CN107694575A - A kind of complex carrier SCR denitration and preparation method - Google Patents
A kind of complex carrier SCR denitration and preparation method Download PDFInfo
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- CN107694575A CN107694575A CN201710831172.7A CN201710831172A CN107694575A CN 107694575 A CN107694575 A CN 107694575A CN 201710831172 A CN201710831172 A CN 201710831172A CN 107694575 A CN107694575 A CN 107694575A
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- complex carrier
- convex rod
- concave convex
- catalyst
- scr denitration
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- 238000002360 preparation method Methods 0.000 title claims description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000314 lubricant Substances 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical group O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 5
- 239000000306 component Substances 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims description 15
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000006210 lotion Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 230000004913 activation Effects 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- 238000001035 drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims 1
- 239000008367 deionised water Substances 0.000 claims 1
- 229910021641 deionized water Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003546 flue gas Substances 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 19
- 238000012360 testing method Methods 0.000 description 11
- 238000011056 performance test Methods 0.000 description 7
- 206010027439 Metal poisoning Diseases 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- 230000001846 repelling effect Effects 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
-
- 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
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of complex carrier SCR denitration, including certain mass than complex carrier, active component, auxiliary agent, lubricant；Complex carrier is the mixture of anatase-type nanometer titanium dioxide and metal ion-modified concave convex rod, and active component is vanadic anhydride.By being acidified concave convex rod, increase specific surface area, increase avtive spot, strengthen the adsorption capacity to element of being easily poisoned in flue gas, make catalyst that there is preferable anti-poisoning capability；Using metal ion-modified concave convex rod and nano titanium oxide as catalyst carrier, catalyst reaction temperatures section is set to widen to 160 DEG C~420 DEG C, efficiency high, stability in the temperature range catalyst denitration are good, selectivity is good, available for all types of industries stove denitration；Using concave convex rod as main material, production cost is effectively reduced；Titanium dioxide nanoparticle can be filled in the space of concave convex rod skeleton so that the stability of catalyst structure is strong, not easy to crack after high-temperature calcination, and wear-resisting intensity is higher.
Description
Technical field
The present invention relates to a kind of complex carrier SCR denitration and preparation method thereof, belong to efficient catalyst and
Atmosphere pollution prevention and control field.
Background technology
Pollution of the nitrogen oxides to environment is very serious, and nitrogen oxides is both the basis of nitric acid type acid rain, is to form light again
One of chemical fumes, the main matter to damage the ozone layer；Nitrogen oxides also has very strong toxicity, can cause pole to health
Macrolesion.In recent years, with the rapid development of economy, the discharge capacity of nitrogen oxides pollution thing increases sharply, life is seriously polluted
State environment.
Coal-burning power plant is the main enterprises of discharged nitrous oxides, its discharge capacity account for national nitrogen oxide emission 25~
40%, country has strictly controlled the discharge capacity of nitrogen oxides in coal-fired plant flue gas.But in increasingly serious pollution control situation
In front, the discharged nitrous oxides of other industrial furnaces will be also strictly controlled, such as the industry such as coking, cement, glass, steel
Pollutant emission national standard is issued, some key areas have progressively started to carry out nitrogen according to most stringent of index in standard
Emissions of oxides controls.
Selective catalytic reduction (SCR) denitration is most widely used, denitrating flue gas skill that technology is most ripe in the world
One of art, its technological core are to have used denitrating catalyst have the advantages that purifying rate is high, reliable, flat catalysis
Agent is very important one kind in denitrating catalyst, has the higher market share.The denitrating catalyst that coal-burning power plant uses is
For many years, technology is more ripe for commercial applications, but the flue gas condition of the industrial furnace such as coking, cement, glass and coal-burning power plant deposit
In larger difference, have the characteristics that cigarette temperature is relatively low, dust burdening is high, poisoning constituent content is higher, current business denitrating catalyst without
Method meets the denitration demand of industrial furnace.
Therefore, need exploitation one kind badly and have inexpensive, high denitration activity, high mechanical properties, wider reaction temperature section concurrently, together
When the denitrating catalyst with preferable anti-poisoning capability, required with meeting that the increasingly strict nitrogen oxides of industrial furnace controls.
The content of the invention
The technical problem to be solved by the invention is to provide a kind of reaction temperature section for widening catalyst, improve
Catalyst sulfur resistive, water resistant, anti-As, alkali metal, alkaline-earth metal poisoning capability, while also with denitration efficiency is high, cost is cheap, machine
The advantages that tool intensity is high, versatile, complex carrier SCR denitration and its preparation suitable for various industrial furnace denitrations
Method.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of complex carrier SCR denitration, including certain mass than complex carrier, active component, auxiliary agent, lubrication
Agent；
The complex carrier is the mixture of anatase-type nanometer titanium dioxide and metal ion-modified concave convex rod,
The active component is vanadic anhydride.
Above-mentioned complex carrier, active component, auxiliary agent, the mass ratio of lubricant are 100：(0.5~5)：(1~10)：(0.2
~2).
The mol ratio of Ti, Si element is 1 in above-mentioned complex carrier：(0.1~0.5).
The mol ratio of metallic element and Si elements is (0.05~0.2) in above-mentioned metal ion-modified concave convex rod:1.
Above-mentioned lubricant is one kind or several in stearic acid, odium stearate, zinc stearate, polyvinyl alcohol or Tissuemat E
Kind.
A kind of preparation method of above-mentioned complex carrier SCR denitration, comprises the following steps：
S1, concave convex rod is placed in inorganic acid solution, stirred, stood after supersound process and remove upper suspension, washed
Solid after centrifugation, drying, grinding obtain acid activation concave convex rod；
S2, above-mentioned acid activation concave convex rod is placed in the solvable saline solution of modified metal element, stirring, after being ultrasonically treated
Drying, metal ion-modified concave convex rod powder is made after calcining, grinding；
S3, compound load is made after above-mentioned metal ion-modified concave convex rod powder is well mixed with nano-titanium dioxide powder
Body；
S4, vanadate is taken to be dissolved in monoethanolamine solution, stirring and dissolving under certain temperature；
S5, in mass ratio that complex carrier, auxiliary agent, mix lubricant is uniform, addition vanadate solution, ammoniacal liquor and deionization
Water, pH to 7~9 is adjusted, lotion catalyst is made；
S6, by catalyst lotion it is coated, it is crimped, shearing, calcining, flat catalyst is prepared.
Inorganic acid in above-mentioned steps S1 is the one or more in hydrochloric acid, sulfuric acid and nitric acid, concentration be 1mol/L~
5mol/L；
Mixing time is 0.5~2h, and ultrasonic time is 10~30min, is washed to washing lotion pH value to be neutral, oven temperature is
90 DEG C~105 DEG C.
Modified metal element described in upper rapid S2 is one or both of Fe, Zr, Ce, La, Mn, Sn；
Mixing time is 0.5~2h, ultrasonic time is 0.5~1h, and oven temperature is 90 DEG C~105 DEG C, and calcining heat is
400 DEG C, calcination time is 0.5~2h.
Vanadate in above-mentioned steps S4 is positive vanadate, pyrovanadate or metavanadate, and solution temperature is 70 DEG C~85
℃。
Calcining heat in above-mentioned steps S5 is 420 DEG C~600 DEG C, and calcination time is 1h~3.5h.
The beneficial effect that the present invention is reached：
1st, specific surface area increase, avtive spot increase after concave convex rod is acidified；Concave convex rod duct increases be acidified simultaneously after, right
Easy poisoning element adsorption capacity enhancing in flue gas, makes catalyst have preferable anti-poisoning capability.
2nd, using metal ion-modified concave convex rod and nano titanium oxide as catalyst carrier, catalyst reaction temperatures area is made
Between widen to 160 DEG C~420 DEG C, catalyst is the temperature range denitration efficiency is high, stability is good, selectivity is good, available for each
Class industrial furnace denitration.
3rd, concave convex rod effectively reduces Catalyst Production cost as main raw material(s), and price is more cheap.
4th, titanium dioxide nanoparticle can be filled in the space of concave convex rod skeleton, make the catalyst structure stability strong,
Not easy to crack after high-temperature calcination, the wear-resisting intensity of catalyst is higher.
Figure of description
Fig. 1 is the local molten front-end geometry change schematic diagram of acid of concave convex rod octahedral cations of the present invention.
Embodiment
Below in conjunction with the accompanying drawings and specific embodiment the invention will be further described.
The following examples are only intended to illustrate the technical solution of the present invention more clearly, and can not limit the present invention with this
Protection domain.
Chemical reagent and equipment and instrument used in embodiments of the invention, are purchased in market.
Wherein, specific surface area test uses full-automatic specific surface area analysis instrument (TriStar II 3020),
Wear-resisting strength test uses rotary abrasion instrument (Taber5135),
The flue gas analyzer model Thermo42i used in denitration performance test.
A kind of complex carrier SCR denitration, is prepared according to following steps：
S1, concave convex rod is placed in 1mol/L~5mol/L inorganic acid solution, stirs 0.5~2h, it is ultrasonically treated 10~
Stood after 30min and remove upper suspension, the solid after washing centrifugation to washing lotion pH value is neutrality, at 90 DEG C~105 DEG C
Drying, grinding obtain acid activation concave convex rod；
S2, above-mentioned acid activation concave convex rod is placed in the solvable saline solution of modified metal element, it is 0.5~2h of stirring, super
After 0.5~1h of sonication, dried at 90 DEG C~105 DEG C, metal ion is made after 0.5~2h, grinding are then calcined at 400 DEG C
Modified attapulgite powder；
S3, compound load is made after above-mentioned metal ion-modified concave convex rod powder is well mixed with nano-titanium dioxide powder
Body；
S4, vanadate is taken to be dissolved in monoethanolamine solution, stirring and dissolving at 70 DEG C~85 DEG C；
S5, in mass ratio that complex carrier, auxiliary agent, mix lubricant is uniform, addition vanadate solution, ammoniacal liquor and deionization
Water, pH to 7~9 is adjusted, lotion catalyst is made；
S6, by catalyst lotion is coated, crimped, shearing, 1h~3.5h is calcined at 420 DEG C~600 DEG C, be prepared flat
Board-like catalyst.
Catalyst performance is tested：
Embodiment 1
Properties of sample：Specific surface area 115m2/ g, wear-resisting intensity 47mg/100U.
Catalyst denitration performance is tested：Reaction temperature is 160 DEG C~420 DEG C, and smoke components are NO (500ppm), NH3
(500ppm)、O2(5%), carrier gas N2, air speed 10000h-1, in the range of reaction temperature, catalyst denitration efficiency is stable
More than 93%, N2Selectivity is more than 95%.
Catalyst sulfur resistive water repelling property is tested：On the basis of denitration performance test condition, be continually fed into 1000ppmSO2 and
10% vapor 24h, other test conditions are constant, in the range of reaction temperature, catalyst denitration efficiency it is stable 91% with
On, N2Selectivity is more than 90%.
Catalyst alkali resistant earth metal poisoning performance is tested：Load 500 μm of ol/g Ca on a catalyst using infusion process2+,
The 4h under 400 DEG C of calcinings, then tests its denitration efficiency (test condition is with above-mentioned catalyst denitration performance test condition), measures
Denitration efficiency in 160 DEG C~420 DEG C reaction intervals is stable more than 88%, N2Selectivity is more than 90%.
Embodiment 2
Properties of sample：Specific surface area 128m2/ g, wear-resisting intensity 39mg/100U.
Catalyst denitration performance is tested：Reaction temperature is 160 DEG C~420 DEG C, and smoke components are NO (500ppm), NH3
(500ppm)、O2(5%), carrier gas N2, air speed 10000h-1, in the range of reaction temperature, catalyst denitration efficiency is stable
More than 96%, N2Selectivity is more than 95%.
Catalyst sulfur resistive water repelling property is tested：On the basis of denitration performance test condition, be continually fed into 1000ppmSO2 and
10% vapor 24h, other test conditions are constant, in the range of reaction temperature, catalyst denitration efficiency it is stable 92% with
On, N2Selectivity is more than 91%.
Catalyst alkali resistant earth metal poisoning performance is tested：Load 800 μm of ol/g K on a catalyst using infusion process+,
The lower 4h of 400 DEG C of calcinings, then tests its denitration efficiency (test condition is with above-mentioned catalyst denitration performance test condition), measures
Denitration efficiency in 160 DEG C~420 DEG C reaction intervals is stable more than 91%, N2Selectivity is more than 90%.
Embodiment 3
Properties of sample：Specific surface area 109m2/ g, wear-resisting intensity 28mg/100U.
Catalyst denitration performance is tested：Reaction temperature is 160 DEG C~420 DEG C, and smoke components are NO (500ppm), NH3
(500ppm)、O2(5%), carrier gas N2, air speed 10000h-1, in the range of reaction temperature, catalyst denitration efficiency is stable
More than 97%, N2Selectivity is more than 95%.
Catalyst sulfur resistive water repelling property is tested：On the basis of denitration performance test condition, be continually fed into 1000ppmSO2 and
10% vapor 24h, other test conditions are constant, in the range of reaction temperature, catalyst denitration efficiency it is stable 90% with
On, N2Selectivity is more than 95%.
Catalyst alkali resistant earth metal poisoning performance is tested：Load 1000 μm of ol/g Na on a catalyst using infusion process+,
The 4h under 400 DEG C of calcinings, then tests its denitration efficiency (test condition is with above-mentioned catalyst denitration performance test condition), measures
Denitration efficiency in 160 DEG C~420 DEG C reaction intervals is stable more than 90%, N2Selectivity is more than 90%.
Accompanying drawing 1 is the local molten front-end geometry change schematic diagram of acid of concave convex rod octahedral cations, and left figure is natural concave convex rod
Structural representation, after concave convex rod is acidified, duct significantly increases (right figure), adsorption capacity enhancing.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, some improvement and deformation can also be made, these are improved and deformation
Also it should be regarded as protection scope of the present invention.
Claims (10)
- A kind of 1. complex carrier SCR denitration, it is characterised in that including certain mass than complex carrier, active component, Auxiliary agent, lubricant；The complex carrier is the mixture of anatase-type nanometer titanium dioxide and metal ion-modified concave convex rod,The active component is vanadic anhydride.
- 2. a kind of complex carrier SCR denitration according to claim 1, it is characterised in that the complex carrier, work Property component, auxiliary agent, lubricant mass ratio be 100：(0.5~5)：(1~10)：(0.2~2).
- 3. a kind of complex carrier SCR denitration according to claim 1, it is characterised in that in the complex carrier The mol ratio of Ti, Si element is 1：(0.1~0.5).
- 4. a kind of complex carrier SCR denitration according to claim 1, it is characterised in that the metal ion changes Property concave convex rod in the mol ratio of metallic element and Si elements be (0.05~0.2):1.
- 5. a kind of complex carrier SCR denitration according to claim 1, it is characterised in that the lubricant is hard One or more in resin acid, odium stearate, zinc stearate, polyvinyl alcohol or Tissuemat E.
- 6. according to a kind of preparation method of any described complex carrier SCR denitrations of claim 1-5, its feature exists In comprising the following steps：S1, concave convex rod is placed in inorganic acid solution, stirred, stood after supersound process and remove upper suspension, washing centrifugation Solid afterwards, drying, grinding obtain acid activation concave convex rod；S2, above-mentioned acid activation concave convex rod is placed in the solvable saline solution of modified metal element, stirring, dried after being ultrasonically treated It is dry, metal ion-modified concave convex rod powder is made after calcining, grinding；S3, complex carrier is made after above-mentioned metal ion-modified concave convex rod powder is well mixed with nano-titanium dioxide powder；S4, vanadate is taken to be dissolved in monoethanolamine solution, stirring and dissolving under certain temperature；S5, in mass ratio that complex carrier, auxiliary agent, mix lubricant is uniform, addition vanadate solution, ammoniacal liquor and deionized water, PH to 7~9 is adjusted, lotion catalyst is made；S6, by catalyst lotion it is coated, it is crimped, shearing, calcining, flat catalyst is prepared.
- 7. the preparation method of a kind of complex carrier SCR denitration according to CLAIM OF BENEFIT 6, it is characterised in that described Inorganic acid in step S1 is the one or more in hydrochloric acid, sulfuric acid and nitric acid, and concentration is 1mol/L~5mol/L；Mixing time is 0.5~2h, and ultrasonic time is 10~30min, and it is neutrality to wash to washing lotion pH value, and oven temperature is 90 DEG C ~105 DEG C.
- A kind of 8. preparation method of complex carrier SCR denitration according to claim 6, it is characterised in that step Modified metal element described in S2 is one or both of Fe, Zr, Ce, La, Mn, Sn；Mixing time is 0.5~2h, ultrasonic time is 0.5~1h, and oven temperature is 90 DEG C~105 DEG C, calcining heat 400 DEG C, calcination time is 0.5~2h.
- 9. the preparation method of a kind of complex carrier SCR denitration according to claim 6, it is characterised in that described Vanadate in step S4 is positive vanadate, pyrovanadate or metavanadate, and solution temperature is 70 DEG C~85 DEG C.
- 10. the preparation method of a kind of complex carrier SCR denitration according to claim 6, it is characterised in that described Calcining heat in step S5 is 420 DEG C~600 DEG C, and calcination time is 1h~3.5h.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109999901A (en) * | 2019-05-10 | 2019-07-12 | 宫子凡 | A kind of porous graphene-molecular sieve complex carries denitrating catalyst and preparation method thereof |
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| CN112007699A (en) * | 2020-10-09 | 2020-12-01 | 黄山天之都环保科技有限公司 | SCR denitration catalyst with ammoniaphilic membrane and preparation method thereof |
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103878032A (en) * | 2014-03-25 | 2014-06-25 | 浙江海亮环境材料有限公司 | SCR denitration catalyst with clay |
| CN104857952A (en) * | 2015-05-04 | 2015-08-26 | 合肥晨晰环保工程有限公司 | Sulfur-resistant nitrogen-oxide-removing attapulgite manganese-based SCR catalyst and preparation method and application thereof |
| CN105214650A (en) * | 2015-09-21 | 2016-01-06 | 盐城复华环保产业开发有限公司 | Containing the low temperature SCR denitration catalyst and preparation method thereof of zirconium manganese oxide |
| CN105413705A (en) * | 2015-11-11 | 2016-03-23 | 福建紫荆环境工程技术有限公司 | Catalyst for removing VOCs through photocatalysis in cooperation with thermal catalytic oxidation and preparation method and application of catalyst |
| JP2016150278A (en) * | 2015-02-16 | 2016-08-22 | イビデン株式会社 | Honeycomb catalyst |
| WO2016148535A1 (en) * | 2015-03-18 | 2016-09-22 | 한국과학기술원 | Biomass saccharification method using solid acid catalyst |
| CN106111118A (en) * | 2016-06-20 | 2016-11-16 | 浙江三龙催化剂有限公司 | A kind of preparation method and applications of denitrating catalyst |
| CN106492790A (en) * | 2016-09-23 | 2017-03-15 | 河北工业大学 | A kind of low temperature SCR denitration catalyst and preparation method thereof |
| CN106732537A (en) * | 2016-11-24 | 2017-05-31 | 北京神雾电力科技有限公司 | It is a kind of to add attapulgite modified low-temperature SCR catalyst and preparation method thereof |
-
2017
- 2017-09-15 CN CN201710831172.7A patent/CN107694575A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103878032A (en) * | 2014-03-25 | 2014-06-25 | 浙江海亮环境材料有限公司 | SCR denitration catalyst with clay |
| JP2016150278A (en) * | 2015-02-16 | 2016-08-22 | イビデン株式会社 | Honeycomb catalyst |
| WO2016148535A1 (en) * | 2015-03-18 | 2016-09-22 | 한국과학기술원 | Biomass saccharification method using solid acid catalyst |
| CN104857952A (en) * | 2015-05-04 | 2015-08-26 | 合肥晨晰环保工程有限公司 | Sulfur-resistant nitrogen-oxide-removing attapulgite manganese-based SCR catalyst and preparation method and application thereof |
| CN105214650A (en) * | 2015-09-21 | 2016-01-06 | 盐城复华环保产业开发有限公司 | Containing the low temperature SCR denitration catalyst and preparation method thereof of zirconium manganese oxide |
| CN105413705A (en) * | 2015-11-11 | 2016-03-23 | 福建紫荆环境工程技术有限公司 | Catalyst for removing VOCs through photocatalysis in cooperation with thermal catalytic oxidation and preparation method and application of catalyst |
| CN106111118A (en) * | 2016-06-20 | 2016-11-16 | 浙江三龙催化剂有限公司 | A kind of preparation method and applications of denitrating catalyst |
| CN106492790A (en) * | 2016-09-23 | 2017-03-15 | 河北工业大学 | A kind of low temperature SCR denitration catalyst and preparation method thereof |
| CN106732537A (en) * | 2016-11-24 | 2017-05-31 | 北京神雾电力科技有限公司 | It is a kind of to add attapulgite modified low-temperature SCR catalyst and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109999901A (en) * | 2019-05-10 | 2019-07-12 | 宫子凡 | A kind of porous graphene-molecular sieve complex carries denitrating catalyst and preparation method thereof |
| CN111330609A (en) * | 2020-02-21 | 2020-06-26 | 大唐南京环保科技有限责任公司 | Anti-alkali metal poisoning denitration catalyst and preparation method thereof |
| CN111330609B (en) * | 2020-02-21 | 2023-02-24 | 大唐南京环保科技有限责任公司 | Denitration catalyst resistant to alkali metal poisoning and preparation method thereof |
| TWI773475B (en) * | 2020-08-04 | 2022-08-01 | 日商三菱動力股份有限公司 | Denitration catalyst and method for purifying combustion exhaust gas |
| CN112007699A (en) * | 2020-10-09 | 2020-12-01 | 黄山天之都环保科技有限公司 | SCR denitration catalyst with ammoniaphilic membrane and preparation method thereof |
| CN113019353A (en) * | 2021-02-04 | 2021-06-25 | 上海大学 | Anti-poisoning ion exchange type attapulgite-based denitration catalyst, and preparation method and application thereof |
| CN113856673A (en) * | 2021-10-27 | 2021-12-31 | 西安热工研究院有限公司 | Catalyst for widening reaction temperature window of SCR (Selective catalytic reduction) catalyst and modification method |
| CN114433071A (en) * | 2021-12-29 | 2022-05-06 | 江苏世清环保科技有限公司 | Denitration catalyst prepared by taking attapulgite as carrier and preparation method thereof |
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