaped bottle, weighing 3.47g of ammonium chloride solid, dissolving in water, adding magnetons, stirring until the solid is dissolved, weighing 1g of attapulgite crude ore, adding into the solution while stirring, adjusting pH to 3 with dilute hydrochloric acid, putting the eggplant-shaped bottle into a constant temperature oil bath kettle at 80 ℃, condensing, refluxing and stirring for 2.5h, centrifugally washing after oil bath until the supernatant is free of chloride ions, putting the eggplant-shaped bottle into a 70 ℃ drying oven for drying, and grinding to obtain the product exchanged with NH4 +The attapulgite clay of (1);
b. and (2) putting 100ml of deionized water into a eggplant-shaped bottle, weighing 1.7895g of manganese nitrate solution and 2.1711g of cerous nitrate hexahydrate, dissolving in water, adding magnetons, stirring until the solids are dissolved, weighing 1g of the solids obtained in the step a, adding the solids into the solution while stirring, putting the eggplant-shaped bottle into a constant-temperature oil bath kettle at 90 ℃, condensing, refluxing and stirring for 3 hours, centrifugally washing for 3 times after oil bath, putting the eggplant-shaped bottle into an oven at 80 ℃ for drying, grinding the eggplant-shaped bottle, and putting the eggplant-shaped bottle into a muffle furnace for calcining at 450 ℃, wherein the obtained product is the ion exchange type attapulgite-based denitration catalyst.
Experimental test analysis:
testing the denitration performance of the catalyst: granulating the prepared catalyst into 20-40 meshes, putting the granules into a reaction furnace for activity and N2Selectivity test is carried out, the reaction temperature is 350-480 ℃, and the space velocity is 50000h-1The denitration efficiency is stabilized to be more than 80 percent under the condition of (1), N2The O yield is low. Simulated flue gas is O25％，NO 500ppm，NH3500 ppm，N2Is diluent gas.
Testing the performance of resisting the heavy metal poisoning of alkaline earth: 2 wt% of Na is loaded on the catalyst by adopting an impregnation method2And O, calcining the catalyst at the temperature of 450 ℃ for 2 hours to obtain a simulated poisoned catalyst, and testing the denitration performance of the catalyst, wherein the reaction temperature is 370-420 ℃, and the space velocity is 50000h-1The denitration efficiency is stabilized to be more than 70 percent under the condition of (1), and the integral N is2The amount of O produced is small. The catalyst of the embodiment is an ion exchange type attapulgite-based selective reduction denitration catalyst with good performance, and the catalyst makes full use of the structural characteristics of attapulgite, so that active metal sites and alkaline earth metal poisoning sites are separated to a great extent, the influence of alkaline earth metal poisoning on the redox capability of the catalyst is reduced, and the alkaline earth metal poisoning effect of the catalyst is improved. The catalyst of the embodiment can ensure the excellent medium and low temperature activity of the catalyst, and simultaneously enhance the alkaline earth metal resistance of the catalyst.
Example 6
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a preparation method of an anti-poisoning ion exchange type attapulgite-based denitration catalyst includes the following steps:
a. placing 20ml deionized water in a eggplant-shaped bottle, weighing 3.47g ammonium chloride solid, dissolving in water, adding magneton, stirring to dissolve solid, weighing 1g attapulgite crude ore, adding into the solution under stirring, adjusting pH to 3 with dilute hydrochloric acid, placing the eggplant-shaped bottle at 80 deg.CIn an oil bath pan, performing condensation reflux stirring for 3h, performing centrifugal washing after oil bath until the supernatant is free of chloride ions, placing in an oven at 80 ℃ for drying, and grinding to obtain the product exchanged with NH4 +The attapulgite clay of (1);
b. and (2) putting 100ml of deionized water into a eggplant-shaped bottle, weighing 1.208g of copper nitrate trihydrate and 2.1711g of cerous nitrate hexahydrate, dissolving in water, adding magnetons, stirring until the solid is dissolved, weighing 1g of the solid obtained in the step a, adding the solid into the solution while stirring, putting the eggplant-shaped bottle into a constant-temperature oil bath kettle at 90 ℃, condensing, refluxing and stirring for 3 hours, centrifugally washing for 3 times after oil bath, putting the bottle into an oven at 80 ℃ for drying, grinding, putting the bottle into a muffle furnace, and calcining at 450 ℃, wherein the obtained product is the ion exchange type attapulgite-based denitration catalyst.
Experimental test analysis:
testing the denitration performance of the catalyst: granulating the prepared catalyst into 20-40 meshes, putting the granules into a reaction furnace for activity and N2Selectivity test is carried out, the reaction temperature is 250-450 ℃, and the space velocity is 50000h-1The denitration efficiency is stabilized to be more than 80 percent under the condition of (1), N2The O yield is low. As can be seen from fig. 1, the denitration catalyst of the present embodiment has good catalytic activity for medium and low temperature denitration. Simulated flue gas is O25％，NO 500ppm，NH3500 ppm，N2Is diluent gas.
And (3) testing the heavy metal poisoning resistance: loading 3 wt% of PbO on the catalyst by adopting an impregnation method, calcining the catalyst at 450 ℃ for 2 hours to obtain a simulated poisoned catalyst, and testing the denitration performance of the simulated poisoned catalyst, wherein the denitration performance is realized at medium and low temperature and at the airspeed of 50000h-1Under the conditions of reaction temperature of 310-400 ℃ and space velocity of 50000h-1Under the condition (2), the denitration efficiency is stabilized to be more than 80%, and the integral byproduct N is generated2The amount of O produced is also low, and the catalyst N2The selection performance is kept at 95% and above. The catalyst is an ion exchange type attapulgite-based selective reduction denitration catalyst with good performance, the catalyst makes full use of the structural characteristics of attapulgite, active metal sites and heavy metal poisoning sites are separated to a great extent, and the influence of heavy metal poisoning on the redox capability of the catalyst is reduced, so that the heavy metal poisoning effect of the catalyst is improved。
Example 7
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a preparation method of an anti-poisoning ion exchange type attapulgite-based denitration catalyst includes the following steps:
a. putting 20ml deionized water into a eggplant-shaped bottle, weighing 3.47g of ammonium chloride solid, dissolving in water, adding magnetons, stirring until the solid is dissolved, weighing 1g of attapulgite crude ore, adding into the solution while stirring, adjusting pH to 3 with dilute hydrochloric acid, putting the eggplant-shaped bottle into a constant temperature oil bath kettle at 80 ℃, condensing, refluxing and stirring for 2h, centrifugally washing after oil bath until the supernatant is free of chloride ions, putting the eggplant-shaped bottle into an oven at 80 ℃, drying, grinding to obtain the product exchanged with NH4 +The attapulgite clay of (1);
b. and (2) putting 100ml of deionized water into a eggplant-shaped bottle, weighing 1.208g of copper nitrate trihydrate and 2.1711g of cerous nitrate hexahydrate, dissolving in water, adding magnetons, stirring until the solid is dissolved, weighing 1g of the solid obtained in the step a, adding the solid into the solution while stirring, putting the eggplant-shaped bottle into a constant-temperature oil bath kettle at 90 ℃, condensing, refluxing and stirring for 3 hours, centrifugally washing for 3 times after oil bath, putting the bottle into an oven at 80 ℃ for drying, grinding, putting the bottle into a muffle furnace, and calcining at 450 ℃, wherein the obtained product is the ion exchange type attapulgite-based denitration catalyst.
Experimental test analysis:
testing the denitration performance of the catalyst: granulating the prepared catalyst into 20-40 meshes, putting the granules into a reaction furnace for activity and N2Selectivity test is carried out, the reaction temperature is 250-450 ℃, and the space velocity is 50000h-1The denitration efficiency is stabilized to be more than 80 percent under the condition of (1), N2The O yield is low. Simulated flue gas is O25％，NO 500ppm，NH3500 ppm，N2Is diluent gas.
Alkali-resistant earth&Testing heavy metal poisoning performance: the catalyst is loaded with 1 wt% of CaO by an impregnation method&3wt％As2O3The denitration performance of the simulated poisoned catalyst obtained after calcining for 2 hours at 450 ℃ is tested again, and the medium and low temperature and the space velocity are 50000h-1Under the conditions of (1), the reaction temperature is 300-410 ℃ and the space velocityIs 50000h-1The denitration efficiency is stabilized at more than 80%, and the whole by-product N2The amount of O produced is also low. The catalyst of the embodiment is an ion exchange type attapulgite-based selective reduction denitration catalyst with good performance, the catalyst makes full use of the structural characteristics of attapulgite, active metal sites and alkaline earth metal and heavy metal poisoning sites are separated to a great extent, the influence of heavy metal poisoning on the redox capability of the catalyst is reduced, and in addition, CaO and As2O3A special counteracting effect is also present on the catalyst, therefore Ca&As co-poisoned catalyst will have better activity than single heavy metal or alkaline earth metal poisoned catalyst, so this example catalyst also has good alkaline earth&Resistance to heavy metal co-poisoning. The catalyst of the embodiment enhances the heavy metal resistance of the catalyst on the basis of ensuring the excellent medium and low temperature activity of the catalyst. The catalyst has excellent low-temperature denitration performance, low requirement on synthesis equipment, better alkaline earth/heavy metal resistance and the like, and is suitable for denitration requirements of fixed sources such as cement plants, waste incineration boilers, biomass fuel boilers, glass furnaces and the like.
Example 8
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a preparation method of an anti-poisoning ion exchange type attapulgite-based denitration catalyst includes the following steps:
a. putting 20ml deionized water into a eggplant-shaped bottle, weighing 4.2792g of ammonium chloride solid, dissolving in water, adding magnetons, stirring until the solid is dissolved, weighing 1g of attapulgite crude ore, adding into the solution while stirring, adjusting pH to 4 with dilute hydrochloric acid, putting the eggplant-shaped bottle into a constant-temperature oil bath pan at 70 ℃, condensing, refluxing and stirring for 3h, centrifugally washing after oil bath until the supernatant is free of chloride ions, putting the eggplant-shaped bottle into a 80 ℃ drying oven for drying, and grinding to obtain the product exchanged with NH4 +The attapulgite clay of (1);
b. and (2) putting 100ml of deionized water into a eggplant-shaped bottle, weighing 2.416g of copper nitrate trihydrate and 4.3422g of cerous nitrate hexahydrate, dissolving in water, adding magnetons, stirring until the solid is dissolved, weighing 1g of the solid obtained in the step a, adding the solid into the solution while stirring, putting the eggplant-shaped bottle into a constant-temperature oil bath kettle at the temperature of 80 ℃, condensing, refluxing and stirring for 5 hours, carrying out oil bath, carrying out centrifugal washing for 5 times, putting the bottle into a drying oven at the temperature of 40 ℃, drying the bottle, grinding the bottle, putting the bottle into a muffle furnace, and calcining the product at the temperature of 450 ℃, wherein the obtained product is the ion.
Experimental test analysis:
testing the denitration performance of the catalyst: granulating the prepared catalyst into 20-40 meshes, putting the granules into a reaction furnace for activity and N2Selectivity test is carried out, the reaction temperature is 250-450 ℃, and the space velocity is 50000h-1The denitration efficiency is stabilized to be more than 80 percent under the condition of (1), N2The O yield is low. As can be seen from the figure I, the denitration catalyst of the embodiment has good medium-low temperature denitration catalytic activity. Simulated flue gas is O25％，NO 500ppm，NH3500 ppm，N2Is diluent gas.
And (3) testing the heavy metal poisoning resistance: 1 wt% PbO is loaded on the catalyst by adopting an impregnation method&The denitration performance of the simulated poisoning catalyst obtained by calcining 1 wt% of CdO at 450 ℃ for 2 hours is tested again, and the denitration performance is controlled at medium and low temperature and at the airspeed of 50000h-1Under the conditions of (1), the reaction temperature is 330-400 ℃, and the space velocity is 50000h-1Under the condition (2), the denitration efficiency is stabilized to be more than 80%, and the integral byproduct N is generated2The amount of O produced is also low. The catalyst is an ion exchange type attapulgite-based selective reduction denitration catalyst with good performance, the catalyst makes full use of the structural characteristics of attapulgite, a large amount of active silanol groups existing in the attapulgite and heavy metals generate a complex or a complex, and heavy metal poisoning sites and active metal sites are separated, so that the catalyst has good resistance to co-poisoning of different heavy metals, and therefore, the catalyst also has good resistance to co-poisoning of double heavy metals.
Example 9
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a preparation method of an anti-poisoning ion exchange type attapulgite-based denitration catalyst includes the following steps:
a. getPutting 20ml deionized water in a eggplant-shaped bottle, weighing 3.47g of ammonium chloride solid, dissolving in water, adding magnetons, stirring until the solid is dissolved, weighing 1g of attapulgite crude ore, adding into the solution while stirring, adjusting pH to 3 with dilute hydrochloric acid, putting the eggplant-shaped bottle in a constant temperature oil bath kettle at 80 ℃, condensing, refluxing and stirring for 2h, centrifugally washing after oil bath until the supernatant is free of chloride ions, putting the eggplant-shaped bottle in an oven at 80 ℃, drying, grinding to obtain the product exchanged with NH4 +The attapulgite clay of (1);
b. and (2) putting 100ml of deionized water into a eggplant-shaped bottle, weighing 4.04g of ferric nitrate nonahydrate and 4.3422g of cerous nitrate hexahydrate, dissolving in water, adding magnetons, stirring until the solid is dissolved, weighing 1g of the solid obtained in the step a, adding the solid into the solution while stirring, putting the eggplant-shaped bottle into a constant-temperature oil bath kettle at 90 ℃, condensing, refluxing and stirring for 3 hours, carrying out oil bath, centrifugally washing for 3 times, putting the bottle into an oven at 80 ℃ for drying, grinding, putting the bottle into a muffle furnace, and calcining at 500 ℃, wherein the obtained product is the ion exchange type attapulgite-based denitration catalyst.
Experimental test analysis:
testing the denitration performance of the catalyst: granulating the prepared catalyst into 20-40 meshes, putting the granules into a reaction furnace for activity and N2Selectivity test is carried out, the reaction temperature is 290-390 ℃, and the space velocity is 50000h-1The denitration efficiency is stabilized to be more than 80 percent under the condition of (1), N2The O yield is low. Simulated flue gas is O25％，NO 500ppm，NH3500 ppm，N2Is diluent gas.
Testing the alkaline earth metal poisoning resistance: the catalyst is loaded with 1 wt% of CaO by an impregnation method, and the denitration performance of the simulated poisoning catalyst obtained after calcining the catalyst for 2 hours at 450 ℃ is tested again, wherein the denitration performance is realized at medium and low temperature and at the airspeed of 50000h-1Under the conditions of reaction temperature of 320-380 ℃ and space velocity of 50000h-1The denitration efficiency is stabilized to be more than 70 percent under the condition of (1), and the integral byproduct N is generated2The amount of O produced is also low. The catalyst of the embodiment is an ion exchange type attapulgite-based selective reduction denitration catalyst with good performance, and the catalyst makes full use of the structural characteristics of attapulgite, separates active metal sites and alkaline earth metal poisoning sites to a great extent, and reduces alkaline earth metal poisoning pairsThe effect of the redox ability of the catalyst, therefore, the catalyst of this example also has good heavy metal resistance.
Example 10
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a preparation method of an anti-poisoning ion exchange type attapulgite-based denitration catalyst includes the following steps:
a. putting 20ml deionized water into a eggplant-shaped bottle, weighing 3.47g of ammonium chloride solid, dissolving in water, adding magnetons, stirring until the solid is dissolved, weighing 1g of attapulgite crude ore, adding into the solution while stirring, adjusting pH to 3 with dilute hydrochloric acid, putting the eggplant-shaped bottle into a constant-temperature oil bath pan at 70 ℃, condensing, refluxing and stirring for 4 hours, centrifugally washing after oil bath until the supernatant is free of chloride ions, putting the eggplant-shaped bottle into a 90 ℃ drying oven for drying, and grinding to obtain the product exchanged with NH4 +The attapulgite clay of (1);
b. and (2) putting 100ml of deionized water into an eggplant-shaped bottle, weighing 2.9079g of nickel nitrate hexahydrate, dissolving in water, adding magnetons, stirring until the solid is dissolved, weighing 1g of the solid obtained in the step a, adding into the solution while stirring, putting the eggplant-shaped bottle into a constant-temperature oil bath kettle at 90 ℃, condensing, refluxing and stirring for 3 hours, carrying out centrifugal washing for 3 times after oil bath, putting into a drying oven at 90 ℃, drying, grinding, putting into a muffle furnace, and calcining at 550 ℃, wherein the obtained product is the ion exchange type attapulgite-based denitration catalyst.
Experimental test analysis:
testing the denitration performance of the catalyst: granulating the prepared catalyst into 20-40 meshes, putting the granules into a reaction furnace for activity and N2Selectivity test is carried out, the reaction temperature is 320-380 ℃, and the space velocity is 50000h-1The denitration efficiency is stabilized to be more than 80 percent under the condition of (1), N2The O yield is low. Simulated flue gas is O25％，NO 500ppm，NH3500 ppm，N2Is diluent gas.
And (3) testing the heavy metal poisoning resistance: loading 1 wt% of PdO on the catalyst by adopting an impregnation method, calcining the catalyst at 450 ℃ for 2 hours to obtain a simulated poisoned catalyst, and testing the denitration performance of the simulated poisoned catalyst, wherein the denitration performance is realized at medium and low temperature and at the airspeed of 50000h-1Under the conditions of (1), reactingThe temperature is 330-370 ℃, and the space velocity is 50000h-1Under the condition (2), the denitration efficiency is stabilized to be more than 70 percent, and the integral byproduct N2The amount of O produced is also low. The catalyst of the embodiment is an ion exchange type attapulgite-based selective reduction denitration catalyst with good performance, and the catalyst makes full use of the structural characteristics of attapulgite, separates active metal sites and heavy metal poisoning sites to a great extent, and reduces the influence of heavy metal poisoning on the redox capability of the catalyst, so the catalyst of the embodiment also has good heavy metal resistance.
Example 11
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a preparation method of an anti-poisoning ion exchange type attapulgite-based denitration catalyst includes the following steps:
a. putting 20ml deionized water into a eggplant-shaped bottle, weighing 4.8141g of ammonium chloride solid, dissolving in water, adding magnetons, stirring until the solid is dissolved, weighing 1g of attapulgite crude ore, adding into the solution while stirring, adjusting pH to 3 with dilute hydrochloric acid, putting the eggplant-shaped bottle into a constant temperature oil bath kettle at 80 ℃, condensing, refluxing and stirring for 2h, centrifugally washing after oil bath until the supernatant is free of chloride ions, putting the eggplant-shaped bottle into an oven at 80 ℃, drying, grinding to obtain the product exchanged with NH4 +The attapulgite clay of (1);
b. and (2) putting 100ml of deionized water into a eggplant-shaped bottle, weighing 2.9079g of nickel nitrate hexahydrate and 4.3422g of cerous nitrate hexahydrate, dissolving in water, adding magnetons, stirring until the solids are dissolved, weighing 1g of the solids obtained in the step a, adding the solids into the solution while stirring, putting the eggplant-shaped bottle into a constant-temperature oil bath kettle at 85 ℃, condensing, refluxing and stirring for 4 hours, centrifugally washing for 2 times after oil bath, putting the eggplant-shaped bottle into an oven at 80 ℃ for drying, grinding the eggplant-shaped bottle, and putting the eggplant-shaped bottle into a muffle furnace for calcining at 450 ℃, wherein the obtained product is the ion exchange type attapulgite-based denitration catalyst.
Experimental test analysis:
testing the denitration performance of the catalyst: granulating the prepared catalyst into 20-40 meshes, putting the granules into a reaction furnace for activity and N2Selectivity test is carried out, the reaction temperature is 310-420 ℃, and the space velocity is 50000h-1Conditions of (2)The denitration efficiency is stabilized to be more than 80 percent, N2The O yield is low. Simulated flue gas is O25％，NO 500ppm，NH3500 ppm，N2Is diluent gas.
And (3) testing the heavy metal poisoning resistance: loading 3 wt% of PdO on the catalyst by adopting an impregnation method, calcining the catalyst at 450 ℃ for 2 hours to obtain a simulated poisoned catalyst, and testing the denitration performance of the simulated poisoned catalyst, wherein the denitration performance is realized at medium and low temperature and at the airspeed of 50000h-1Under the conditions of (1), the reaction temperature is 330-390 ℃, and the space velocity is 50000h-1Under the condition (2), the denitration efficiency is stabilized to be more than 70 percent, and the integral byproduct N2The amount of O produced is also low. The catalyst of the embodiment is an ion exchange type attapulgite-based selective reduction denitration catalyst with good performance, and the catalyst makes full use of the structural characteristics of attapulgite, separates active metal sites and heavy metal poisoning sites to a great extent, and reduces the influence of heavy metal poisoning on the redox capability of the catalyst, so the catalyst of the embodiment also has good heavy metal resistance.
In conclusion, the catalyst is an ion exchange type attapulgite-based selective reduction denitration catalyst with good performance, and has high alkali/alkaline earth/heavy metal resistance. The catalyst is prepared by a two-step exchange method, and the active components of the catalyst obtained by the exchange method have high dispersion degree, so that the catalyst has good medium-low temperature denitration performance; and a large amount of active silanol hydroxyl groups in the attapulgite structure can be well combined with alkali/alkaline earth/heavy metal ions, and the influence of poisoning metal ions on active components is reduced, so that the catalyst also has good alkali/alkaline earth/heavy metal resistance. The catalyst disclosed by the invention has excellent low-temperature denitration performance, low requirements on synthesis equipment, better alkali/alkaline earth/heavy metal resistance and the like, and is suitable for denitration requirements of fixed sources such as cement plants, waste incineration boilers, biomass fuel boilers, glass furnaces and the like.
The embodiments of the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to the embodiments, and various changes and modifications can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention shall be equivalent substitutions, as long as the purpose of the present invention is met, and the present invention shall fall within the protection scope of the present invention without departing from the technical principle and inventive concept of the present invention.
Claims (10)
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