CN107138151A - Preparation method of denitration catalyst with improved specific surface area - Google Patents
Preparation method of denitration catalyst with improved specific surface area Download PDFInfo
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- CN107138151A CN107138151A CN201710436286.1A CN201710436286A CN107138151A CN 107138151 A CN107138151 A CN 107138151A CN 201710436286 A CN201710436286 A CN 201710436286A CN 107138151 A CN107138151 A CN 107138151A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 136
- 238000002360 preparation method Methods 0.000 title claims description 40
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 39
- 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
- 239000010936 titanium Substances 0.000 claims abstract description 37
- 238000002156 mixing Methods 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 34
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 32
- 239000010937 tungsten Substances 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000007789 sealing Methods 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 239000012065 filter cake Substances 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 38
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 36
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 21
- 239000011148 porous material Substances 0.000 claims description 16
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 15
- 230000010355 oscillation Effects 0.000 claims description 14
- 238000013019 agitation Methods 0.000 claims description 9
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 5
- -1 vanadic acid amine Chemical class 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 238000010348 incorporation Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 210000002700 urine Anatomy 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 56
- 239000002002 slurry Substances 0.000 abstract description 35
- 238000000034 method Methods 0.000 abstract description 22
- 238000005406 washing Methods 0.000 abstract description 21
- 239000003546 flue gas Substances 0.000 abstract description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003795 chemical substances by application Substances 0.000 abstract description 9
- 230000008021 deposition Effects 0.000 abstract description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 2
- 239000011733 molybdenum Substances 0.000 abstract description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 238000004537 pulping Methods 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 24
- 238000004523 catalytic cracking Methods 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 15
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 description 12
- 238000001556 precipitation Methods 0.000 description 11
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 241000219782 Sesbania Species 0.000 description 9
- 206010001497 Agitation Diseases 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 229910001930 tungsten oxide Inorganic materials 0.000 description 6
- 238000000975 co-precipitation Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000003814 drug Substances 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
- 229940079593 drug Drugs 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction 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
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 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
- BQODPTQLXVVEJG-UHFFFAOYSA-N [O].C=C Chemical compound [O].C=C BQODPTQLXVVEJG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 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
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 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
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000003245 coal 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
- 239000006185 dispersion Substances 0.000 description 1
- 238000011156 evaluation Methods 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
- 239000008187 granular material Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 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
- 238000005360 mashing 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
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 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
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material 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
- B01J23/16—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
- 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
- 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
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/088—Decomposition of a metal salt
-
- 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)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a denitration catalyst with improved specific surface area, which comprises the following steps: (1) pulping the activated alumina; (2) dissolving a titanium source precursor; (3) dissolving a tungsten source precursor, and mixing the tungsten source precursor with the solution obtained in the step (1) and the step (2); (4) adjusting the pH value of the mixed solution obtained in the step (3) to 8-13, precipitating, filtering and washing to obtain a filter cake; (5) adding deionized water into the filter cake obtained in the step (4), adjusting into slurry, adding a vanadium source precursor solution, uniformly mixing, drying, and roasting to form powder; (6) and (3) mixing the solution formed by the molybdenum source precursor and the powder in the step (5) into slurry, stirring, adding a pore-forming agent, stirring for the second time, sealing, standing, drying and roasting to obtain the denitration catalyst. The denitration catalyst prepared by the method can improve the specific surface area of the catalyst, resist the uneven deposition of heavy metals in flue gas on the surface of the catalyst and improve the performance of the catalyst.
Description
Technical field
The present invention relates to a kind of preparation method for the denitrating catalyst for improving specific surface area, especially a kind of resistance flue
The preparation method of the uneven denitrating catalyst of vanadium deposition in 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 method for the denitrating catalyst for improving specific surface area, with gram
The clothes unbalanced defect in denitrating catalyst activated centre in high-temperature flue gas in the prior art, and catalyst of the present invention can be with
Resist oxide in flue gas and, in its surface nonuniform deposition, increase specific surface area of catalyst again, improve catalyst performance.
The object of the present invention is achieved like this, a kind of preparation method for the denitrating catalyst for improving specific surface area, system
Preparation Method comprises the following steps：
(1) activated alumina is 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, add vanadium source precursor solution, mixing is equal
After even, it is dried, is calcined, forms powder；
(6) by powder mixing pulp of the solution of tungsten source presoma formation with step (5), after stirring, plus pore creating material,
After secondary agitation, sealing and standing, drying, roasting form denitrating catalyst.
Titanium source presoma, tungsten source presoma, vanadium source presoma, pore creating material, activated alumina 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 alumina described in step (1) of the present invention, also known as activated bauxite, in the catalyst using the usual of aluminum oxide
Specially it is referred to as " activated alumina ", it is a kind of porous, the solid material of high degree of dispersion, there is very big surface area, its micropore table
Face possesses the characteristic required by catalytic action, such as absorption property, surface-active, excellent heat endurance, so by widely
Catalyst and catalyst carrier as chemical reaction.Granularity is recommended as 10~500 mesh, and preferably 180~400 mesh compare surface
Product is preferably 60~200m2/ g, pore volume is preferably 0.40~0.80cm3/g。
In the inventive method, the activated alumina quality described in step (1) is with titanium source presoma (with TiO2Meter) mass ratio
Preferably 3~20:100, preferably 3~10:100.
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 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 0.5~2.0:100.
The preparation method of denitrating catalyst of the present invention, wherein, sintering temperature in the step (5) and step (6)
It it is preferably 400~650 DEG C, roasting time is preferably 4~10h.
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.
Tungsten source used forerunner's weight is with WO in step (6)3Meter, the titanium source presoma is with TiO2Meter, tungsten source presoma is used
The mass ratio of amount and titanium source presoma consumption is preferably 0.5~2:100.
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 alumina, it is internal nanometer level microporous with what is enriched,
Add the active sites of catalytic inner.After activated alumina is mixed with the titanium and tungsten of ionic state, unformed oxidation can be promoted
The even closer parcel activated alumina of titanium, tungsten oxide, improves catalyst strength, due to having used activated alumina also to improve simultaneously
(specific surface area is in 130m for specific surface area of catalyst2/ more than g) and porosity, the efficiency of catalyst is improved, while in catalyst
Inert gas shielding is not needed in preparation process, preparation cost is reduced.
(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 tungsten oxide layer on its surface, while plus
Pore creating material is entered, has made catalyst particle surface that there are more tungsten 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.
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 preferably 15~40g/L.
If less than 15g/L, solution is too dilute, and the combination of other materials is more loose, and production efficiency is relatively low；If being more than 40g/L, by
In concentration it is too high and with other materials mixing intensity reduction, cause fusion it is 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)。
Activated alumina：Activated alumina：Granularity is 300 mesh, specific surface area 150m2/ g, pore volume 0.70cm3/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：
15g activated aluminas are beaten to form slurries (a), will be contained with TiO2It is molten that meter 500g titanyl sulfate is dissolved in sulfuric acid
In liquid, formed and contain TiO2For 35g/L solution (b), it will contain with WO3Meter 22.5g secondary tungsten acid ammonium solution is mixed with (a), (b) material,
After supersonic oscillations 2h, it is gradually added ammoniacal liquor and adjusts pH value to 9.0, after precipitation is complete, filtering, washing；After washing again
Material spends ion water making into the slurry that moisture content is 60%, adds with V2O54.5g ammonium metavanadate solution is counted, while stirring
After supersonic oscillations 1.5h, convection drying, in 620 DEG C of roasting temperature 4h；After roasting powder again with WO3Count 7.5g inclined tungsten
Sour ammonium is configured to aqueous 30% slurry, and 4g sesbania powders, stirring 40min, sealing and standing 8h, drying, 620 DEG C of roastings are added after stirring
Denitrating catalyst is obtained after burning 4h.Specific surface area of catalyst 135m2/g.Above-mentioned gained fresh catalyst and contain with catalytic cracking
Vanadium dead catalyst high temperature mixing rear catalyst is evaluated respectively, the results are shown in Table 1 data.
Comparative example 1：
Activated alumina is added without in catalyst manufacturing process, will be contained with TiO2Meter 500g titanyl sulfate is dissolved in
In sulfuric acid solution, formed and contain TiO2For 35g/L solution, add and contain with WO3In the secondary tungsten acid ammonium solution for counting 22.5g, using ultrasonic wave
Vibrate after 2h, be gradually added ammoniacal liquor and adjust pH value to 9.0, after precipitation is complete, filtering, washing；Again by material after washing spend from
The slurry that moisture content is 60% is made in sub- water, adds with V2O5Count 4.5g ammonium metavanadate solution, supersonic oscillations while stirring
After 1.5h, convection drying, in 620 DEG C of roasting temperature 4h；After roasting powder again with WO3Meter 7.5g ammonium metatungstate, which is made, to be contained
The slurry of water 30%, is taken off after 4g sesbania powders, stirring 40min, sealing and standing 8h, drying, 620 DEG C of roasting 4h are added after stirring
Denox catalyst.Specific surface area of catalyst 128m2/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.
Embodiment 2
20g activated aluminas are beaten to form slurries (a), will be contained with TiO2Meter 500g metatitanic acid is dissolved in sulfuric acid solution
In, formed and contain TiO2For 35g/L solution (b), (a), (b) are added and contained with WO3Count 20g secondary tungsten acid ammonium solution, mechanical agitation 1h
After be gradually added ammoniacal liquor and adjust pH value to 9.5, precipitation completely after, filtering, washing；Again by material after washing spend ion water making into
Moisture content is 45% slurry, is added with V2O5Count 5g ammonium metavanadate solution, mechanical agitation 1h while stirring, convection drying
Afterwards, 6h is calcined at 550 DEG C；After roasting powder again with WO3Aqueous 30% slurry is made in meter 5g ammonium metatungstate, adds after stirring
Denitrating catalyst is obtained after entering 3g urea, stirring 30min, sealing and standing 20h, drying, 550 DEG C of roasting 8h.Above-mentioned gained is 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.
Comparative example 2
Vanadium source is added after being calcined in first time, i.e., be beaten to form slurries (a) by 20g activated aluminas, will contain with TiO2Meter
500g metatitanic acid is dissolved in sulfuric acid solution, is formed and is contained TiO2For 35g/L solution (b), (a), (b) are added and contained with WO3Meter
Ammoniacal liquor is gradually added after 20g secondary tungsten acid ammonium solution, mechanical agitation 1h and adjusts pH value to 9.5, after precipitation is complete, filter, wash,
After drying, 6h is calcined at 550 DEG C；After roasting powder with WO3Meter 5g ammonium metatungstate be made aqueous 30% slurry, and with
V2O55g ammonium metavanadate solution mixing is counted, 3g urea, stirring 30min, sealing and standing 20h, drying, 550 DEG C of roastings are added after stirring
Denitrating catalyst is obtained after burning 8h.Above-mentioned gained fresh catalyst and it is catalyzed after being mixed with catalytic cracking vanadium-containing wasting catalyst high temperature
Agent is evaluated respectively, the results are shown in Table 1 data.
Embodiment 3
20g activated aluminas are beaten to form slurries (a), will be contained with TiO2Meter 500g metatitanic acid is dissolved in sulfuric acid solution
In, formed and contain TiO2For 35g/L solution (b), (a), (b) are added and contained with WO3Count 15g secondary tungsten acid ammonium solution, mechanical agitation 1h
After be gradually added ammoniacal liquor adjust pH value to 10.5 precipitation completely after, filtering, washing；Material after washing is made of distilled water again and contained
Water rate is 40% slurry, is added with V2O5Count after 5g ammonium metavanadate solution, mechanical agitation 1h, convection drying, roasted at 500 DEG C
Burn 6h；After roasting powder again with WO3Aqueous 28% slurry is made in meter 3.5g ammonium metatungstate solution, and 2.5g is added after stirring
Denitrating catalyst is obtained after sesbania powder, stirring 40min, sealing and standing 20h, drying, 500 DEG C of roasting 4h.Above-mentioned gained is fresh to urge
Agent and evaluated respectively with catalytic cracking vanadium-containing wasting catalyst high temperature mixing rear catalyst, the results are shown in Table 1 data.
Comparative example 3
The process of catalyst is prepared only with being once calcined, i.e., is beaten to form slurries (a) by 20g activated aluminas, will contain
With TiO2Meter 500g metatitanic acid is dissolved in sulfuric acid solution, is formed and is contained TiO2For 35g/L solution (b), (a), (b) are added and contained
With WO3Count 15g secondary tungsten acid ammonium solution, be gradually added after mechanical agitation 1h ammoniacal liquor adjust pH value to 10.5 precipitations completely after, mistake
Filter, washing；The slurry that moisture content is 40% is made of distilled water for material after washing again, is added with V2O5Count 5g ammonium metavanadate
Solution, and add with WO3Aqueous 28% slurry is made in meter 3.5g ammonium metatungstate solution, and 2.5g sesbanias are added after stirring
Powder, 4h obtains denitrating catalyst after stirring 40min, sealing and standing 20h, drying, 500 DEG C of roastings.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 4
30g activated aluminas are beaten to form slurries, and will be contained with TiO2It is molten that meter 500g metatitanic acid is dissolved in sulfuric acid
In liquid, formed and contain TiO2For 35g/L solution, add and contain with WO3Count and progressively add after 20g ammonium metatungstate solution, supersonic oscillations 2h
Enter ammoniacal liquor and adjust pH value to 8.5, after precipitation is complete, filtering, washing；Material after washing is made into moisture content with distilled water again is
40% slurry, is added with V2O5Count after 5g ammonium metavanadate solution, supersonic oscillations 1h while stirring, convection drying, 550
6h is calcined at DEG C；After roasting powder again with WO3Aqueous 30% slurry is made in meter 5g ammonium metatungstate, and 3g is added after stirring and is gathered
Denitrating catalyst is obtained after oxygen ethene, stirring 40min, sealing and standing 20h, drying, 550 DEG C of roasting 5h.Above-mentioned gained is fresh to urge
Agent and evaluated respectively with catalytic cracking vanadium-containing wasting catalyst high temperature mixing rear catalyst, the results are shown in Table 1 data.
Comparative example 4
Pore creating material is added without after being once calcined, i.e., is beaten to form slurries by 30g activated aluminas, and will contain with TiO2Meter
500g metatitanic acid is dissolved in sulfuric acid solution, is formed and is contained TiO2For 35g/L solution, add and contain with WO3Count 20g ammonium metatungstate
Ammoniacal liquor is gradually added after solution, supersonic oscillations 2h and adjusts pH value to 8.5, after precipitation is complete, filtering, washing；After washing again
The slurry that moisture content is 40% is made of distilled water for material, adds with V2O55g ammonium metavanadate solution is counted, it is ultrasonic while stirring
Ripple is vibrated after 1h, convection drying, and 6h is calcined at 550 DEG C；After roasting powder again with WO3Meter 5g ammonium metatungstate solution, which is made, to be contained
Denitrating catalyst is obtained after the slurry of water 30%, stirring 40min, sealing and standing 20h, drying, 550 DEG C of roasting 5h.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 5
15g activated aluminas are beaten to form slurries, and will be contained with TiO2It is molten that meter 500g metatitanic acid is dissolved in sulfuric acid
In liquid, formed and contain TiO2For 35g/L solution, add and contain with WO3Count after 10g ammonium metatungstate solution, supersonic oscillations 0.5h progressively
Add ammoniacal liquor and adjust pH value to 9.5, after precipitation is complete, filtering, washing；Material after washing is made into moisture content with distilled water again is
40% slurry, is added with V2O5Count after 10g ammonium metavanadate solution, supersonic oscillations 1h while stirring, convection drying, 550
6h is calcined at DEG C；After roasting powder again with WO3Aqueous 30% slurry is made in meter 10g ammonium metatungstate, and 10g is added after stirring
Denitrating catalyst is obtained after sesbania powder composite drug, stirring 10min, sealing and standing 20h, drying, 550 DEG C of roasting 5h.Above-mentioned institute
Obtain 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.
Comparative example 5
Tungsten source presoma is once added, i.e., is beaten to form slurries by 15g activated aluminas, and will be contained with TiO2Meter
500g metatitanic acid is dissolved in sulfuric acid solution, is formed and is contained TiO2For 35g/L solution, add and contain with WO3Count 20g ammonium metatungstate
Ammoniacal liquor is gradually added after solution, supersonic oscillations 0.5h and adjusts pH value to 9.5, after precipitation is complete, filtering, washing；Again will washing
The slurry that moisture content is 40% is made of distilled water for material afterwards, adds with V2O510g ammonium metavanadate solution is counted, while stirring
After supersonic oscillations 1h, convection drying, 6h is calcined at 550 DEG C；Powder is configured to aqueous 30% slurry after roasting, adds
Denitrating catalyst is obtained after 10g sesbania powder composite drugs, stirring 10min, sealing and standing 20h, drying, 550 DEG C of roasting 5h.It is 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
50g activated aluminas are beaten to form slurries, and will be contained with TiO2It is molten that meter 500g metatitanic acid is dissolved in sulfuric acid
In liquid, formed and contain TiO2For 35g/L solution, add and contain with WO3Count and progressively add after 25g ammonium metatungstate solution, supersonic oscillations 3h
Enter ammoniacal liquor and adjust pH value to 8.5, after precipitation is complete, filtering, washing；Material after washing is made into moisture content with distilled water again is
40% slurry, is added with V2O5Count after 2.5g ammonium metavanadate solution, supersonic oscillations 1h while stirring, convection drying,
6h is calcined at 550 DEG C；After roasting powder again with WO3Aqueous 30% slurry is made in meter 2.5g ammonium metatungstate, adds after stirring
Denitrating catalyst is obtained after entering 2.5g sesbania powders, stirring 40min, sealing and standing 20h, drying, 550 DEG C of roasting 6h.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.
The embodiment of table 1 and comparative example evaluating data contrast table
Found by embodiment and comparative example：The high-specific surface area denitrating catalyst of embodiment, resistance vanadium deposition inequality
Denitrating catalyst has good effect, preliminary by ultrasonic wave mixing in situ, the mixing rank of active material is reached molecular level
Not, the nano particle slightly evacuated through co-precipitation, then barium oxide is introduced in particle surface and shallow-layer, it is catalyzed after roasting
Agent intermediate, then strengthens and final catalysis is produced after introducing co-catalyst, roasting again in the presence of pore creating material such as sesbania powder
NO in agent, evaluating catalystxConversion ratio when ammonia nitrogen ratio is 1, up to more than 99%, through with catalytic cracking vanadium-containing wasting catalyst
After mixed processing, SO2/SO3Conversion ratio does not almost increase, and illustrates that catalyst surface does not almost produce the polycrystalline of barium oxide
Deposition, catalyst performance is excellent；In denitrating catalyst preparation method, if being handled without (6) step, only retain after being calcined for the first time
Vanadium tungsten titanium catalyst sample, after catalytic cracking vanadium-containing wasting catalyst mixed processing, SO2/SO3Conversion ratio has increased slightly；If (6)
Pore creating material is not added with step processing, after catalytic cracking vanadium-containing wasting catalyst mixed processing, SO2/SO3Conversion ratio also has increased slightly；If
Catalyst is formed in preparation process using once roasting, or vanadium source is added after being once calcined, and catalyst is in evaluation procedure
Middle NOxConversion ratio be slightly decreased, while SO2/SO3Conversion ratio has increased slightly.In a word, the fresh denitration catalyst that prepared by the present invention
Catalyst after agent and processing with the conditions of when evaluating, SO2/SO3Conversion ratio is lower than other comparative examples, with good
The effect of barium oxide nonuniform deposition in anti-flue gas.
Catalyst is added after activated alumina is beaten it can be seen from embodiment and comparative example specific surface area degrees of data
In preparation process in situ, specific surface area of catalyst is significantly increased, and catalytic efficiency is improved.
Beneficial effects of the present invention：
(1) in catalyst preparation process of the present invention, using activated alumina, it is internal nanometer level microporous with what is enriched,
Add the active sites of catalytic inner.After activated alumina is mixed with the titanium and tungsten of ionic state, unformed oxidation can be promoted
The even closer parcel activated alumina of titanium, tungsten oxide, improves catalyst strength, improves specific surface area of catalyst and porosity,
The efficiency of catalyst is improved, while not needing inert gas shielding in catalyst preparation process, preparation cost is reduced.
(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 tungsten oxide layer on its surface, while plus
Pore creating material is entered, has made catalyst particle surface that there are more tungsten 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 denitrating catalyst for improving specific surface area, it is characterised in that preparation method includes following step
Suddenly：
(1) activated alumina is 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 presoma, after being well mixed, enter
Row is dried, roasting, forms powder；
(6) by powder mixing pulp of the solution of tungsten source presoma formation with step (5), after stirring, plus pore creating material, it is secondary
After stirring, sealing and standing, drying, roasting form denitrating catalyst.
2. preparation method according to claim 1, it is characterised in that the activated alumina described in step (1), granularity 10~
500 mesh, preferably 180~400 mesh, specific surface area are 60~200m2/ g, 0.40~0.80cm of pore volume3/g。
3. preparation method according to claim 1, it is characterised in that activated alumina described in step (1) with TiO2Meter
Titanium source forerunner body mass ratio be 3~20:100, preferably 3~10:100.
4. 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, it is used in step (6)
Tungsten source presoma is 0.5~2 with titanium source forerunner body mass ratio:100.
5. 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；The mixing of step (3) and step (5)
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.
6. preparation method according to claim 1, it is characterised in that in the vanadium source precursor solution in the step (5)
Vanadium source presoma is with V2O5Meter, the titanium source presoma is with TiO2The quality of meter, vanadium source presoma consumption and titanium source presoma consumption
Than for 0.5~2.0:100.
7. preparation method according to claim 1, it is characterised in that the titanium source presoma is with TiO2Meter, the step
(6) mass ratio of the addition of pore creating material and titanium source presoma is 0.5~1.5 in:100.
8. preparation method according to claim 1, it is characterised in that sintering temperature is equal in the step (5) and step (6)
For 400~650 DEG C, roasting time is 4~10h.
9. preparation method according to claim 1, it is characterised in that tungsten source presoma is ammonium metatungstate or wolframic acid
Ammonium；Titanium source presoma is titanyl sulfate or metatitanic acid；Vanadium source presoma is ammonium metavanadate or vanadic acid amine.
10. preparation method according to claim 1, it is characterised in that the pore creating material that the step (6) is added is urine
One or more in element, 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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Application publication date: 20170908 |