CN106861673B - Denitration catalyst and preparation method thereof - Google Patents
Denitration catalyst and preparation method thereof Download PDFInfo
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- CN106861673B CN106861673B CN201510923102.5A CN201510923102A CN106861673B CN 106861673 B CN106861673 B CN 106861673B CN 201510923102 A CN201510923102 A CN 201510923102A CN 106861673 B CN106861673 B CN 106861673B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 118
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 33
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 239000002002 slurry Substances 0.000 claims abstract description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 21
- 230000010355 oscillation Effects 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 21
- 239000010936 titanium Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 18
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 14
- 239000010937 tungsten Substances 0.000 claims abstract description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 238000007789 sealing Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 3
- 239000012065 filter cake Substances 0.000 claims abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 16
- 239000002202 Polyethylene glycol Substances 0.000 claims description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims description 15
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 11
- 239000000908 ammonium hydroxide Substances 0.000 claims description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- 238000012644 addition polymerization Methods 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 206010001497 Agitation Diseases 0.000 claims 1
- 238000013019 agitation Methods 0.000 claims 1
- ZYPJORZNHDXKSD-UHFFFAOYSA-N oxotitanium;sulfuric acid Chemical compound [Ti]=O.OS(O)(=O)=O ZYPJORZNHDXKSD-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 16
- 239000003546 flue gas Substances 0.000 abstract description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 11
- 230000008021 deposition Effects 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical group [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 abstract 2
- 229910001935 vanadium oxide Inorganic materials 0.000 abstract 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 abstract 1
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 33
- 239000000463 material Substances 0.000 description 22
- 238000004523 catalytic cracking Methods 0.000 description 15
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 14
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 150000003863 ammonium salts Chemical class 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 6
- 238000000975 co-precipitation Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000012266 salt solution Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005360 mashing Methods 0.000 description 3
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical compound [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 description 3
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method 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
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000003365 glass fiber 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
- 238000010438 heat treatment Methods 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
- 238000004519 manufacturing process 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
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- IBYSTTGVDIFUAY-UHFFFAOYSA-N vanadium monoxide Chemical compound [V]=O IBYSTTGVDIFUAY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
-
- 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
- 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
-
- 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)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (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)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a denitration catalyst and a preparation method thereof, wherein (1) a titanium source precursor is dissolved in sulfuric acid to form a solution; (2) dissolving a tungsten source precursor in water, and adding the tungsten source precursor into the solution obtained in the step (1); (3) after the solution obtained in the step (2) is subjected to ultrasonic oscillation, ammonia water is used for adjusting the pH value to be more than 9.0, and precipitation, filtration and washing are carried out; (4) adding deionized water into the filter cake obtained in the step (3), adjusting into slurry, adding a vanadium source precursor solution, and directly drying and roasting after ultrasonic oscillation to form powder; and (5) mixing the powder in the step (4) and an ammonium metatungstate solution into slurry, stirring, adding polyethylene oxide, stirring for the second time, sealing, standing, drying and roasting to form the denitration catalyst. The denitration catalyst prepared by the invention can resist the uneven deposition of vanadium oxide on the surface of the vanadium oxide in flue gas, can ensure high catalyst performance, and has relatively stable catalytic performance.
Description
Technical field
The present invention relates to a kind of preparation method of catalyst for denitrating flue gas, vanadium is deposited not in especially a kind of resistance flue gas
Equal denitrating catalyst preparation method, the invention belong to New Inorganic Materials technical field.
Background technique
Nitrogen oxides (NOx) it is one of main atmosphere pollution, emission request is increasingly strict.China's " " 12th Five-Year Plan " section
Can emission reduction comprehensive programme of work " in regulation: by 2015, the decline 10% in than 2010 of national discharged nitrous oxides total amount.
The GB13223-2001 " fossil-fuel power plant atmospheric pollutant emission standard " that 2011 Nian9Yue State Ministry of Environmental Protection promulgate arranges thermal power plant NOx
Put concentration and made more strict requirements: the regulation third period is newly-built, extends, the coal-burning boiler of reconstruction, and NOx highest allows to discharge
Concentration is 100mg/m3." petroleum refining industry pollutant emission standard " requirement that State Ministry of Environmental Protection promulgates: on July 1st, 2015
It rises, creates nitrogen oxides in catalytic cracking unit discharge regenerated flue gas and require to be less than 200mg/m3, special emission limit requires small
In 100mg/m3, on July 1st, 2017, existing enterprise also executed the standard.In numerous gas denitrifying technologies, selective catalysis is also
Former method (Selective Catalytic Reduction, SCR) is the technology for being still international mainstream, NOxRemoval efficiency is reachable
To 80%~90%.Wherein, denitrating catalyst is the core of SCR technology, and developed country just has developed in the eighties in last century
For a series of denitrating catalysts of coal characteristics, boiler type etc., many R&D institutions, China and enterprise are coal-fired for China
Boiler and catalytic cracking flue gas situation have also carried out a series of research, and develop some denitrating catalysts.
CN201010537130 proposes the method for preparing denitrating catalyst using hydrothermal method, first by titanium source presoma
It is mixed with tungsten source presoma, is placed in autoclave and carries out hydro-thermal reaction, be filtered, washed and dried to obtain titanium tungsten powder denitration catalyst
Agent, while the elements such as vanadium and molybdenum can be also introduced, prepare multi-metal-oxide catalyst.The catalyst activity component of this method preparation
Crystal grain is small, specific surface area is larger, but since by being sufficiently mixed process, it is higher not may cause material aggregation extent of the same race
Phenomenon occurs, and has certain influence to catalyst activity.
CN201110345605 proposes a kind of preparation method of denitrating catalyst, sequentially adds tungsten into metatitanic acid slurry
Sour ammonium, ammonium molybdate and ammonium metavanadate, ultrasonic wave mashing, then pH value is adjusted to 4.0~6.5, it stands, separate, drying is catalyzed
Agent powder.It is this method simple process, at low cost, but ammonium metavanadate is added with solid, the dissolubility of vanadium is still to be tested, vanadium dispersion
Although activity very high, SO when uneven2/SO3Conversion ratio can be higher, influences catalyst service 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 simple process, but titanium-tungsten
Mixing intensity is lower, can have a certain impact to the performance of material.
In conclusion 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 90% or more, illustrate special metal oxygen
The catalytic activity of compound is higher, and dispersion unevenness can still obtain higher NOxConversion ratio.The superiority and inferiority of catalyst overall performance is also
It needs to be verified from otherwise characterization, while the preparation of catalyst will also take into account the operability of industry amplification.
Summary of the invention
The main purpose of the present invention is to provide a kind of denitrating catalysts and preparation method thereof, are taken off in the prior art with overcoming
Denox catalyst activated centre in high-temperature flue gas is unbalanced, the unstable defect of activity.
The object of the present invention is achieved like this, and a kind of preparation method of denitrating catalyst, this method comprises the following steps:
(1) titanium source presoma vitriolization is formed into solution；
(2) tungsten source presoma is soluble in water, and add it in the solution of step (1)；
(3) after to step (2) acquired solution supersonic oscillations, pH value to more than 9.0 is adjusted with ammonium hydroxide, is precipitated, filtering is washed
It washs；
(4) deionized water is added in the filter cake obtained by step (3), is tuned into pulpous state, vanadium source precursor solution, ultrasonic wave is added
It after oscillation, is directly dried, roasts, form powder；And
(5) by the powder of step (4) and ammonium metatungstate solution mixing pulp, after stirring, addition polymerization ethylene oxide is secondary
After stirring, sealing and standing, drying, roasting form denitrating catalyst.
The preparation method of denitrating catalyst of the present invention, wherein the titanium source presoma be preferably titanyl sulfate or
Metatitanic acid, the step (1) form solution with TiO2Meter, content is preferably 15~40g/L.
The preparation method of denitrating catalyst of the present invention, wherein tungsten source presoma be preferably ammonium paratungstate or
Ammonium metatungstate, the step (2) obtains in solution, with WO3And TiO2Mass ratio meter, preferably 2.0~5.0:100.
The preparation method of denitrating catalyst of the present invention, wherein ultrasonic wave shakes in the step (3) and step (4)
Swinging the time is both preferably 0.5~3h, and mixing time is both preferably 10~60min in the step (5), close in the step (5)
Sealing time of repose is preferably 8~30h.
The preparation method of denitrating catalyst of the present invention, wherein vanadium source presoma in the precursor solution of the vanadium source
Preferably ammonium metavanadate, the vanadium source presoma dosage is with V2O5Meter, the titanium source presoma dosage is with TiO2Meter, V2O5And TiO2
Mass ratio is preferably 0.5~2.0:100.
The preparation method of denitrating catalyst of the present invention, wherein slurry water content is preferably in the step (4)
35~55%.
The preparation method of denitrating catalyst of the present invention, wherein the dosage of ammonium metatungstate solution in the step (5)
With WO3Meter, the titanium source presoma dosage is with TiO2Meter, WO3And TiO2Mass ratio is preferably 0.5~2.0:100.
The preparation method of denitrating catalyst of the present invention, wherein slurry water content is preferably in the step (5)
25~40%.
The preparation method of denitrating catalyst of the present invention, wherein the titanium source presoma dosage is with TiO2Meter, it is described
The additional amount of polyethylene glycol oxide in step (5), with and TiO2Mass ratio indicate be preferably 0.3~1.0:100.
The preparation method of denitrating catalyst of the present invention, wherein maturing temperature in the step (4) and step (5)
Both preferably 400~650 DEG C, calcining time is both preferably 4~10h.
It is prepared by the preparation method of above-mentioned denitrating catalyst the present invention also provides a kind of denitrating catalyst.
Beneficial effects of the present invention:
(1) using the method mixed in situ, titanium atom and tungsten atom is mixed in molecule rank, causes subsequent co-precipitation
The crystal generated in the process, lattice defect is more, and mixed-metal oxides partial size is small and uniform, and specific surface is big, improves simultaneously
Titanium dioxide crystal turns brilliant temperature, conducive to the performance of catalytic activity；
(2) mixed method is assisted using ultrasonic wave, keeps the mixing of various materials atomic level more uniform；
(3) vanadium source addition when titanium dioxide-tungstic acid co-precipitation material does not roast, in titanium-tungsten particle surface penetration
Deeper, connection is closer, and dispersion more evenly, it is more stable to be fired rear catalyst activity；
(4) the vanadium tungsten titanium powder material prepared covers one layer of tungstic acid into after once roasting excessively, and on its surface, simultaneously
It joined polyethylene glycol oxide, possess catalyst particle surface also while there is the attachment of more tungsten oxides nanometer level microporous, both
Barium oxide can be resisted in flue gas in its surface nonuniform deposition, and can guarantee high catalyst performance.
Specific embodiment
Elaborate below to the embodiment of the present invention: the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually 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, usually limits
It is set to titanyl sulfate or metatitanic acid, with TiO in titanium source precursor solution2Meter, titanium source presoma content are 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 lower；If more than 40g/L, then due to dense
Du Taigao and with the mixing intensity of other materials reduce, cause to merge bad.
Each material proportion in denitrating catalyst:
In the present invention, denitrating catalyst mainly includes titanium source presoma, tungsten source presoma, vanadium source presoma, ammonium metatungstate
And polyethylene glycol oxide, respectively with TiO2、WO3、V2O5、WO3, polyethylene glycol oxide note, mass ratio be 100:2.0~5.0:0.5~
2.0:0.5~2.0:0.3~1.0 will affect the dispersion of active material vanadium, lead to catalyst performance if tungsten source presoma is less
It can be poor；If ammonium metatungstate is less, lead to that SO cannot be effectively reduced2/SO3Conversion ratio；It, can shadow if polyethylene glycol oxide amount is more
Tungstic acid is rung in the absorption of particle surface, influences catalyst surface porosity if very little.
Catalyst sample and catalytic cracking spent catalyst hybrid technique: screening takes 20 after the fresh catalyst of preparation is crushed
~40 mesh powders；40~60 mesh powders are taken after catalytic cracking spent catalyst screening, barium oxide contains in catalytic cracking spent catalyst
Amount about 1%.Two kinds of powders 1:1 in mass ratio mixing, in air atmosphere, at 350 DEG C, mixing for 24 hours, screens out catalyst later
Powder is evaluated.It, can be by waste acetic acid in fresh catalyst and waste acetic acid contact mixed process
In active material vanadium it is non-uniform be transferred on fresh catalyst, lead to fresh catalyst surface reactive material barium oxide collection
Middle accumulation causes catalyst Topically active to enhance, and then will increase the SO of catalyst2/SO3It is whole to reduce denitrating catalyst for conversion ratio
Body performance.
NOxConversion ratio evaluation condition: air speed 4000h-1, 350 DEG C of reaction temperature, air inlet NOxFor 600mg/Nm3、SO2For
1000mg/Nm3, ammonia nitrogen ratio be 1, water content 10%.
NOx、SO2Method for measurement of concentration: flue gas continuous on-line analysis instrument, Siemens ULTRAMAT23.
SO2/SO3Conversion ratio measuring method: wet desulfurization of flue gas by limestone-gypsum method device performance acceptance test specification (DL/
T998-2006)。
Following embodiment is illustrated to of the invention, and " % " described in embodiment and comparative example refers to that quality percentage contains
Amount.
Embodiment 1:
It will contain with TiO2The titanyl sulfate of meter 500g is dissolved in sulfuric acid solution, is added containing with WO3Count the para-tungstic acid of 22.5g
Ammonium salt solution forms and contains TiO2For 35g/L mixed solution, it is gradually added ammonium hydroxide after supersonic oscillations 2h and adjusts pH value to 9.5, precipitating
After completely, it is filtered, washed；Material after washing is spent into the slurry that ion water making is 50% at moisture content again, is added with V2O5Meter
The ammonium metavanadate solution of 4.5g, supersonic oscillations 1.5h while stirring after convection drying, roast 8h at 620 DEG C；Powder after roasting
Body is again and with WO3Aqueous 30% slurry is made in the ammonium metatungstate solution of meter 7.5g, and 4g polyethylene glycol oxide, stirring are added after stirring
40min, sealing and standing for 24 hours, drying, obtain denitrating catalyst after 620 DEG C of roasting 8h.Above-mentioned gained fresh catalyst and with catalysis
Cracking vanadium-containing wasting catalyst high temperature mixing rear catalyst is evaluated respectively, the results are shown in Table 1 data.
Comparative example 1:
It will contain with TiO2The titanyl sulfate of meter 500g is dissolved in sulfuric acid solution, is added containing with WO3Count the para-tungstic acid of 22.5g
Ammonium salt solution forms and contains TiO2For 35g/L mixed solution, it is gradually added ammonium hydroxide after supersonic oscillations 2h and adjusts pH value to 10, precipitating
After completely, it is filtered, washed；Material after washing is spent into the slurry that ion water making is 50% at moisture content again, is added with V2O5Meter
The ammonium metavanadate solution of 4.5g, supersonic oscillations 1.5h while stirring after convection drying, roast 8h and obtain denitration at 620 DEG C
Catalyst；It above-mentioned gained fresh catalyst and evaluates, ties respectively with catalytic cracking vanadium-containing wasting catalyst high temperature mixing rear catalyst
Fruit is shown in Table 1 data.
Embodiment 2
It will contain with TiO2The titanyl sulfate of meter 500g is dissolved in sulfuric acid solution, is added containing with WO3Count the para-tungstic acid of 22.5g
Ammonium salt solution forms and contains TiO2For 30g/L mixed solution, it is gradually added ammonium hydroxide after supersonic oscillations 1.5h and adjusts pH value to 10, sinks
After forming sediment completely, it is filtered, washed；Material after washing is spent into the slurry that ion water making is 50% at moisture content again, is added with V2O5Meter
The ammonium metavanadate solution of 4.5g, supersonic oscillations 1.5h while stirring after convection drying, roast 8h at 600 DEG C；Powder after roasting
Body is again and with WO3Aqueous 35% slurry is made in the ammonium metatungstate solution of meter 5g, and 3.5g polyethylene glycol oxide, stirring are added after stirring
Denitrating catalyst is obtained after 30min, sealing and standing 16h, drying, 600 DEG C of roastings.It above-mentioned gained fresh catalyst and is split with catalysis
Change vanadium-containing wasting catalyst high temperature mixing rear catalyst to evaluate respectively, the results are shown in Table 1 data.
Comparative example 2
It will contain with TiO2The titanyl sulfate of meter 500g is dissolved in sulfuric acid solution, is added containing with WO3Count the para-tungstic acid of 22.5g
Ammonium salt solution forms and contains TiO2For 30g/L mixed solution, it is gradually added ammonium hydroxide after supersonic oscillations 1.5h and adjusts pH value to 9.0 heavy
After forming sediment completely, it is filtered, washed；Material after washing is spent into the slurry that ion water making is 50% at moisture content again, is added with V2O5Meter
The ammonium metavanadate solution of 4.5g, supersonic oscillations 1.5h while stirring after convection drying, roast 8h at 600 DEG C；Powder after roasting
Body is again and with WO3Aqueous 35% slurry is made in the ammonium metatungstate solution of meter 5g, after stirring 30min, drying, 600 DEG C of roastings
To denitrating catalyst.It above-mentioned gained fresh catalyst and is commented respectively with catalytic cracking vanadium-containing wasting catalyst high temperature mixing rear catalyst
Valence the results are shown in Table 1 data.
Embodiment 3
It will contain with TiO2The metatitanic acid of meter 500g is dissolved in sulfuric acid solution, is added containing with WO3The ammonium paratungstate for counting 20g is molten
Liquid forms and contains TiO2For 30g/L mixed solution, it is gradually added ammonium hydroxide after supersonic oscillations 1h and adjusts pH value to 9.5, precipitating is complete
Afterwards, it is filtered, washed；Material after washing is spent into the slurry that ion water making is 45% at moisture content again, is added with V2O5Count the inclined of 5g
Ammonium Vanadate Solution, supersonic oscillations 1h while stirring after convection drying, roast 6h at 550 DEG C；After roasting powder again with
WO3Aqueous 30% slurry is made in the ammonium metatungstate solution of meter 5g, and 3g polyethylene glycol oxide, stirring 30min, sealing are added after stirring
Denitrating catalyst is obtained after standing 20h, drying, 550 DEG C of roastings.It above-mentioned gained fresh catalyst and urges with catalytic cracking containing vanadium is useless
Agent high temperature mixing rear catalyst is evaluated respectively, the results are shown in Table 1 data.
Comparative example 3
Technique used presses CN201110345605 embodiment 1, and metatitanic acid dust technology is dispersed mashing, is filtered to neutrality,
It adds water for metatitanic acid to be beaten and disperse, metatitanic acid slurry is made.Ammonium tungstate, ammonium molybdate and vanadium are sequentially added in metatitanic acid slurry
Sour ammonium, making the mass ratio of three kinds of ammonium salts and metatitanic acid is respectively 1/100,1/100 and 0.1/100, is then used mixed material super
Sound wave mashing allows the ammonium salt of addition to dissolve, disperse, and so that ammonium salt is sufficiently adsorbed to metatitanic acid surface, extremely with nitre acid for adjusting pH value
5.0.It stands, dry, 300 DEG C of heat treatment 4h obtain catalyst.Above-mentioned gained fresh catalyst and useless containing vanadium with catalytic cracking
Catalyst high temperature mixing rear catalyst is evaluated respectively, the results are shown in Table 1 data.
Embodiment 4
It will contain with TiO2The metatitanic acid of meter 500g is dissolved in sulfuric acid solution, is added containing with WO3The ammonium paratungstate for counting 15g is molten
Liquid forms and contains TiO2For 20g/L mixed solution, ammonium hydroxide is gradually added after supersonic oscillations 1h, and to adjust pH value complete to 10.5 precipitatings
Afterwards, it is filtered, washed；The slurry that moisture content is 40% is made with distilled water in material after washing again, is added with V2O5Count the inclined vanadium of 5g
Acid ammonium solution, supersonic oscillations 1h while stirring after convection drying, roast 6h at 500 DEG C；Powder is again and with WO after roasting3
Aqueous 28% slurry is made in the ammonium metatungstate solution of meter 3.5g, and 2.5g polyethylene glycol oxide, stirring 40min, close are added after stirring
Envelope obtains denitrating catalyst after standing 20h, drying, 500 DEG C of roastings.Above-mentioned gained fresh catalyst and useless containing vanadium with catalytic cracking
Catalyst high temperature mixing rear catalyst is evaluated respectively, the results are shown in Table 1 data.
Comparative example 4
Technique used presses CN103143396 embodiment 1, a kind of honeycomb type flue gas denitration catalyst, with the raw material of parts by weight
Through extrusion molding, be sintered: 83 parts of nano-titanium dioxide, 8.3 parts of nano silica, ammonium metatungstate are with WO3Count 10 weight
Part, ammonium metavanadate are with V2O5Count 1 parts by weight, 6.7 parts of glass fibre, 0.42 part of extrusion aid, 0.17 part of cellulose, polyethylene glycol oxide
0.25 part, 0.17 part of sesbania powder.Honeycombed catalyst is crushed to 20~40 mesh and is evaluated.Above-mentioned gained fresh catalyst and
It is evaluated respectively with catalytic cracking vanadium-containing wasting catalyst high temperature mixing rear catalyst, the results are shown in Table 1 data.
Embodiment 5
It will contain with TiO2The metatitanic acid of meter 500g is dissolved in sulfuric acid solution, is added containing with WO3The ammonium metatungstate for counting 20g is molten
Liquid forms and contains TiO2For 30g/L mixed solution, it is gradually added ammonium hydroxide after supersonic oscillations 1h and adjusts pH value to 10.5, has precipitated
Quan Hou is filtered, washed；The slurry that moisture content is 40% is made with distilled water in material after washing again, is added with V2O5Count the inclined of 4g
Ammonium Vanadate Solution, supersonic oscillations 1h while stirring after convection drying, roast 6h at 550 DEG C；After roasting powder again with
WO3Aqueous 30% slurry is made in the ammonium metatungstate solution of meter 5g, and 3g polyethylene glycol oxide, stirring 40min, sealing are added after stirring
Denitrating catalyst is obtained after standing 20h, drying, 550 DEG C of roastings.It above-mentioned gained fresh catalyst and urges with catalytic cracking containing vanadium is useless
Agent high temperature mixing rear catalyst is evaluated respectively, the results are shown in Table 1 data.
1 embodiment and comparative example of table evaluates data contrast table
Found by embodiment and comparative example: the denitrating catalyst that the resistance vanadium deposition of embodiment is uneven has good effect
Fruit, it is preliminary by ultrasonic wave mixing in situ, so that the mixing rank of active material is reached molecule rank, is 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
Strengthen the co-catalyst for being introduced into and hindering barium oxide nonuniform deposition in gas phase under the action of (polyethylene glycol oxide) again, after roasting i.e.
Obtain final catalyst, NO in evaluating catalystxConversion ratio when ammonia nitrogen ratio is 1, up to 99% or more, through containing with catalytic cracking
After vanadium dead catalyst mixed processing, SO2/SO3Conversion ratio illustrates catalyst surface almost without increase almost without vanadium oxygen is generated
The polycrystalline of compound deposits, and catalyst performance is excellent；In denitrating catalyst preparation method, if handling without second step, only retain the
Vanadium tungsten titanium catalyst sample after primary roasting, after catalytic cracking vanadium-containing wasting catalyst mixed processing, SO2/SO3Conversion ratio slightly increases
Add；If pore creating material is not added in second step processing, after catalytic cracking vanadium-containing wasting catalyst mixed processing, SO2/SO3Conversion ratio is also slightly
There is increase.In short, fresh denitrating catalyst prepared by the present invention and treated when catalyst evaluates under the conditions of same, SO2/SO3
Conversion ratio is lower than other comparative examples, has the effect of barium oxide nonuniform deposition in good anti-flue gas.
Beneficial effects of the present invention:
(1) using the method mixed in situ, titanium atom and tungsten atom is mixed in molecule rank, causes subsequent co-precipitation
The crystal generated in the process, lattice defect is more, and mixed-metal oxides partial size is small and uniform, and specific surface is big, improves simultaneously
Titanium dioxide crystal turns brilliant temperature, conducive to the performance of catalytic activity.
(2) mixed method is assisted using ultrasonic wave, keeps the mixing of various materials atomic level more uniform.
(3) vanadium source addition when titanium dioxide-tungstic acid co-precipitation material does not roast, in titanium-tungsten particle surface penetration
Deeper, connection is closer, and dispersion more evenly, it is more stable to be fired rear catalyst activity；
(4) the vanadium tungsten titanium powder material prepared covers one layer of tungstic acid into after once roasting excessively, and on its surface, simultaneously
It joined polyethylene glycol oxide, possess catalyst particle surface also while there is the attachment of more tungsten oxides nanometer level microporous, both
Barium oxide can be resisted in flue gas in its surface nonuniform deposition, and can guarantee high catalyst performance.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to the protection scope of the claims in the present invention.
Claims (9)
1. a kind of preparation method of denitrating catalyst, which is characterized in that this method comprises the following steps:
(1) titanium source presoma vitriolization is formed into solution, titanium source presoma is in the solution with TiO2Meter, content are 15~40g/
L；
(2) tungsten source presoma is soluble in water, and add it in the solution of step (1)；
(3) after to step (2) acquired solution supersonic oscillations, pH value to more than 9.0 is adjusted with ammonium hydroxide, is precipitated, is filtered, washing；
(4) deionized water is added in the filter cake obtained by step (3), is tuned into pulpous state, vanadium source precursor solution, supersonic oscillations are added
Afterwards, it is directly dried, roasts, form powder；And
(5) by the powder of step (4) and ammonium metatungstate solution mixing pulp, after stirring, addition polymerization ethylene oxide, secondary agitation
Afterwards, sealing and standing, drying, roasting form denitrating catalyst；
Wherein, titanium source presoma, tungsten source presoma, vanadium source presoma, ammonium metatungstate and polyethylene glycol oxide, respectively with TiO2、WO3、
V2O5、WO3With polyethylene glycol oxide meter, mass ratio is 100:2.0~5.0:0.5~2.0:0.5~2.0:0.3~1.0.
2. the preparation method of denitrating catalyst according to claim 1, which is characterized in that the titanium source presoma is sulfuric acid
Oxygen titanium or metatitanic acid.
3. the preparation method of denitrating catalyst according to claim 1, which is characterized in that tungsten source presoma is secondary tungsten
Sour ammonium or ammonium metatungstate.
4. the preparation method of denitrating catalyst according to claim 1, which is characterized in that the step (3) and step (4)
The middle supersonic oscillations time is 0.5~3h, and mixing time is 10~60min in the step (5), in the step (5)
The sealing and standing time is 8~30h.
5. the preparation method of denitrating catalyst according to claim 1, which is characterized in that in the precursor solution of the vanadium source
Vanadium source presoma is ammonium metavanadate.
6. the preparation method of denitrating catalyst according to claim 1, which is characterized in that slurry in the step (4)
Water content is 35~55%.
7. the preparation method of denitrating catalyst according to claim 1, which is characterized in that slurry in the step (5)
Water content is 25~40%.
8. the preparation method of denitrating catalyst according to claim 1, which is characterized in that the step (4) and step (5)
Middle maturing temperature is 400~650 DEG C, and calcining time is 4~10h.
9. a kind of denitrating catalyst is prepared by the preparation method of the described in any item denitrating catalysts of claim 1 to 8.
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| CN101791549A (en) * | 2010-03-30 | 2010-08-04 | 东南大学 | Method for preparing formed selective catalytic reduction denitration catalyst by using ultrasonic mixing sedimentation method |
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