CN107096524A - A kind of preparation method for the Faveolate denitration catalyst for improving specific surface area - Google Patents
A kind of preparation method for the Faveolate denitration catalyst for improving specific surface area Download PDFInfo
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- CN107096524A CN107096524A CN201710433408.1A CN201710433408A CN107096524A CN 107096524 A CN107096524 A CN 107096524A CN 201710433408 A CN201710433408 A CN 201710433408A CN 107096524 A CN107096524 A CN 107096524A
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- catalyst
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- source presoma
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- activated carbon
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- 239000003054 catalyst Substances 0.000 title claims abstract description 145
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 86
- 238000002156 mixing Methods 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 41
- 239000000843 powder Substances 0.000 claims abstract description 40
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 39
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 39
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 38
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 38
- 239000010936 titanium Substances 0.000 claims abstract description 36
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 34
- 239000010937 tungsten Substances 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 25
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 22
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 17
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 17
- 230000001413 cellular effect Effects 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 238000013019 agitation Methods 0.000 claims abstract description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 239000011733 molybdenum Substances 0.000 claims abstract description 9
- 239000012065 filter cake Substances 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 229910052756 noble gas Inorganic materials 0.000 claims abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 48
- 235000014633 carbohydrates Nutrition 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 230000010355 oscillation Effects 0.000 claims description 18
- 238000007789 sealing Methods 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 15
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 13
- 239000008103 glucose Substances 0.000 claims description 13
- 238000012545 processing Methods 0.000 claims description 10
- -1 polyoxyethylene Polymers 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 150000002016 disaccharides Chemical class 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- 238000010348 incorporation Methods 0.000 claims description 2
- 229920001282 polysaccharide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 150000002772 monosaccharides Chemical class 0.000 claims 1
- 238000005406 washing Methods 0.000 abstract description 24
- 206010001497 Agitation Diseases 0.000 abstract description 12
- 239000003546 flue gas Substances 0.000 abstract description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 9
- 230000008021 deposition Effects 0.000 abstract description 8
- 229910001385 heavy metal Inorganic materials 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 73
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 54
- 239000002002 slurry Substances 0.000 description 44
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 28
- 229910052757 nitrogen Inorganic materials 0.000 description 27
- 238000000034 method Methods 0.000 description 26
- 238000004523 catalytic cracking Methods 0.000 description 21
- 239000002253 acid Substances 0.000 description 16
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 15
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 description 14
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 14
- 239000011609 ammonium molybdate Substances 0.000 description 14
- 229940010552 ammonium molybdate Drugs 0.000 description 14
- 235000018660 ammonium molybdate Nutrition 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 14
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 14
- 235000013162 Cocos nucifera Nutrition 0.000 description 13
- 244000060011 Cocos nucifera Species 0.000 description 13
- 241000219782 Sesbania Species 0.000 description 13
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 12
- 238000001556 precipitation Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000005360 mashing Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000000975 co-precipitation Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 4
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical compound [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 241000256844 Apis mellifera Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000010237 hybrid technique Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a kind of preparation method for the Faveolate denitration catalyst for improving specific surface area, step is as follows：(1) activated carbon is mixed with saccharide solution, be beaten；(2) titanium source presoma is dissolved；(3) tungsten source presoma is dissolved, and it is mixed with the material of step (1), (2)；(4) material adjusts pH value to 8~13 after step (3) is mixed, and precipitates, filters, washing and to obtain filter cake；(5) step (4) filter cake is tuned into pulpous state, adds vanadium source precursor solution, dried after mixing, roasting forms powder under noble gas protection；(6) the powder mixing pulp of the solution for forming molybdenum source presoma and step (5), after stirring, plus pore creating material, stood after secondary agitation, be squeezed into it is cellular, surface coating nanometer level tungsten oxide, is calcined in inert-gas environment, obtains catalyst after drying.Catalyst of the present invention can improve specific surface area of catalyst, can also resist the heavy metal in flue gas in its surface nonuniform deposition.
Description
Technical field
The present invention relates to a kind of preparation method for the Faveolate denitration catalyst for improving specific surface area, especially one kind is supported
The preparation method of the uneven denitrating catalyst of vanadium deposition in anti-flue gas, the invention belongs to New Inorganic Materials technical field.
Background technology
Nitrogen oxides (NOx) it is one of main atmosphere pollution, emission request is increasingly strict.China《" 12 " are saved
Can the comprehensive programme of work of emission reduction》Middle regulation：By 2015, national discharged nitrous oxides total amount declined 10% than 2010.
The GB13223-2001 that the national environmental protection of in September, 2011 portion is promulgated《Fossil-fuel power plant atmospheric pollutant emission standard》Thermal power plant NOx is arranged
Put concentration and make more strict requirements：Newly-built the 3rd period, enlarging, the coal-burning boiler of reconstruction are provided, NOx highests allow discharge
Concentration is 100mg/m3.What national environmental protection portion was promulgated《Petroleum refining industry pollutant emission standard》It is required that：On July 1st, 2015
Rise, nitrogen oxides requirement is less than 200mg/m in newly-built catalytic cracking unit discharge regenerated flue gas3, special emission limit requires small
In 100mg/m3, on July 1st, 2017, existing enterprise also performed the standard.In numerous gas denitrifying technologies, selective catalysis is also
The technology that it is still international mainstream that former method (Selective Catalytic Reduction, SCR), which is, its NOxRemoval efficiency is reachable
To 80%~90%.Wherein, denitrating catalyst is the core of SCR technology, and developed country just have developed in the eighties in last century
For a series of denitrating catalysts of coal characteristics, boiler type etc., many R＆D institutions of China are coal-fired for China with enterprise
Boiler and catalytic cracking flue gas situation have also carried out a series of research, and develop some denitrating catalysts.
CN201010537130 proposes the method that denitrating catalyst is prepared using hydrothermal method, first by titanium source presoma
With the mixing of tungsten source presoma, it is placed in autoclave and carries out hydro-thermal reaction, be filtered, washed and dried and obtain titanium tungsten powder denitration catalyst
Agent, while can also introduce the elements such as vanadium and molybdenum, prepares multi-metal-oxide catalyst.Catalyst activity component prepared by this method
Crystal grain is small, specific surface area is larger, but by being sufficiently mixed process material aggregation extent of the same race may be caused higher due to no
Phenomenon occurs, and certain influence is had on catalyst activity.
CN201110345605 proposes a kind of preparation method of denitrating catalyst, and tungsten is sequentially added into metatitanic acid slurry
Sour ammonium, ammonium molybdate and ammonium metavanadate, ultrasonic wave mashing, then pH value is adjusted to 4.0~6.5, stand, separate, drying is catalyzed
Agent powder.This method technique is simple, cost is low, but ammonium metavanadate is added with solid, and the dissolubility of vanadium is still to be tested, and vanadium disperses
Although activity very high, SO when uneven2/SO3Conversion ratio can be higher, influences catalyst performance.
CN201210400949 proposes a kind of preparation method of titanium dioxide-tungstic acid composite granule, by para-tungstic acid
Ammonium salt solution is added in metatitanic acid slurries, and directly vacuum drying obtains finished product after stirring.This method technique is simple, but titanium-tungsten
Mixing intensity is relatively low, and the performance to material can have a certain impact.
In summary, the preparation of denitrating catalyst is directed to the mixing of Multimetal oxide, hybrid mode and technique
Difference can not distinguish the denitration performance of catalyst, NO completelyxConversion ratio can reach more than 90%, illustrate special metal oxygen
The catalytic activity of compound is higher, and scattered inequality can still obtain higher NOxConversion ratio.The quality of catalyst overall performance is also
Need to be verified from otherwise sign, while the preparation of catalyst will also take into account the operability of industry amplification.
The content of the invention
It is a primary object of the present invention to provide a kind of preparation side for the Faveolate denitration catalyst for improving specific surface area
Method, to overcome the unbalanced defect in denitrating catalyst activated centre in high-temperature flue gas in the prior art, and the present invention is urged
Agent can resist barium oxide in flue gas and, in its surface nonuniform deposition, increase specific surface area of catalyst again, improve catalysis
Agent performance.
The object of the present invention is achieved like this, a kind of preparation side for the Faveolate denitration catalyst for improving specific surface area
Method, comprises the following steps：
(1) activated carbon is mixed with saccharide solution, be then beaten；
(2) titanium source presoma is dissolved to form solution；
(3) tungsten source presoma is dissolved, and it is well mixed with the solution of step (1), (2)；
(4) the well mixed rear solution of step (3) is adjusted into pH value to 8~13, precipitated, filter cake is washed to obtain in filtering；
(5) deionized water is added in filter cake obtained by step (4), is tuned into pulpous state, add vanadium source precursor solution, mixing is equal
After even, it is dried, is then calcined again under inert gas shielding, forms powder；
(6) the powder mixing pulp of the solution for forming molybdenum source presoma and step (5), after stirring, plus pore creating material,
After secondary agitation, sealing and standing, it is squeezed into cellular, surface coating nanometer level tungsten oxide after drying, noble gas protection is lower is calcined, shape
Into denitrating catalyst.
Titanium source presoma, tungsten source presoma, vanadium source presoma, molybdenum source presoma, pore creating material are used in the present invention
Denitrating catalyst prepares conventional material in the prior art, and consumption selects appropriate amount also according to process characteristic, and the present invention is
It is not any limitation as especially.The present invention also recommended preferred scheme.
Activated carbon described in step (1) of the present invention can first use normal activated carbon commodity, can be wood activated charcoal, can also
For the activated carbon of shell class, used activated carbon is Powdered Activated Carbon, and granularity is 10~500 mesh, preferably 180~300 mesh,
Specific surface area is preferably 600~2000m2/ g, pore volume is preferably 0.60~1.6cm3/g。
In the inventive method, the activated carbon described in step (1) is first handled with carbohydrate, is then beaten.Described carbohydrate is single
One or more in sugar, disaccharide and polysaccharide, preferably carbon atom are 3~18 carbohydrate, more preferably in sucrose and glucose
It is one or two kinds of.The quality of the carbohydrate accounts for the 3~40% of the quality of activated carbon, preferably 10~20%.The processing of carbohydrate can
Add activated carbon so that sugar is dissolved in after water and be well mixed.
In the inventive method, the quality of activated carbon described in step (1) is with titanium source presoma (with TiO2Meter) mass ratio is best
For 1~20:100.
The preparation method of denitrating catalyst of the present invention, wherein, the titanium source presoma described in step (2) is best
For titanyl sulfate or metatitanic acid, the dissolving of titanium source presoma, solvent for use is preferably sulfuric acid, water, nitric acid or oxalic acid.
The preparation method of denitrating catalyst of the present invention, wherein, the tungsten source presoma described in step (3) is preferably secondary
Ammonium tungstate or ammonium metatungstate, tungsten source presoma is with WO3Meter, titanium source presoma is with TiO2Meter, tungsten source forerunner used in step (3)
The mass ratio of body and titanium source presoma is preferably 2.0~5.0:100.
The preparation method of denitrating catalyst of the present invention, wherein, in the step (3), step (5) and step (6)
Hybrid mode be mechanical agitation mixing, fluid dynamic mixing or and supersonic oscillations mixing, step (3) and step (5) are mixed
The conjunction time is preferably 0.5~3h, and the incorporation time of step (6) is preferably 10~60min, the sealing and standing time of step (6)
Preferably 8~30h.
The preparation method of denitrating catalyst of the present invention, wherein, pH value adjusts medicament used most in the step (4)
It is well ammoniacal liquor or potassium hydroxide, pH value is preferably 8~13 after conciliation.
The preparation method of denitrating catalyst of the present invention, wherein, in the vanadium source precursor solution in the step (5)
Vanadium source presoma is preferably ammonium metavanadate or vanadic acid amine, and vanadium source presoma is with V2O5Meter, the titanium source presoma is with TiO2
The mass ratio of meter, vanadium source presoma consumption and titanium source presoma consumption is preferably 1.0~6.0:100.
The preparation method of denitrating catalyst of the present invention, wherein, sintering temperature in the step (5) and step (6)
It is preferably 400~650 DEG C, roasting time is preferably 4~10h, needs in roasting process to add inert gas shielding.
The preparation method of denitrating catalyst of the present invention, wherein, roasting process in the step (5) and step (6)
In need to add inert gas shielding, inert gas can be nitrogen or helium, preferably nitrogen.
Molybdenum source presoma described in the preparation method of denitrating catalyst of the present invention, wherein step (6) is preferably molybdenum
Sour ammonium, the molybdenum source presoma is with MoO3Meter, titanium source presoma is with TiO2Meter, the matter of molybdenum source presoma and titanium source presoma used
Measure ratio preferably 0.5~2:100.
The preparation method of denitrating catalyst of the present invention, wherein the pore creating material added in the step (6) is best
For the one or more in urea, polyoxyethylene, sesbania powder, the addition and the mass ratio of titanium source presoma of pore creating material are preferably
0.5~1.5:100.
Nanoscale tungsten quality described in the preparation method of denitrating catalyst of the present invention, wherein step (6) with
WO3Meter, titanium source presoma is with TiO2The mass ratio of meter, tungsten oxide used and titanium source presoma is 1~10:100, preferably 3~6:
100。
Present invention also offers a kind of denitrating catalyst, it is prepared by the preparation method of above-mentioned denitrating catalyst.
Beneficial effects of the present invention：
(1) in catalyst preparation process of the present invention, using activated carbon, beaten again after handling activated carbon in particular by carbohydrate
Slurry, carbohydrate is adsorbed in activated carbon, and by follow-up roasting, the carbohydrate breakdown in the middle of activated carbon is carbonized to form new unformed titanium
The combination of tungsten is closer, and the carbohydrate activated carbon interior trim surface new through being decomposed to form, adds table in activated carbon on activated carbon endoporus
The active sites in face.Therefore, carbohydrate processing activated carbon, can promote the even closer parcel activated carbon of amorphous titanium oxide, tungsten oxide,
Catalyst strength is improved, (specific surface area is in 140m while improving specific surface area of catalyst2/ more than g) and porosity, raising urges
The efficiency of agent.
(2) using the method for mixing in situ, titanium atom and tungsten atom is mixed in atomic level, cause follow-up co-precipitation
During the crystal that produces, lattice defect is more, and mixed-metal oxides particle diameter is small and homogeneous, bigger than surface, improves simultaneously
Turn brilliant temperature of titanium dioxide crystal, beneficial to the performance of catalytic activity；
(3) method mixed using ultrasonic assistant, is more uniformly distributed the mixing of various materials atomic level；
(4) vanadium source is added when titanium source, tungsten source co-precipitation material are not calcined, and vanadium source is deeper in titanium-tungsten particle surface penetration,
Connection is closer, disperses evenly, fired rear catalyst activity is more stable；
(5) the vanadium tungsten titanium powder material prepared entered after once roasting, and covered one layer of molybdenum oxide on its surface, while plus
Pore creating material is entered, has made catalyst particle surface that there are more molybdenum oxides to adhere to, while also possessing abundant spatial network shape nanometer
Level micropore, can both resist barium oxide in flue gas, in its surface nonuniform deposition, can ensure high catalyst performance again；
(6) after shaping of catalyst is dried, one layer of nanoscale tungsten is applied on its surface, the performance of catalyst is improved.
Embodiment
Embodiments of the invention are elaborated below：The present embodiment is carried out lower premised on technical solution of the present invention
Implement, give detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
The experimental method of unreceipted actual conditions in example, generally according to normal condition.
Titanium source precursor solution：
In the present invention, solution is formed in titanium source presoma vitriolization, there is no particular restriction to titanium source presoma, generally limit
It is set in titanyl sulfate or metatitanic acid, titanium source precursor solution with TiO2Meter, titanium source presoma content is 15~40g/L.If small
In 15g/L, then solution is too dilute, and the combination of other materials is more loose, and production efficiency is relatively low；If more than 40g/L, due to dense
Du Taigao and reduced with the mixing intensities of other materials, cause fusion bad.
Catalyst sample and catalytic cracking spent catalyst hybrid technique：Screening takes 20 after the fresh catalyst of preparation is crushed
~40 mesh powders；Vanadium in 40~60 mesh powders, catalytic cracking spent catalyst is taken after catalytic cracking spent catalyst (LDC series) screening
Oxide content about 1%.Two kinds of powders in mass ratio 1:1 mixing, in air atmosphere, at 350 DEG C, mixes 24h, sieves afterwards
Go out catalyst powder to be evaluated.Fresh catalyst is contacted in mixed process with waste acetic acid, can be split useless catalysis
Change catalyst in active material vanadium it is uneven be transferred on fresh catalyst, cause fresh catalyst surface reactive material vanadium
Oxide concentrates accumulation, causes catalyst Topically active to strengthen, and then can increase the SO of catalyst2/SO3Conversion ratio, reduces denitration
Catalyst overall performance.
NOxConversion ratio appreciation condition：Air speed 20000h-1, 350 DEG C of reaction temperature, air inlet NOxFor 600mg/Nm3、SO2For
1000mg/Nm3, ammonia nitrogen ratio be that 1, water content is 10%.
NOx、SO2Method for measurement of concentration：Flue gas continuous on-line analysis instrument, Siemens ULTRAMAT23.
SO2/SO3Conversion ratio assay method：Wet desulfurization of flue gas by limestone-gypsum method device performance acceptance test specification (DL/
T998-2006)。
Cocoanut active charcoal：The mesh of granularity 300, specific surface area 8000m2/ g, pore volume 1.0cm3/g
Wood activated charcoal：The mesh of granularity 300, specific surface area 600m2/ g, pore volume 0.60cm3/g
Following examples are that the present invention is illustrated, and " % " described in embodiment and comparative example refers to quality percentage and contained
Amount.
Embodiment 1：
20g cocoanut active charcoals are added in glucose solution, mashing forms slurries after mixing fully, and will contain with TiO2
Meter 500g titanyl sulfate is dissolved in sulfuric acid solution, is formed and is contained TiO2For 35g/L solution, add and contain with WO3Count 10g secondary tungsten
Ammoniacal liquor is gradually added after acid ammonium solution, supersonic oscillations 2h and adjusts pH value to 9.5, after precipitation is complete, filtering, washing；It will wash again
Wash rear material and spend ion water making into the slurry that moisture content is 50%, add with V2O5Count 5g ammonium metavanadate solution, stirring it is same
When supersonic oscillations 1.5h, after convection drying, using nitrogen environment in 620 DEG C of roasting temperature 6h；After roasting powder again with
MoO3Meter 10g ammonium molybdate is configured to aqueous 30% slurry, and 4g sesbania powders, stirring 40min, sealing and standing are added after stirring
24h, be squeezed into it is cellular after dry after coating nanometer level tungsten oxide 15g, 8h is calcined at 600 DEG C using nitrogen environment after taken off
Denox catalyst.Specific surface area of catalyst 144m2/g.Above-mentioned gained fresh catalyst and high with catalytic cracking vanadium-containing wasting catalyst
Temperature mixing rear catalyst is evaluated respectively, the results are shown in Table 1 data.
Comparative example 1：
Activated carbon is added without in catalyst manufacturing process, will be contained with TiO2Meter 500g titanyl sulfate is dissolved in sulfuric acid
In solution, formed and contain TiO2For 35g/L solution, add and contain with WO3Count after 10g secondary tungsten acid ammonium solution, supersonic oscillations 2h progressively
Add ammoniacal liquor and adjust pH value to 9.5, after precipitation is complete, filtering, washing；Material after washing is spent into ion water making into moisture content again
For 50% slurry, add with V2O5Count after 5g ammonium metavanadate solution, supersonic oscillations 1.5h while stirring, convection drying,
Using nitrogen environment in 620 DEG C of roasting temperature 6h；After roasting powder again with MoO3Meter 10g ammonium molybdate is configured to aqueous
30% slurry, adds 4g sesbania powders after stirring, stir 40min, sealing and standing 24h, be squeezed into coating after cellular rear drying
Nanoscale tungsten 15g, using nitrogen environment 600 DEG C be calcined 8h after obtain denitrating catalyst.The specific surface area of catalyst
121m2/g.Above-mentioned gained fresh catalyst and evaluate, tie respectively with catalytic cracking vanadium-containing wasting catalyst high temperature mixing rear catalyst
Fruit is shown in Table 1 data.
Embodiment 2
15g cocoanut active charcoals are added in glucose solution, mashing forms slurries after mixing fully, and will contain with TiO2
Meter 500g titanyl sulfate is dissolved in sulfuric acid solution, is formed and is contained TiO2For 35g/L solution, add and contain with WO3Count 20g secondary tungsten
Ammoniacal liquor is gradually added after acid ammonium solution, mechanical agitation 2h and adjusts pH value to 9.0, after precipitation is complete, filtering, washing；Again will washing
Material spends ion water making into the slurry that moisture content is 50% afterwards, adds with V2O5Count 10g ammonium metavanadate solution, mechanical agitation
After 1.5h, convection drying, using nitrogen environment in 500 DEG C of roasting temperature 6h；After roasting powder again with MoO3Count 2.5g's
Ammonium molybdate is configured to aqueous 30% slurry, and 3g sesbania powders are added after stirring, stirs 40min, sealing and standing 10h, is squeezed into honeybee
Coating nanometer level tungsten oxide 18g after being dried after nest shape, 8h is calcined at 550 DEG C using nitrogen environment after obtain denitrating catalyst.On
State gained fresh catalyst and evaluated respectively with catalytic cracking vanadium-containing wasting catalyst high temperature mixing rear catalyst, the results are shown in Table 1 number
According to.
Comparative example 2
Activated carbon does not use sugared leaching in catalyst manufacturing process, will contain and be added to the water 15g cocoanut active charcoals, mixing
Mashing forms slurries after fully, and will contain with TiO2Meter 500g titanyl sulfate is dissolved in sulfuric acid solution, is formed and is contained TiO2For
35g/L solution, adds and contains with WO3Count 20g secondary tungsten acid ammonium solution, be gradually added after mechanical agitation 2h ammoniacal liquor adjust pH value to
9.0, after precipitation is complete, filtering, washing；Material after washing is spent into ion water making into the slurry that moisture content is 50% again, added
With V2O5Count after 10g ammonium metavanadate solution, mechanical agitation 1.5h, convection drying, roasted using nitrogen environment at a temperature of 500 DEG C
Burn 6h；After roasting powder again with MoO3Meter 2.5g ammonium molybdate is configured to aqueous 30% slurry, and 3g sesbanias are added after stirring
Powder, stirs 40min, sealing and standing 10h, is squeezed into coating nanometer level tungsten oxide 18g after cellular rear drying, using nitrogen environment
Denitrating catalyst is obtained after being calcined 8h at 550 DEG C.Specific surface area of catalyst 147m2/g.Above-mentioned gained fresh catalyst and with
Catalytic cracking vanadium-containing wasting catalyst high temperature mixing rear catalyst is evaluated respectively, the results are shown in Table 1 data.
Embodiment 3
20g cocoanut active charcoals are added in glucose solution, mashing forms slurries after mixing fully, and will contain with TiO2
Meter 500g titanyl sulfate is dissolved in sulfuric acid solution, is formed and is contained TiO2For 40g/L solution, add and contain with WO3Count 15g secondary tungsten
Ammoniacal liquor is gradually added after acid ammonium solution, supersonic oscillations 1h and adjusts pH value to 9.0, after precipitation is complete, filtering, washing；It will wash again
Wash rear material and spend ion water making into the slurry that moisture content is 50%, add with V2O520g ammonium metavanadate solution is counted, stirring
While after supersonic oscillations 1.5h, convection drying, using nitrogen environment in 400 DEG C of roasting temperature 6h；After roasting powder again with
With MoO3Meter 3g ammonium molybdate is configured to aqueous 30% slurry, and 4g sesbania powders, stirring 40min, sealing and standing are added after stirring
10h, be squeezed into it is cellular after dry after coating nanometer level tungsten oxide 25g, 8h is calcined at 500 DEG C using nitrogen environment after taken off
Denox catalyst.Above-mentioned gained fresh catalyst and evaluated respectively with catalytic cracking vanadium-containing wasting catalyst high temperature mixing rear catalyst,
It the results are shown in Table 1 data.
Comparative example 3
Nanoscale tungsten is added without in catalyst preparation process, i.e., 20g cocoanut active charcoals are added into glucose solution
In, mashing forms slurries after mixing fully, and will contain with TiO2Meter 500g titanyl sulfate is dissolved in sulfuric acid solution, is formed
Containing TiO2For 40g/L solution, add and contain with WO3Count and ammoniacal liquor tune is gradually added after 40g secondary tungsten acid ammonium solution, supersonic oscillations 1h
PH value is saved to 9.0, after precipitation is complete, filtering, washing；Material after washing is spent into ion water making into the slurry that moisture content is 50% again
Material, is added with V2O5Count after 20g ammonium metavanadate solution, supersonic oscillations 1.5h while stirring, convection drying, using nitrogen
Environment is in 400 DEG C of roasting temperature 6h；After roasting powder again with MoO3Meter 3g ammonium molybdate is configured to aqueous 30% slurry,
After stirring add 4g sesbania powders, stirring 40min, sealing and standing 10h, be squeezed into it is cellular after drying, using nitrogen environment 500
DEG C roasting 8h after obtain denitrating catalyst.Above-mentioned gained fresh catalyst and after being mixed with catalytic cracking vanadium-containing wasting catalyst high temperature
Catalyst is evaluated respectively, the results are shown in Table 1 data.
Embodiment 4
20g cocoanut active charcoals are added in glucose solution, mashing forms slurries after mixing fully, and will contain with TiO2
Meter 500g titanyl sulfate is dissolved in sulfuric acid solution, is formed and is contained TiO2For 40g/L solution, add and contain with WO3Count the secondary of 12.5g
Ammoniacal liquor is gradually added after ammonium tungstate solution, supersonic oscillations 3h and adjusts pH value to 10.5, after precipitation is complete, filtering, washing；Again will
Material spends ion water making into the slurry that moisture content is 35% after washing, adds with V2O5Count 30g ammonium metavanadate solution, stirring
While supersonic oscillations 1.5h, after convection drying, using nitrogen environment in 400 DEG C of roasting temperature 6h；Powder is again after roasting
With with MoO3Meter 3g ammonium molybdate is configured to aqueous 30% slurry, and 4g sesbania powders are added after stirring, and stirring 40min, sealing are quiet
10h is put, coating nanometer level tungsten oxide 25g after cellular rear drying is squeezed into, is obtained using nitrogen environment after 500 DEG C of roasting 8h
Denitrating catalyst.Above-mentioned gained fresh catalyst and commented respectively with catalytic cracking vanadium-containing wasting catalyst high temperature mixing rear catalyst
Valency, the results are shown in Table 1 data.
Comparative example 4
Vanadium source is added after being calcined in first time, i.e., add 20g cocoanut active charcoals in glucose solution, is beaten after mixing fully
Slurry forms slurries, and will contain with TiO2Meter 500g titanyl sulfate is dissolved in sulfuric acid solution, is formed and is contained TiO2It is molten for 40g/L
Liquid, adds and contains with WO3Count and ammoniacal liquor regulation pH value be gradually added after 12.5g secondary tungsten acid ammonium solution, supersonic oscillations 3h to 10.5,
After precipitation is complete, after filtering, washing are dried, using nitrogen environment in 400 DEG C of roasting temperature 6h；After roasting powder again with
MoO3Meter 3g ammonium molybdate is configured to aqueous 30% slurry, and adds with V2O5Meter 30g ammonium metavanadate solution is made aqueous
30% slurry, adds 4g sesbania powders after stirring, stir 40min, sealing and standing 10h, be squeezed into coating after cellular rear drying
Nanoscale tungsten 25g, using nitrogen environment 500 DEG C be calcined 8h after obtain denitrating catalyst.Above-mentioned gained fresh catalyst
And evaluated respectively with catalytic cracking vanadium-containing wasting catalyst high temperature mixing rear catalyst, it the results are shown in Table 1 data.
Embodiment 5
25g cocoanut active charcoals are added in glucose solution, mashing forms slurries after mixing fully, and will contain with TiO2
Meter 500g titanyl sulfate is dissolved in sulfuric acid solution, is formed and is contained TiO2For 40g/L solution, add and contain with WO3Count 25g secondary tungsten
Ammoniacal liquor is gradually added after acid ammonium solution, mechanical agitation 3h and adjusts pH value to 10.5, after precipitation is complete, filtering, washing；Again will washing
Material spends ion water making into the slurry that moisture content is 35% afterwards, adds with V2O5Count 30g ammonium metavanadate solution, stirring it is same
When supersonic oscillations 0.5h, after convection drying, using nitrogen environment in 650 DEG C of roasting temperature 6h；After roasting powder again with
MoO3Meter 2.5g ammonium molybdate is configured to aqueous 30% slurry, and 2.5g sesbania powders are added after stirring, and stirring 40min, sealing are quiet
10h is put, coating nanometer level tungsten oxide 15g after cellular rear drying is squeezed into, is obtained using nitrogen environment after 650 DEG C of roasting 8h
Denitrating catalyst.Above-mentioned gained fresh catalyst and commented respectively with catalytic cracking vanadium-containing wasting catalyst high temperature mixing rear catalyst
Valency, the results are shown in Table 1 data.
Comparative example 5
The process of catalyst is prepared only with being once calcined, i.e., is added 25g cocoanut active charcoals in glucose solution, mixing
Mashing forms slurries after fully, and will contain with TiO2Meter 500g titanyl sulfate is dissolved in sulfuric acid solution, is formed and is contained TiO2For
40g/L solution, adds and contains with WO3Count 25g secondary tungsten acid ammonium solution, be gradually added after mechanical agitation 3h ammoniacal liquor adjust pH value to
10.5, after precipitation is complete, filtering, washing；Material after washing is spent into ion water making into the slurry that moisture content is 35% again, added
With V2O5Count 30g ammonium metavanadate solution, supersonic oscillations 0.5h while stirring, then with MoO3Meter 2.5g ammonium molybdate is matched somebody with somebody
Aqueous 30% slurry is made, after stirring add 2.5g sesbania powders, stirring 40min, sealing and standing 10h, be squeezed into it is cellular after
Coating nanometer level tungsten oxide 15g after drying, 8h is calcined at 650 DEG C using nitrogen environment after obtain denitrating catalyst.Above-mentioned gained
Fresh catalyst and evaluated respectively with catalytic cracking vanadium-containing wasting catalyst high temperature mixing rear catalyst, the results are shown in Table 1 data.
Embodiment 6
5g cocoanut active charcoals are added in glucose solution, mashing forms slurries after mixing fully, and will contain with TiO2
Meter 500g titanyl sulfate is dissolved in sulfuric acid solution, is formed and is contained TiO2For 35g/L solution, add and contain with WO3Count 10g secondary tungsten
Ammoniacal liquor is gradually added after acid ammonium solution, supersonic oscillations 0.5h and adjusts pH value to 9.0, after precipitation is complete, filtering, washing；Again will
Material spends ion water making into the slurry that moisture content is 35% after washing, adds with V2O55g ammonium metavanadate solution is counted, stirring
While after supersonic oscillations 0.5h, convection drying, using nitrogen environment in 400 DEG C of roasting temperature 6h；After roasting powder again with
With MoO3Meter 10g ammonium molybdate is configured to aqueous 35% slurry, and 7.5g sesbania powders are added after stirring, and stirring 40min, sealing are quiet
10h is put, coating nanometer level tungsten oxide 30g after cellular rear drying is squeezed into, is obtained using nitrogen environment after 400 DEG C of roasting 8h
Denitrating catalyst.Above-mentioned gained fresh catalyst and commented respectively with catalytic cracking vanadium-containing wasting catalyst high temperature mixing rear catalyst
Valency, the results are shown in Table 1 data.
Comparative example 6
Pore creating material is added without after being once calcined, i.e., is added 5g cocoanut active charcoals in glucose solution, is beaten after mixing fully
Slurry forms slurries, and will contain with TiO2Meter 500g titanyl sulfate is dissolved in sulfuric acid solution, is formed and is contained TiO2It is molten for 35g/L
Liquid, adds and contains with WO3Count and ammoniacal liquor regulation pH value is gradually added after 10g secondary tungsten acid ammonium solution, mechanical agitation 0.5h to 9.0, sink
After forming sediment completely, filtering, washing；Material after washing is spent into ion water making into the slurry that moisture content is 35% again, added with V2O5Meter
After 5g ammonium metavanadate solution, mechanical agitation 0.5h, convection drying, using nitrogen environment in 400 DEG C of roasting temperature 6h；Roasting
Afterwards powder again with MoO3Meter 10g ammonium molybdate is configured to aqueous 35% slurry, stirring 40min, sealing and standing 10h, extruding
Into after drying after cellular coating nanometer level tungsten oxide 30g, 8h is calcined at 400 DEG C using nitrogen environment after obtain denitration catalyst
Agent.Above-mentioned gained fresh catalyst and evaluate, as a result seen respectively with catalytic cracking vanadium-containing wasting catalyst high temperature mixing rear catalyst
The data of table 1.
Embodiment 7
12.5g cocoanut active charcoals are added in glucose solution, mashing forms slurries after mixing fully, and will contain with
TiO2Meter 500g titanyl sulfate is dissolved in sulfuric acid solution, is formed and is contained TiO2For 35g/L solution, add and contain with WO3Count 17.5g
Secondary tungsten acid ammonium solution, ammoniacal liquor is gradually added after mechanical agitation 2h and adjusts pH value to 9.5, precipitation completely after, filtering, washing；Again
Material after washing is spent into ion water making into the slurry that moisture content is 40%, added with V2O515g ammonium metavanadate solution is counted, is stirred
After supersonic oscillations 2h while mixing, convection drying, using nitrogen environment in 530 DEG C of roasting temperature 6h；Powder is again after roasting
With with MoO3Meter 5g ammonium molybdate is configured to aqueous 35% slurry, and 5g sesbania powders are added after stirring, and stirring 40min, sealing are quiet
20h is put, coating nanometer level tungsten oxide 20g after cellular rear drying is squeezed into, is obtained using nitrogen environment after 520 DEG C of roasting 8h
Denitrating catalyst.Above-mentioned gained fresh catalyst and commented respectively with catalytic cracking vanadium-containing wasting catalyst high temperature mixing rear catalyst
Valency, the results are shown in Table 1 data.
The embodiment of table 1 and comparative example evaluating data contrast table
Found by embodiment and comparative example：The denitrating catalyst that the resistance vanadium deposition of embodiment is uneven has good effect
Really, it is preliminary by ultrasonic wave mixing in situ, the mixing rank of active material is reached molecule rank, slightly evacuated through co-precipitation
Nano particle, then introduce barium oxide in particle surface and shallow-layer, catalyst intermediate obtained after roasting, then in pore creating material
In the presence of strengthen NO in final catalyst, evaluating catalyst is produced after introducing co-catalyst, roasting againxConversion ratio in ammonia nitrogen
Than for 1 when, up to more than 99%, through with after catalytic cracking vanadium-containing wasting catalyst mixed processing, SO2/SO3Conversion ratio does not almost have
Increase, illustrates that catalyst surface does not almost produce the polycrystalline deposition of barium oxide, catalyst performance is excellent；Denitrating catalyst system
In Preparation Method, if being handled without (6) step, only retain vanadium tungsten titanium catalyst sample after being calcined for the first time, it is useless containing vanadium through catalytic cracking
After catalyst mixed processing, SO2/SO3Conversion ratio has increased slightly；If being not added with pore creating material in the processing of (6) step, contain through catalytic cracking
After vanadium dead catalyst mixed processing, SO2/SO3Conversion ratio also has increased slightly；If catalyst is in preparation process, using being once calcined
Form, or vanadium source is added after being once calcined, catalyst NO in evaluation procedurexConversion ratio be slightly decreased, while SO2/
SO3Conversion ratio also has increased slightly.In a word, the catalyst after the fresh denitrating catalyst for preparing of the present invention and processing is with the conditions of
During evaluation, SO2/SO3Conversion ratio is lower than other comparative examples, with barium oxide nonuniform deposition in good anti-flue gas
Effect.
It can be seen from embodiment and comparative example specific surface area degrees of data by activated carbon after sugar processing, catalyst ratio
Surface area is significantly increased, and catalytic efficiency is further improved.
Beneficial effects of the present invention：
(1) in catalyst preparation process of the present invention, using activated carbon, beaten again after handling activated carbon in particular by carbohydrate
Slurry, carbohydrate is adsorbed in activated carbon, and by follow-up roasting, the carbohydrate breakdown in the middle of activated carbon is carbonized to form new unformed titanium
The combination of tungsten is closer, and the carbohydrate activated carbon interior trim surface new through being decomposed to form, adds table in activated carbon on activated carbon endoporus
The active sites in face.Therefore, carbohydrate processing activated carbon, can promote the even closer parcel activated carbon of amorphous titanium oxide, tungsten oxide,
Catalyst strength is improved, while improving specific surface area of catalyst and porosity, the efficiency of catalyst is improved.
(2) using the method for mixing in situ, titanium atom and tungsten atom is mixed in atomic level, cause follow-up co-precipitation
During the crystal that produces, lattice defect is more, and mixed-metal oxides particle diameter is small and homogeneous, bigger than surface, improves simultaneously
Turn brilliant temperature of titanium dioxide crystal, beneficial to the performance of catalytic activity；
(3) method mixed using ultrasonic assistant, is more uniformly distributed the mixing of various materials atomic level；
(4) vanadium source is added when titanium source, tungsten source co-precipitation material are not calcined, and vanadium source is deeper in titanium-tungsten particle surface penetration,
Connection is closer, disperses evenly, fired rear catalyst activity is more stable；
(5) the vanadium tungsten titanium powder material prepared entered after once roasting, and covered one layer of molybdenum oxide on its surface, while plus
Pore creating material is entered, has made catalyst particle surface that there are more molybdenum oxides to adhere to, while also possessing abundant spatial network shape nanometer
Level micropore and higher crushing strength, can both resist barium oxide in flue gas, in its surface nonuniform deposition, can protect again
The high catalyst performance of card.
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (10)
1. a kind of preparation method for the Faveolate denitration catalyst for improving specific surface area, it is characterised in that preparation method includes
Following steps：
(1) activated carbon is mixed with saccharide solution, be then beaten；
(2) titanium source presoma is dissolved to form solution；
(3) tungsten source presoma is dissolved, and it is well mixed with the material of step (1), (2)；
(4) the well mixed rear solution of step (3) is adjusted into pH value to 8~13, precipitated, filter cake is washed to obtain in filtering；
(5) deionized water is added in filter cake obtained by step (4), is tuned into pulpous state, added vanadium source precursor solution, be well mixed
Afterwards, it is dried, is then calcined again under inert gas shielding, forms powder；
(6) the powder mixing pulp of the solution for forming molybdenum source presoma and step (5), after stirring, plus pore creating material, it is secondary
After stirring, extruding is in cellular after sealing and standing, and coating nanometer level tungsten oxide, the lower roasting of noble gas protection, form denitration after drying
Catalyst.
2. preparation method according to claim 1, it is characterised in that the activated carbon described in step (1) can be first with common living
Property charcoal commodity, can be wood activated charcoal, or the activated carbon of shell class, used activated carbon be Powdered Activated Carbon,
Granularity is 10~500 mesh, and preferably 180~300 mesh, specific surface area is 600~2000m2/ g, 0.60~1.6cm of pore volume3/g。
3. preparation method according to claim 1, it is characterised in that carbohydrate described in step (1) for monosaccharide and disaccharide and
One or more in polysaccharide, preferably carbon atom are 1~18 carbohydrate, more preferably one or both of sucrose and glucose；
The quality of the carbohydrate accounts for the 3~40% of the quality of activated carbon, preferably 10~20%；Sugar can be dissolved in after water by the processing of carbohydrate
Activated carbon is added to be well mixed.
4. preparation method according to claim 1, it is characterised in that titanium source presoma is with TiO2Meter, step (1) is described
Quality of activated carbon and titanium source forerunner body mass ratio be 1~20:100.
5. preparation method according to claim 1, it is characterised in that in step (3), tungsten source presoma is with WO3Meter, titanium
Source presoma is with TiO2The mass ratio of meter, tungsten source used presoma and titanium source presoma is 2.0~5.0:100.
6. preparation method according to claim 1, it is characterised in that in the step (3), step (5) and step (6)
Hybrid mode be mechanical agitation mixing, fluid dynamic mixing or and supersonic oscillations mixing, step (3) and step (5) are mixed
The conjunction time is 0.5~3h, and the incorporation time of step (6) is 10~60min, and the sealing and standing time of step (6) is 8~30h.
7. preparation method according to claim 1, it is characterised in that the vanadium source presoma in the step (5) is with V2O5
Meter, the titanium source presoma is with TiO2The mass ratio of meter, vanadium source presoma consumption and titanium source presoma consumption is 1~6:100.
8. preparation method according to claim 1, it is characterised in that titanium source presoma is with TiO in the step (6)2
Meter, the addition of nanometer tungsten oxide is 3~6 with the mass ratio of titanium source presoma:100.
9. preparation method according to claim 1, it is characterised in that sintering temperature in the step (5) and step (6)
It it is 400~650 DEG C, roasting time is 4~10h.
10. preparation method according to claim 1, it is characterised in that the pore creating material added in the step (6) is
One or more in urea, polyoxyethylene, sesbania powder, the addition of pore creating material and the mass ratio of titanium source presoma be 0.5~
1.5:100。
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