CN101513620A - Preparation method for titanium dioxide group catalyst carrier - Google Patents
Preparation method for titanium dioxide group catalyst carrier Download PDFInfo
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- CN101513620A CN101513620A CNA2009100292352A CN200910029235A CN101513620A CN 101513620 A CN101513620 A CN 101513620A CN A2009100292352 A CNA2009100292352 A CN A2009100292352A CN 200910029235 A CN200910029235 A CN 200910029235A CN 101513620 A CN101513620 A CN 101513620A
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- titanium dioxide
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- binding agent
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000003054 catalyst Substances 0.000 title abstract description 41
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 37
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 16
- 238000000465 moulding Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001125 extrusion Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 229910001868 water Inorganic materials 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 8
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 4
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 3
- 239000011230 binding agent Substances 0.000 claims description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- 229920002472 Starch Polymers 0.000 claims description 9
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 claims description 9
- 229940063655 aluminum stearate Drugs 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 9
- 235000011187 glycerol Nutrition 0.000 claims description 9
- 239000008107 starch Substances 0.000 claims description 9
- 235000019698 starch Nutrition 0.000 claims description 9
- 241000219793 Trifolium Species 0.000 claims description 7
- 229920000609 methyl cellulose Polymers 0.000 claims description 7
- 239000001923 methylcellulose Substances 0.000 claims description 7
- 235000010981 methylcellulose Nutrition 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- 229910001593 boehmite Inorganic materials 0.000 claims description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000012188 paraffin wax Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 230000001413 cellular effect Effects 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical group CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 3
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 3
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 3
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 235000015424 sodium Nutrition 0.000 claims description 3
- 239000002383 tung oil Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 9
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 238000010531 catalytic reduction reaction Methods 0.000 abstract 1
- 235000011194 food seasoning agent Nutrition 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 235000010215 titanium dioxide Nutrition 0.000 description 30
- 230000006835 compression Effects 0.000 description 14
- 238000007906 compression Methods 0.000 description 14
- 239000002245 particle Substances 0.000 description 11
- 229910010413 TiO 2 Inorganic materials 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 150000004996 alkyl benzenes Chemical class 0.000 description 3
- 239000000440 bentonite Substances 0.000 description 3
- 229910000278 bentonite Inorganic materials 0.000 description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 241001466460 Alveolata Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 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 2
- 238000004537 pulping Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 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
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- HFDCVHDLKUZMDI-UHFFFAOYSA-N sulfuric acid titanium Chemical compound [Ti].OS(O)(=O)=O HFDCVHDLKUZMDI-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention provides a preparation method for a titanium dioxide group catalyst carrier with excellent moldability, high strength and high specific surface. The method comprises the following steps: using titanium dioxide or metatitanic acid prepared by hydrolyzation and neutralization of precipitate with titanium tetrachloride as the raw material; by weight portions, mixing and grinding 60-85% of titanium dioxide or dried metatitanic acid powder (counted as titanium dioxide), 1-10% of temporary adhesive and 1-5% of pore-forming material into uniform powder; adding 5-35% of constitutive adhesive, 0.5-2% of molding adhesion promoter, 1-10% of extrusion aid and water followed by evenly mixing and making into mud; extruding for molding after the mud decays; seasoning the extrudate at room temperature; baking and dehydrating at a temperature below 80 DEG C; and then iglossing at 400-600 DEG C to obtain the titanium dioxide group carrier. After molding, the specific surface of the carrier is 80-150m<2>/g, and the pressive strength thereof is 15-100N/mm. The carrier is mainly used for selective catalytic reduction (SCR) to remove nitrogen oxide.
Description
Technical field
The present invention relates to a kind of preparation method of TiO 2-based catalyst carrier, in particular to a kind of preparation method who is used for the TiO 2-based catalyst carrier of SCR (SCR) denitration.
Background technology
Nitrogen oxide (the NO of discharging such as power plant boiler system, Industrial Stoves and the incinerator of China
x) be the main stationary source that causes atmosphere pollution.China has begun to impose the nitrogen oxide charges for disposing pollutants on July 1st, 2004, also will progressively force NO such as power plant boiler system, Industrial Stoves and incinerator according to " discharge standard of air pollutants (GB16297-1996) "
xEmission compliance.In the current technology that removes the nitrogen oxide in the burnt gas, mainstream technology is SCR (SCR), and the catalyst in this technology is to be that carrier, load vanadic anhydride and tungsten oxide isoreactivity component constitute with the anatase titanium dioxide.In actual application, this carrier or catalyst need manufacture suitable geometries such as cellular or strip usually, and need carrier when keeping, to have sufficiently high surface area, thereby be adapted to the requirement that the denitration engineering has suitable mechanical life and SCR catalytic activity in using than high-wearing feature and intensity.
What known together is, titania powder is because the adhesive property of self is poor, and the mouldability of raw material is very poor, carrier at high temperature need be carried out roasting usually and just can give carrier enough intensity, but such high-temperature roasting meeting makes the material sintering, thereby causes the specific area of carrier quite little.Chinese patent CN01128861.2 discloses a kind of manufacture method of TiO 2-based catalyst carrier, this method is a raw material with the wet metatitanic acid of the intermediate product of sulfuric acid titanium white production, adopt titanyl sulfate liquid as binding agent, under 800-950 ℃, carry out roasting and make the TiO 2-based catalyst carrier particle, gained carrier compression strength is 80-150N/, and specific area is 4-20m
2/ g.Chinese patent application CN200510046863.3 discloses a kind of preparation method of multi-component titanium-based catalyst carrier, this method adopt titanium dioxide as the mixture of first carrier component, zirconium, rare earth or zirconium and rare earth as second carrier component, titanyl sulfate liquid as binding agent, under 500-900 ℃, carry out roasting and make the titanium-based catalyst carrier particle, the gained carrier side is to compression strength 36-150N/mm, and specific area is 6-19m
2/ g.
In order to make carrier have higher mechanical life (compression strength and wearability), bigger specific area, and higher SCR catalyst activity, prior art shows, contains an amount of sulfate radical (SO in the titanium dioxide raw material
4 2-) be favourable.Chinese patent application CN200710097827.9 discloses a kind of Ti-base catalyst that is used for coal steam-electric plant smoke SCR denitration and preparation method thereof, the metatitanic acid that this invention is used contains 3～4% sulfate radical, the gained catalyst has bigger specific area and higher denitration activity, and catalyst strength also is improved.Chinese patent CN95193331.0 discloses a kind of TiO 2-based catalyst carrier, this carrier is a raw material with Analysis of Hydrolysis Production of Titanium " hydrate slurry ", and containing 1～8% sulfuric acid amount, gained titanium dioxide base carrier has good compression strength and wearability.Chinese patent application CN03122008.8 discloses a kind of cellular catalyst for treating waste gas with titania powder and catalyst for treating waste gas, wherein the extrusion molding of catalyst and wearability and intensity are subjected to the size of crystallite particle diameter of amount, titanium dioxide of the sulfate radical in the raw material titanium dioxide and the influence that distributes, and this invention shows that containing 0.3～5.0% sulfate radical in the rutile titanium dioxide powder is favourable to honeycomb moulding intensity.In a word, in order to obtain having the carrier of suitable compression strength and specific area, it has been generally acknowledged that containing an amount of sulfate radical in the titanium dioxide raw material is necessary that sulfate radical can improve the mechanical performance of moulding extrudate.But the existence of sulfate radical can cause molding adhesive sulphation gradually in the catalyst use, thereby the mechanical strength of catalyst carrier is descended, and this has very adverse influence for catalyst life.
Therefore be necessary good high strength, the high-ratio surface TiO 2-based catalyst carrier of a kind of mouldability of preparation under the prerequisite of sulfur-bearing not.
Summary of the invention
The purpose of this invention is to provide a kind of high strength that the preparation mouldability is good under low sintering temperature, the method for high-ratio surface TiO 2-based catalyst carrier, this carrier can be applicable to the NO in the combustion tail gas
xRemove catalyst, have excellent catalytic performance and mechanical stability.
The present invention includes a kind of preparation method of titanium dioxide base carrier, its preparation is finished by following processing step:
A) percentage by weight of molding materials each component is as follows:
(1) titanium dioxide or dried metatitanic acid, content 60～85%,
(2) structural binding agent: content 5～35%,
(3) temporary binding agent: content 1～10%,
(4) extrusion aid: content 1～10%,
(5) pore creating material: content 1～5%,
(6) moulding adhesion promoter: content 0.5～2%,
(7) all the other are water;
B) titanium dioxide or dried metatitanic acid powder, temporary binding agent and pore creating material are mixed into uniform powder, again that structural binding agent, moulding adhesion promoter, extrusion aid and water adding mixer kneader is even, and be kneaded into mud;
C) pug is old;
D) with mould with the pug extrusion molding;
E) with extrudate ageing at room temperature;
F) extrudate be not higher than drying and dewatering under 80 ℃ the condition;
G) article shaped is obtained described titanium dioxide base carrier 400～600 ℃ of following calcinations.
The gained shaping carrier can infusion process load set ratio vanadic anhydride, tungsten oxide or molybdenum oxide isoreactivity component, thereby be prepared into catalyst.
Titanium dioxide that the present invention is used or dried metatitanic acid raw material are to be that the preparation of raw material ordinary-temp hydrolysis neutralization precipitation gets with the titanium tetrachloride.We find that the catalyst carrier compression strength for preparing with this type of powder moulding can reach 15～100N/mm, because sintering temperature is low, the carrier specific area can reach 80～150m simultaneously
2/ g is the titania-based carrier material of a kind of high strength, high-ratio surface.In addition, owing to avoided the existence of sulfate radical in the raw material, thus can effectively solve the problem of catalyst carrier along with the growth mechanical strength decline of service time.
The group of following each the thing composition of the optional freedom of described structural binding agent: boehmite, for example the PA98 type boehmite of Nanjing petrochemical industry alkylbenzene factory production; Silica or silicic acid liquid; Natural clay is as bentonite, kaolin etc.; The hydrated titanium dioxide colloidal solution; And arbitrarily both or both above combination in the above mentioned binding agent.This class binding agent provides the fundamental strength of carrier article shaped, can give carrier suitable structural strength.
Described temporary binding agent can be methylcellulose, hydroxypropyl methylcellulose, carboxymethyl cellulose or sodium type, starch, polyethylene glycol or analog.
Described extrusion aid can be glycerine, tung oil, starch, paraffin, water, graphite, talcum powder or analog.
Described pore creating material can be aluminum stearate, starch, carbon dust, paraffin or analog.
Described moulding adhesion promoter can be nitric acid, citric acid, benzoic acid or analog.
Describedly oldly last 12～72 hours.
Described ageing lasted more than 12 hours.
Described article shaped can be shapes such as columned or clover, and article shaped compression strength is: stripe shape 15～100N/mm, particle 35～160N/, clover 10～60N/mm; Also can be cellular, extrude size: Ф 20～150mm or 40 * 40mm～150 * 150mm, 10～60cpsi, wall thickness 1.0～2.0mm, article shaped compression strength can reach 20～60Kg/cm
2About 80～the 150m of above-mentioned article shaped specific area
2/ g.
The specific embodiment
Below the present invention is described in detail by specific embodiment, but should be appreciated that the present invention is not only limited to described embodiment.
Prepare embodiment: stir down the 160L titanium tetrachloride is dissolved in the 1000Kg pure water.The concentrated ammonia liquor of adding 25% is neutralized to pH greater than 9 in above-mentioned solution.After the gained sediment washed after filtration and removes chlorion, filter cake was dry under 80～150 ℃, and products therefrom is a metatitanic acid, about 125Kg.Above-mentioned metatitanic acid is become Nano titanium dioxide in 400～600 ℃ of following calcinations, about 115Kg.The particle size of obtained titanium dioxide is: more than 90%≤and 60nm; Specific area :～90m
2/ g; The anatase titanium dioxide proportion is not less than 90%.
Embodiment 1: get the titanium dioxide 1000g for preparing the embodiment preparation, titanium dioxide powder is crushed to particle diameter less than 325 orders, add 230g bentonite, 60g sodium carboxymethylcellulose, 25g aluminum stearate, after mixed grinding is even, add 30g glycerine, the red fuming nitric acid (RFNA) of 10g 65%, 300g distilled water, mixer kneader becomes mud in kneader.Pug being lower than under 25 ℃ the condition old 12 hours, with the mould of Ф 4, is extruded into the cylindrical of Ф 4 or cloverleaf pattern mud bar with extruder.After the mud bar at room temperature placed 12 hours, be cut into 2mm long post grain or clover.The carrier that will wet was dried 12 hours in 60 ℃ of following air atmospheres, in 500 ℃ of following calcinations 6 hours, made required catalyst carrier again.The side direction compression strength of this carrier is～25N/mm that specific area is～85m
2/ g.
Embodiment 2: get the metatitanic acid 1000g (in titanium dioxide) for preparing the embodiment preparation, the metatitanic acid powder is crushed to particle diameter less than 325 orders, add 230g kaolin, 60g methylcellulose, 25g aluminum stearate, after mixed grinding is even, add 30g glycerine, the red fuming nitric acid (RFNA) of 10g 65%, 250g distilled water, mixer kneader becomes mud in kneader.Pug being lower than under 25 ℃ the condition old 12 hours, with the mould of Ф 4, is extruded into the cylindrical of Ф 4 or cloverleaf pattern mud bar with extruder.After the mud bar at room temperature placed 12 hours, be cut into 2mm long post grain or clover.The carrier that will wet was dried 12 hours in 60 ℃ of following air atmospheres, in 500 ℃ of following calcinations 6 hours, made required catalyst carrier again.The side direction compression strength of this carrier is～32N/mm that specific area is～85m
2/ g.
Embodiment 3: get the titanium dioxide 1000g for preparing the embodiment preparation, titanium dioxide powder is crushed to particle diameter less than 325 orders, add 20g silica, 60g methylcellulose, 25g aluminum stearate, mixed grinding is even.Other gets 100g boehmite (PA98 type, Nanjing petrochemical industry alkylbenzene factory produces), with its nitric acid mixing pulping with 200g 0.5M, joins in the above-mentioned mixed powder.Add 30g glycerine, 10g citric acid, 100g distilled water again, mixer kneader becomes mud in kneader.Pug being lower than under 25 ℃ the condition old 12 hours, with the mould of Ф 4, is extruded into the cylindrical of Ф 4 or cloverleaf pattern mud bar with extruder.After the mud bar at room temperature placed 12 hours, be cut into 2mm long post grain or clover.The carrier that will wet was dried 12 hours in 60 ℃ of following air atmospheres, in 500 ℃ of following calcinations 6 hours, made required catalyst carrier again.The side direction compression strength of this carrier is～35N/mm that specific area is～94m
2/ g.
Embodiment 4: get the metatitanic acid 1000g (in titanium dioxide) for preparing the embodiment preparation, the metatitanic acid powder is crushed to particle diameter less than 325 orders, add 20g silica, 60g methylcellulose, 25g aluminum stearate, mixed grinding is even.Other gets 380ml silicic acid liquid (solids content 33%) and 120g hydrated titanium dioxide colloidal solution joins in the above-mentioned mixed powder.Add 30g glycerine, 10g citric acid again, mixer kneader becomes mud in kneader.Pug being lower than under 25 ℃ the condition old 12 hours, with the mould of Ф 4, is extruded into the cylindrical of Ф 4 or cloverleaf pattern mud bar with extruder.After the mud bar at room temperature placed 12 hours, be cut into 2mm long post grain or clover.The carrier that will wet was dried 12 hours in 60 ℃ of following air atmospheres, in 500 ℃ of following calcinations 6 hours, made required catalyst carrier again.The side direction compression strength of this carrier is～60N/mm that specific area is～105m
2/ g.
Embodiment 5: get the titanium dioxide 1000g for preparing the embodiment preparation, titanium dioxide powder is crushed to particle diameter less than 325 orders, add 230g bentonite, 60g sodium carboxymethylcellulose, 25g aluminum stearate, after mixed grinding is even, add 30g glycerine, the red fuming nitric acid (RFNA) of 10g 65%, 300g distilled water, mixer kneader becomes mud in kneader.In pug, add 100g glass fibre or silicon oxide fibre, further mediate evenly.Pug is being lower than under 25 ℃ the condition old 12 hours, on extruder, is being extruded into the carrier of alveolate texture with porous mold with extrusion pressure greater than 6.5MPa.It is cylindrical extruding honeycomb substrate, and hole wall is thick to be 1.2mm, and hole count is 60cpsi.After the carrier that will wet was at room temperature placed 12 hours, oven dry was 12 hours in 60 ℃ of following air atmospheres, in 500 ℃ of following calcinations 6 hours, makes required catalyst carrier again.The axial compression strength of this carrier is～35Kg/cm
2, specific area is～100m
2/ g.
Embodiment 6: get the titanium dioxide 10000g for preparing the embodiment preparation, titanium dioxide powder is crushed to particle diameter less than 325 orders, add 200g silica, 600g methylcellulose, 250g aluminum stearate, mixed grinding is even.Add 1000g hydrated titanium dioxide colloidal solution subsequently, mediate evenly.Other gets 1000g boehmite (PA98 type, Nanjing petrochemical industry alkylbenzene factory produces), with its nitric acid mixing pulping with 2000g 0.5M, joins in the said mixture.Add 300g glycerine, 100g citric acid, 200g distilled water again, mixer kneader becomes mud in kneader.In pug, add 1000g glass fibre or silicon oxide fibre, further mediate evenly.Pug is lower than under 25 ℃ the condition old 12 hours, under the 20MPa extrusion pressure, is being extruded into the carrier of alveolate texture with porous mold.It is square extruding honeycomb substrate, and the aperture pitch is 7.4mm, and hole wall is thick to be 1.2mm, and hole count is 11cpsi.After the carrier that will wet was at room temperature placed 12 hours, oven dry was 12 hours in 60 ℃ of following air atmospheres, in 500 ℃ of following calcinations 6 hours, makes required catalyst carrier again.The axial compression strength of this carrier is～45Kg/cm
2, specific area is～119m
2/ g.
Application Example: with the saturated dipping of carrier of above-mentioned forming method preparation with the 10g ammonium vanadate: 24g ammonium tungstate: the red fuming nitric acid (RFNA) of 60g ammonium molybdate: 15ml 95%: the mixed solution that the ratio of 200g water is mixed with.Dry 12h down in 100 ℃ of air atmospheres then, roasting 6h under 500 ℃ of air atmospheres is prepared into catalyst.This catalyst is applied to SCR, and to remove the test effect of NOx as shown in the table.The result shows that the titanium dioxide base carrier for preparing with the inventive method moulding is a kind of good catalyst carrier, has advantages of high catalytic activity with this denitrating catalyst for preparing, and compares with fine catalyst, and catalytic performance is approaching substantially.
Catalyst activity appreciation condition: the SCR performance that adopts the simulation reaction device evaluate catalysts.310 ℃ of reaction temperatures, bed gas pressure 0.1MPa, gas composition NO 910ppm, O
24vol%, NH
3/ NO (mol ratio)=1.1, all the other are N
2, gas space velocity 10,000mL/ (g.h).Adopt hydrochloride naphthodiamide colorimetric method (Saltzman method, GB/T 15436-1995) to measure NO
xConcentration.
Claims (10)
1. the preparation method of a titanium dioxide base carrier, it is characterized in that: the titanium dioxide or the dried metatitanic acid that make with the titanium tetrachloride hydrolysis neutralization precipitation are raw material, with titanium dioxide or dried metatitanic acid powder, temporary binding agent becomes uniformed powder with the first mixed grinding of pore creating material, again with structural binding agent, the moulding adhesion promoter, extrusion aid and water adding mix, and be kneaded into mud, after pug is old, extrusion molding, after extrudate ageing at room temperature, be not higher than drying and dewatering under 80 ℃ the condition, become described titanium dioxide base carrier 400～600 ℃ of following calcinations then, wherein, the percentage by weight of each component is respectively: (1) titanium dioxide or dried metatitanic acid content 60～85%, and dried metatitanic acid is in titanium dioxide weight; (2) structural binder content 5～35%; (3) temporary binder content 1～10%; (4) extrusion aid content 1～10%; (5) pore creating material content 1～5%; (6) moulding adhesion promoter content 0.5～2%; (7) all the other are water.
2. preparation method according to claim 1, it is characterized in that: described structural binding agent is selected from the group that is made up of following each thing: boehmite, silica or silicic acid liquid, natural clay, hydrated titanium dioxide colloidal solution, and arbitrarily both or both above combination in the above mentioned binding agent.
3. preparation method according to claim 1 is characterized in that: described temporary binding agent is methylcellulose, hydroxypropyl methylcellulose, carboxymethyl cellulose or sodium type, starch, or polyethylene glycol.
4. preparation method according to claim 1 is characterized in that: described extrusion aid is glycerine, tung oil, starch, paraffin, water, graphite, or talcum powder.
5. preparation method according to claim 1 is characterized in that: described pore creating material is aluminum stearate, starch, carbon dust, or paraffin.
6. preparation method according to claim 1 is characterized in that: described moulding adhesion promoter is nitric acid, citric acid, or benzoic acid.
7. preparation method according to claim 1 is characterized in that: describedly oldly last 12～72 hours.
8. preparation method according to claim 1 is characterized in that: described ageing lasted more than 12 hours.
9. preparation method according to claim 1, it is characterized in that: described structural binding agent is selected from the group that is made up of following each thing: boehmite, silica or silicic acid liquid, natural clay, hydrated titanium dioxide colloidal solution, and arbitrarily both or both above combination in the above mentioned binding agent; Described temporary binding agent is methylcellulose, hydroxypropyl methylcellulose, carboxymethyl cellulose or sodium type, starch, or polyethylene glycol; Described extrusion aid is glycerine, tung oil, starch, paraffin, water, graphite, or talcum powder; Described pore creating material is aluminum stearate, starch, carbon dust, or paraffin; Described moulding adhesion promoter is nitric acid, citric acid, or benzoic acid; Describedly oldly last 12～72 hours; Described ageing lasted more than 12 hours.
10. each described preparation method in requiring according to aforesaid right, it is characterized in that: described article shaped is cellular, cylindric or the clover shape.
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