CN104941628A - Method for preparing waste gas treatment catalyst utilizing used catalyst and waste gas treatment catalyst - Google Patents
Method for preparing waste gas treatment catalyst utilizing used catalyst and waste gas treatment catalyst Download PDFInfo
- Publication number
- CN104941628A CN104941628A CN201510140096.6A CN201510140096A CN104941628A CN 104941628 A CN104941628 A CN 104941628A CN 201510140096 A CN201510140096 A CN 201510140096A CN 104941628 A CN104941628 A CN 104941628A
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- Prior art keywords
- catalyst
- waste gas
- treating waste
- titanium oxide
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- 238000000034 method Methods 0.000 title claims abstract description 59
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- 239000008117 stearic acid Substances 0.000 description 1
- 229960004274 stearic acid Drugs 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
- Exhaust Gas After Treatment (AREA)
Abstract
The invention provides a method for preparing a waste gas treatment catalyst utilizing a used catalyst, the used catalyst contains titanium oxide, and the prepared waste gas treatment catalyst is good in moldability, intensity, and wear resistance. The method for preparing the waste gas treatment catalyst comprises smashing used waste gas treatment catalyst containing titanium oxide into powder whose average grain diameter is in the range from 0.1 to 15 [mu]m; mixing a titanyl sulfate aqueous solution and/or a metatitanic acid slurry, and the used waste gas treatment catalyst containing titanium oxide powder to form a mixed slurry, wherein the ratio of the concentration (CT), taking TiO2 into account, of the titanyl sulfate aqueous solution and/or the metatitanic acid slurry to the concentration (CRC), taking solid component in to account, of the used waste gas treatment catalyst is (CT)/(CRC) in the range from 0.1 to 9.0; filtering the mixed slurry, adding an alkali compound to neutralize titanyl sulfate and/or metatitanic acid, so as to prepare titanium oxide gel whose pH is within 7 to 12.; sintering the gel, smashing to prepare titanium oxide micro powder; and mixing the titanium oxide micro powder and reinforcing material, moulding and sintering the mixture.
Description
Technical field
The present invention relates to manufacture method and the catalyst for treating waste gas of the catalyst for treating waste gas utilizing the catalyst used.
Background technology
In the past, to polluter, especially NO that the mobile generation source such as fixing generation source, automobile such as from power station is discharged
xuse honeycomb catalyst as selective reduction type NO
xcatalyst (hereinafter referred to as SCR catalyst) processes.
Although coal, mink cell focus, timber etc. are used as fuel when the fixing generation source such as known power station, but such as when coal, grade containing V, Ni, Fe, Hg, As, Si, Ca, Mg, S composition, ash in burnt gas, these deposit in catalyst for treating waste gas, accumulation, and catalyst physical, chemical property are deteriorated.So when performance degradation acquires a certain degree, the catalyst for treating waste gas more renewed runs.
Here, if by directly discarded for the catalyst used taken out, can environmental problem be caused, in addition, in the catalyst used, a large amount of composition, the active metal components useful containing titanium oxide, Mo, W, V etc., therefore study the method being regenerated, recycle.Japanese Patent Laid-Open 2005-185928 publication (patent document 1), Japanese Patent Laid-Open 2011-251245 publication (patent document 2)
Such as, disclosing the renovation process of the following catalyst for treating waste gas used in Japanese Patent Laid-Open 2005-185928 publication (patent document 1): after the catalyst for treating waste gas of the burnt gas for super mink cell focus is heated, denitration performance and SO can be made by carrying out cleaning with oxalic acid aqueous solution
2oxidability is recovered.
In addition, the renovation process of the following catalyst for treating waste gas used is disclosed: the catalyst for treating waste gas used to be pulverized, miniaturization in Japanese Patent Laid-Open 2011-251245 publication (patent document 2), be made into matrix formed body, in addition new catalyst for treating waste gas is pulverized, be made into slurry liquid, this slurry liquid is overlayed on the surface of matrix formed body.
Prior art document
Patent document
Patent document 1: Japanese Patent Laid-Open 2005-185928 publication
Patent document 2: Japanese Patent Laid-Open 2011-251245 publication
Summary of the invention
Invent technical problem to be solved
But, in the method that patent document 1 is recorded, denitration performance and SO
2the recovery of oxidability is not necessarily abundant, and need to containing the impurity such as vanadium, sulfate ion and for the treatment of a large amount of cleaning waste liquids of oxalic acid process, economy has problems.
In addition, in the method for patent document 2, use the insufficient formability of mouldability than common catalyst for treating waste gas of the formed body of the catalyst for treating waste gas used pulverized, sometimes the article formed into honeycomb that shaping heavy caliber, thin-walled or hole count are many is difficult to, and fully do not remove attachment material by burning till step for regeneration, initial stage exhaust-gas treatment performance and catalyst life deficiency compared with common catalyst for treating waste gas.
Technical problem of the present invention be utilize use containing titanium oxide catalyst for treating waste gas, be provided in mouldability, intensity, abrasion resistance etc. excellent while the manufacture method of catalyst for treating waste gas of catalyst for treating waste gas function admirable and catalyst for treating waste gas.
The technical scheme that technical solution problem adopts
So, the present inventor conscientiously studies rear discovery, if when preparing the titanium oxide based micropowder used in the preparation section of catalyst for treating waste gas in the past, mix in the titanyl sulfate used usually used as raw material or metatitanic acid slurry through using of pulverizing containing titanium oxide catalyst for treating waste gas filtering, then can remove the Na as the composition causing catalyst degradation, K, the alkali metal such as Ca, alkaline-earth metal, if it can be used as main material to use, mouldability is excellent, the intensity of the catalyst for treating waste gas obtained, abrasion resistance, exhaust-gas treatment performances etc. are excellent, thus complete the present invention.
The feature of the manufacture method of catalyst for treating waste gas of the present invention is,
After by pulverizing containing titanium oxide catalyst for treating waste gas of using, to make average grain diameter be the powder of 0.1 ~ 15 μm,
By aqueous solution of titanyle sulfate and/or metatitanic acid slurry and mixing containing titanium oxide catalyst for treating waste gas powder of using, prepare mixed slurry, make aqueous solution of titanyle sulfate and/or metatitanic acid slurry with TiO
2concentration (the C of meter
t) and the concentration (C of solid constituent containing titanium oxide catalyst for treating waste gas used through pulverizing
rC) concentration ratio (C
t)/(C
rC) reach 0.1 ~ 9.0 scope,
After filtering this mixed slurry, add alkali compounds and titanyl sulfate and/or metatitanic acid neutralized, the titanium oxide gel of preparation pH in the scope of 7 ~ 12,
This gel is burnt till, then pulverizes, preparation titanium oxide based micropowder,
Mix this titanium oxide fine powder end and reinforcing material,
To mixture carry out shaping after burn till.
Can in being undertaken by alkali compounds and before mixed active component precursor compound, also can be mixed together active component precursors compound with reinforcing material.
Active component precursors compound is the compound of at least a kind of element being selected from V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, Ir, comprises this metal element and the compound that can generate oxide.
Catalyst for treating waste gas of the present invention is obtained by said method, it is characterized in that,
Containing (i) titanium oxide based micropowder and (ii) reinforcing material, the content of (i) titanium oxide based micropowder is in the scope of 60 ~ 97 % by weight, and the content of (ii) reinforcing material is in the scope of 3 ~ 15 % by weight.
Further, preferably containing (iii) active component, should the content of (iii) active component with oxide basis in the scope of 0.001 ~ 15 % by weight.
The content of the titanium oxide based oxide (or composition) containing titanium oxide catalyst for treating waste gas that deriving from above-mentioned (i) titanium oxide based micropowder uses is preferably in the scope of 8.5 ~ 90 % by weight.
Further, preferably containing filler, the content of this filler is in the scope of 0.5 ~ 15 % by weight.
Above-mentioned catalyst for treating waste gas is honeycomb formed article, and the external diameter of this honeycomb is preferably in the scope of 30 ~ 400mm, and length is preferably in the scope of 3 ~ 1500mm, and hole density is preferably in the scope of 6 ~ 500cpsi, and thickness is preferably in the scope of 0.1 ~ 1.9mm.
Above-mentioned active component is preferably selected from metal or the metal oxide of at least a kind of element of V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, Ir.
The content of above-mentioned active component with oxide basis preferably in the scope of 0.001 ~ 15 % by weight.
The effect of invention
If employing the present invention, then can provide mouldability, intensity, abrasion resistance and catalyst for treating waste gas function admirable, and the manufacture method of catalyst for treating waste gas also excellent in economy and catalyst for treating waste gas.
Detailed description of the invention
First, the manufacture method of catalyst for treating waste gas of the present invention is described.
[manufacture method of catalyst for treating waste gas]
The manufacture method of catalyst for treating waste gas of the present invention comprises makes containing the pulverizing of titanium oxide catalyst for treating waste gas the operation (operation (a)) that average grain diameter is the powder of 0.1 ~ 15 μm by what use.
operation (a)
To pulverizing containing titanium oxide catalyst for treating waste gas of using.
As use containing titanium oxide catalyst for treating waste gas, mainly can use the above-mentioned polluter that the mobile generation source such as fixing generation source, automobile is discharged from power station etc., in particular for NO
xthe catalyst of the selective reduction process of gas.
Except ash described later grades, what use contains titanium oxide catalyst for treating waste gas with TiO
2meter is preferably containing more than 50 % by weight titanium oxide.
Be applicable to using the waste gas produced for the treatment of fixing generation sources such as power stations coal, mink cell focus, timber etc. used as fuel cellular use contain titanium oxide catalyst for treating waste gas.
Especially when using coal as fuel, grade containing V, Ni, Fe, Hg, As, Si, Ca, Mg, Na, K, S composition, ash in burnt gas, these compositions contain deposition in titanium oxide catalyst for treating waste gas, accumulation what use, if adopt manufacture method of the present invention, then these compositions contained in the catalyst for treating waste gas that optionally minimizing or removal finally obtain.
As the breaking method containing titanium oxide catalyst for treating waste gas used, as long as can pulverize as desired size is then not particularly limited, known method can be adopted.Such as, atomizer, Henschel mixer, pulverizer, Ya Liya pulverizer (ヤ リ ヤ powder crushed Machine) etc. can be used to pulverize.
Through the size containing titanium oxide catalyst for treating waste gas of using of pulverizing from the viewpoint of the funds such as the energy, equipment, the rate of recovery of pulverizing process, the filterability required for pulverizing with remove inside particles impurity etc., average grain diameter is 0.1 ~ 15 μm, more preferably the scope of 0.5 ~ 10.0 μm.
If through the lower limit of average grain diameter lower than above-mentioned scope containing titanium oxide catalyst for treating waste gas used pulverized, the funds such as the energy, equipment then sometimes required for pulverizing improve, and the rate of recovery of pulverizing process declines, the filterability decline of slurry sometimes, the removal of impurity become insufficient; If average grain diameter is excessive, although then filterability improves, owing to can not remove the impurity of the inside particles containing titanium oxide catalyst for treating waste gas used through pulverizing, cleaning performance is insufficient sometimes.
In the present invention, by laser diffraction formula particle size distribution analyzer, (hole field makes made the average grain diameter containing the titanium oxide based micropowder in titanium oxide catalyst for treating waste gas and operation (h) described later used through pulverizing: LA-300) measure.
Then, by aqueous solution of titanyle sulfate and/or metatitanic acid slurry and through using of pulverizing containing the mixing of titanium oxide catalyst for treating waste gas, make mixed slurry, make aqueous solution of titanyle sulfate and/or metatitanic acid slurry with TiO
2concentration (the C of meter
t) and the concentration (C of solid constituent containing titanium oxide catalyst for treating waste gas used through pulverizing
rC) concentration ratio (C
t)/(C
rC) reach 0.1 ~ 9.0 scope (operation (b) and (c)).
operation (b)
By aqueous solution of titanyle sulfate and/or metatitanic acid slurry and through using of pulverizing containing the mixing of titanium oxide catalyst for treating waste gas, make mixed slurry.
Here, metatitanic acid slurry refer to and be hydrolyzed titanium sulfate after containing the slurry of titanium hydroxide.
Aqueous solution of titanyle sulfate in mixed slurry and/or metatitanic acid slurry with TiO
2concentration (the C of meter
t) be 5 ~ 40 % by weight, the more preferably scope of 10 ~ 30 % by weight.If the above-mentioned concentration (C in mixed slurry
t) low, then economy declines; If the above-mentioned concentration (C in mixed slurry
t) too high, then the viscosity of operation (b) and the middle slurry of operation (d) uprises, and sometimes stirs and becomes difficulty.
If be dispersed in titanyl sulfate and/or metatitanic acid by the titanium oxide catalyst for treating waste gas that contains used pulverized, then pH becomes acidity, especially becomes the salt centered by alkali composition and dissolves.In addition, sulphur composition becomes sulfate ion.These are removed by filtration, dehydration procedure.In addition, undertaken neutralizing (alkalescence) by the interpolation of alkali compounds described later, produce titanium oxide gel by titanyl sulfate and/or metatitanic acid.Because this gel is to cover the form generating containing titanium oxide catalyst for treating waste gas used through pulverizing, therefore with after preparing gel in advance again with carry out compared with situation about mixing through using of pulverizing containing titanium oxide catalyst for treating waste gas, can make that the mouldability of catalyst for treating waste gas is high and intensity etc. are excellent.
In addition, in mixed slurry use containing titanium oxide catalyst for treating waste gas with the concentration (C of solid component meter
rC) be 3 ~ 55 % by weight, the preferred scope with 9 ~ 25 % by weight contains further.
If above-mentioned concentration (C
rC) low, then low from the viewpoint of recycling the efficiency containing titanium oxide catalyst for treating waste gas used.If above-mentioned concentration (C
rC) too high, then the viscosity of mixed slurry uprises, and sometimes stirs and becomes difficulty.
Now, above-mentioned concentration (C
t) and above-mentioned concentration (C
rC) concentration ratio (C
t)/(C
rC) be 0.1 ~ 9.0, further preferably 1.0 ~ 5.0 scope.
If concentration ratio (C
t)/(C
rC) too low, then through using of pulverizing insufficient containing the Impurity removal in titanium oxide catalyst for treating waste gas while formability deteriorates sometimes, in addition, the denitration performance of the catalyst for treating waste gas sometimes finally obtained is not enough.If concentration ratio (C
t)/(C
rC) too high, then the use amount containing titanium oxide catalyst for treating waste gas owing to using is few, therefore low from the viewpoint of recycling the efficiency containing titanium oxide waste air process catalyst used.
The all solids constituent concentration of mixed slurry is 8 ~ 60 % by weight, further preferably 19 ~ 39 % by weight scope.
If all solids constituent concentration of mixed slurry is low, then the filtrate in operation (c) becomes many, and owing to needing to process the low filtrate of impurity concentration in a large number, treatment effeciency and economy decline sometimes.If all solids constituent concentration of mixed slurry is too high, then the viscosity of mixed slurry uprises, and causes obstacle, be sometimes difficult to carry out subsequent handling to stirring or filtration.In addition, when all solids constituent concentration of mixed slurry is too high, dilution water can be added as required.
In addition, the pH of usual mixed slurry in the scope of 0.5 ~ 4, further preferably 1.0 ~ 3.0 scope.When mixed slurry pH lower than 0.5, because the clearance of the impurity such as alkali when filtering in aftermentioned operation (c), alkaline-earth metal can not uprise further, use quantitative change for the alkali compounds neutralized in operation (d) is many, therefore uneconomical.
If the pH of mixed slurry is more than 4, then the removal of the impurity such as alkali, alkaline-earth metal becomes insufficient sometimes.
In addition, when the pH of mixed slurry is not in above-mentioned scope, acid can be added or pH is adjusted to above-mentioned scope by alkali.
As acid, the organic acids such as inorganic acid or oxalic acid such as hydrochloric acid, nitric acid, sulfuric acid can be used.In addition, as alkali, NaOH, potassium hydroxide, sodium carbonate, NH can be used
4oH etc.
In addition, mixed slurry can heat as required.
As heating condition, as long as the impurity such as Ca, K, Na can be removed efficiently in the filtration of operation (c) then, be not particularly limited, roughly preferably the scope of 40 ~ 60 DEG C, now, can not stir, but preferably stir.
By heating mixed slurry, can promote, with the neutralization reaction of the impurity such as Ca, K, Na, impurity can be removed efficiently by impurity being become soluble-salt.
operation (c)
As above the mixed slurry prepared is filtered, dewatered.Be not particularly limited as filtration, dewatering, known method can be adopted.
Such as, vacuum filtration process, compression filtration, weight filtration method, centrifugation etc. can be exemplified.
Due to Ca, K, Na, S (SO of stripping in filtrate can be removed by filtering, dewatering
4) etc. or ash grade and cause the composition of catalyst degradation, therefore finally can obtain the catalyst for treating waste gas of good activity.
Filter, the solid constituent amount of filter cake after dehydration has change to a certain degree according to the size of particle, but more than 30 % by weight, preferably in the scope of 45 ~ 55 % by weight.
If the solid component concentration of the filter cake after filtration, dehydration is low, then dewater insufficient, impurity is remaining in a large number, and the performance of the catalyst for treating waste gas sometimes obtained is not enough.
Filter, dehydration after filter cake in add alkali compounds titanyl sulfate and/or metatitanic acid are carried out in and, preparation the titanium oxide gel of pH in the scope of 7 ~ 12 (operation (d)).
operation (d)
Filter, dehydration after filter cake in add alkali compounds titanyl sulfate and/or metatitanic acid are carried out in and, prepare titanium oxide gel.
As alkali compounds, as long as titanyl sulfate and/or metatitanic acid are made titanium oxide gel by neutralization, NH can be exemplified
4oH, NaOH, potassium hydroxide etc.
In the present invention, never consider containing alkali-metal aspect, be applicable to using NH
4oH.
The pH of the titanium oxide gel after neutralization is 7 ~ 12, further preferably 8 ~ 10 scope.
The pH of titanium oxide gel after the neutralization lower than 7 when, sulfate ion is remaining in a large number sometimes, and mouldability becomes insufficient sometimes.In addition, the specific area of the raw material after burning till in operation (g) diminishes, and the performance of the catalyst for treating waste gas sometimes obtained is not enough.
If the pH of the titanium oxide gel after neutralization is more than 12, then the use quantitative change of alkali compounds is many, and economy declines sometimes.
In the present invention, can interpolation alkali compounds neutralisation of sulphuric acid oxygen titanium and/or metatitanic acid before mixed active component precursor compound (A).
As active component precursors compound (A), use the compound being selected from least a kind of element of V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, Ir.
Specifically, ammonium metavanadate, vanadic sulfate, ammonium paratungstate, ammonium metatungstate, wolframic acid, ammonium molybdate, chromic nitrate, chromium acetate, manganese nitrate, manganese acetate, palladium nitrate, ferric sulfate, nickel nitrate, copper nitrate, silver nitrate, yttrium nitrate, cerous nitrate, chlorauride, iridium chloride etc. can be exemplified.
Preferably active component precursors compound (A) is used as solution, although different according to the kind of compound, are preferably dissolved in the acid such as the alkali such as water, MEA, oxalic acid and use.
For the combined amount of active component precursors compound (A), consider the above-mentioned content containing the active component in titanium oxide catalyst for treating waste gas used, to be 0.001 ~ 15 % by weight with the content of the oxide basis of element in the catalyst for treating waste gas finally obtained, preferably the scope of 0.3 ~ 12 % by weight uses further.If the content of active component is few, then such as selective reduction type NO
xwhen catalyst uses, the NO of catalyst for treating waste gas sometimes
xclearance not enough.If the content of active component is too much, then compressive strength, the resistance to anti-thread breakage deficiency of formed body.
Then, after neutralizing the pH scope into afore mentioned rules, preferably carry out heating, slaking.
Now, curing temperature is 40 ~ 95 DEG C, further the preferred scope of 50 ~ 75 DEG C, and the curing time is different according to curing temperature, but is roughly 1 ~ 24 hour.
If curing temperature is in above-mentioned scope, then gel homogenizes, and the mouldability in operation (k) improves, and the crackle of the formed body obtained is suppressed, can obtain the catalyst for treating waste gas that intensity, abrasion resistance etc. are excellent.
operation (e)
Then, the titanium oxide gel after neutralization is cleaned.In addition, not to clean, but as cleaning method, as long as can to reduce, remove Ca, K, Na, SO
4then be not particularly limited Deng impurity, known method can be adopted.
Such as, use the device identical with above-mentioned operation (c), after the titanium oxide gel after neutralization is filtered, dewatered, by watering, preferably watering warm water and clean.
Now, if use weak aqua ammonia in water, then can remove the anion such as sulfate ion efficiently.
operation (f)
Drying is carried out to the gel obtained in operation (e).
As drying means, as long as this gel powderization then can be not particularly limited, known method can be adopted.
Baking temperature is different according to drying time, but is roughly the scope of 70 ~ 120 DEG C.
The gel of as above powdered is burnt till, then pulverizes, preparation titanium oxide based micropowder (operation (g) and (h)).
operation (g)
Firing temperature is 450 ~ 700 DEG C, further the preferred scope of 500 ~ 650 DEG C.
If firing temperature is low, then because the crystallization of titanium oxide is insufficient, mixing being difficult in operation (i) is carried out, and sometimes make mouldability not enough due to the bleeding (Japanese: From water) when easily causing extrusion forming.
If firing temperature is too high, then advance the crystallization of titanium oxide, specific area diminishes, use it and the catalyst for treating waste gas that obtains performance is not enough sometimes.
Firing time is different according to firing temperature, but is roughly 1 ~ 24 hour.
operation (h)
After burning till, pulverize and the average grain diameter of titanium oxide based micropowder that obtains is 0.1 ~ 15 μm, further the preferred scope of 0.5 ~ 5 μm.
The funds such as the energy, equipment required for the pulverizing to the above-mentioned range lower limit of titanium oxide based micropowder improve, and mouldability also can not improve further, thus not preferred.If average grain diameter is excessive, then mouldability in operation (k) declines, and the formed body sometimes obtained cracks, and intensity, abrasion resistance etc. are not enough and not preferred.
As long as breaking method now makes average grain diameter in above-mentioned scope, be not particularly limited, known method can be adopted, such as, the method identical with above-mentioned operation (a), device can be adopted.
Afterwards, by this titanium oxide fine powder end and reinforcing material mixing, after mixture is shaping, carry out drying, burn till (operation (i) ~ (m)).
operation (i)
Be prepared in the mixture (hereinafter referred to as formed body composition) being mixed with reinforcing material in above-mentioned titanium oxide based micropowder.The content of the titanium oxide based micropowder in said composition counts 33 ~ 80 % by weight with solid constituent, further preferably 40 ~ 75 % by weight scope.If the content of the titanium oxide based micropowder in formed body composition is few, then while difficult forming, catalyst performance, such as selective reduction type NO sometimes
xthe NO of catalyst
xclearance not enough.
reinforcing material
As reinforcing material, the fibrous reinforcements such as glass fibre, ceramic fibre can be used.
If containing such reinforcing material, then the generation of the be full of cracks that contraction time dry after can suppressing extrusion molding causes, can prepare the catalyst for treating waste gas that compressive strength, abrasion resistance are excellent.
The content of the reinforcing material in formed body composition counts 1.8 ~ 12.8 % by weight with solid constituent, further preferably 3 ~ 10 % by weight scope.
If the content of the reinforcing material in formed body composition is few, then the be full of cracks that contraction time dry after sometimes there is extrusion molding causes.If the content of the reinforcing material in formed body composition is too much, then during extrusion molding sometimes, reinforcing material blocks in mold for forming, hinders mouldability.
filler
In the present invention, filler can be contained in formed body composition.If containing filler, then can obtain the formed body that compressive strength, abrasion resistance are excellent while carrying out extrusion molding continuously.
As filler, the ceramic powders such as cordierite, aluminium oxide, zirconia, silicon nitride, carborundum, clay mineral can be used.
The content of the filler in formed body composition counts 0.42 ~ 12.8 % by weight with solid constituent, further preferably 1 ~ 10 % by weight scope.
If the content of the filler in formed body composition is few, then continuous extrusion declines, and has the shaping of the honeycomb formed article of the formed body of duration size, especially long size to become difficulty, in addition, sometimes the cleaning of mold for forming or replacing become frequent, and productivity, economy decline.If the content of the filler in formed body composition is too much, then catalyst performance becomes not enough sometimes.
organic additive
In the present invention, can further containing organic additive in formed body composition.
As organic additive, aliphatic acid, fatty acid ester etc. can be used.
Saturated fatty acid represented by the preferred following formula of above-mentioned aliphatic acid (1) and/or the unrighted acid represented by following formula (2).
C
nH
2n-CO
2H················(1)
(wherein, n is the integer of 4 ~ 23)
C
n'H
2n'-2m+1-CO
2H······(2)
(wherein, n' is the integer of 13 ~ 23, and m represents the quantity of double bond, is the integer of 1 ~ 6)
As saturated fatty acid, specifically, stearic acid, laurate, myristic acid, behenic acid, arachidic acid, lignoceric acid, palmitic acid etc. and their mixture can be exemplified.
In addition, as unrighted acid, oleic acid, arachidonic acid, linoleic acid, leukotrienes, eicosapentaenoic acid, DHA etc. and their mixture can be exemplified.
In addition, be also applicable to using fatty acid ester, carboxymethyl cellulose, methylcellulose, hydroxypropyl cellulose, CMC, avicel cellulose, polyethylene glycol, polypropylene glycol, the PEOs etc. such as fatty acid glyceride.
If containing so organic adding material, then can improve the effect such as fissility, mouldability from mold for forming.
The content of the organic additive in formed body composition counts 0.03 ~ 4.3 % by weight with solid constituent, further preferably 0.5 ~ 2 % by weight scope.
If the content of the organic additive in formed body composition is few, then mouldability becomes not enough; If too much, then the pore volume of the formed body catalyst obtained becomes large, becomes outside deficiency, sometimes produce be full of cracks when formed body burns till in compressive strength.
active component precursors compound (B)
And, in this operation (i), can mixed active component precursor compound (B).
As active component precursors compound (B), the compound identical with above-mentioned active component precursors compound (A) can be used.
For the combined amount of active component precursors compound (B), consider above-mentioned use containing the content of active component in titanium oxide catalyst for treating waste gas and the content of active component precursors compound (A), to be 0.001 ~ 15 % by weight with the content of the oxide basis of element in the catalyst for treating waste gas finally obtained, preferably the scope of 0.3 ~ 12 % by weight uses further.
If the content of active component is few, then such as selective reduction type NO
xwhen catalyst uses, the NO of catalyst for treating waste gas sometimes
xclearance not enough.If the content of active component is too much, then compressive strength, the resistance to anti-thread breakage deficiency of formed body.
solvent
Formed body composition can contain solvent beyond mentioned component.As solvent, suitably can select according to application target and forming method.
Specifically, the volatile solvents such as water, methyl alcohol, ethanol, propyl alcohol, methyl ethyl ketone can be exemplified, preferred water.
The concentration of the solvent in such formed body composition is 15 ~ 40 % by weight, the preferably scope of 25 ~ 35 weight, and all solids constituent concentration is 60 ~ 85 % by weight, further preferably 65 ~ 75 % by weight scope.
If all solids constituent concentration of formed body composition is too low, then the conformality of the formed body after extrusion molding, before drying is poor, sometimes deforms.
If all solids constituent concentration of formed body composition is excessive, then sometimes poor by fluency during mould, mouldability, especially continuously shaped property decline.
operation (j)
To the formed body composition as above prepared carry out mixing, knead.As mixing, method of kneading, as long as can the above-mentioned each material of Homogeneous phase mixing, be not particularly limited, known mixed method can be adopted.
Usual use kneader, but also can use continuous kneader, mixer etc.
Mixing and knead and preferably carry out under heating.Temperature is now roughly 80 ~ 140 DEG C, further the preferred scope of 90 ~ 130 DEG C.By carrying out mixing in such temperature range and kneading, the formed body composition that mouldability is excellent can be prepared.
In addition, incorporation time is different according to temperature, but is roughly 0.25 ~ 5 hour.
operation (k)
Forming method that is mixing and pug mill can use known forming machine, suitably can select according to the shape of formed body, kind etc., usually extrusion shaping machine can be used, the applicable vacuum extruding form machine when carrying out shaping to the formed body of the such complex structure of honeycomb type formed body.
operation (l)
As the drying means in drying process (l), as long as can not bend, do not produce deformation, do not carry out evenly dry with cracking in addition, be not particularly limited, known method can be adopted.
Such as, when carrying out drying to article formed into honeycomb, although different according to external diameter, length, hole, thickness etc., the temperature roughly preferably scope of 30 ~ 65 DEG C, drying time the roughly preferably scope of 24 ~ 72 hours.
operation (m)
Burn till afterwards, firing temperature is 450 ~ 700 DEG C, further the preferred scope of 480 ~ 600 DEG C.If firing temperature is low, then causes organic substance residues due to the organic compound etc. used, hinder catalyst performance sometimes.If firing temperature is too high, then the crystallization of titanium oxide excessively carries out, and specific area and the pore volume of the catalyst for treating waste gas obtained diminish sometimes, and catalyst performance becomes not enough sometimes.
Firing time is different according to firing temperature, but is roughly 1 ~ 24 hour.
Catalyst for treating waste gas of the present invention can be manufactured through above each operation.
[catalyst for treating waste gas]
The feature of catalyst for treating waste gas of the present invention is, manufactured by said method, containing (i) titanium oxide based micropowder and (ii) reinforcing material, i the content of () titanium oxide based micropowder is in the scope of 60 ~ 97 % by weight, the content of (ii) reinforcing material is in the scope of 3 ~ 15 % by weight.
(i) titanium oxide based micropowder
The content of (i) titanium oxide based micropowder in catalyst for treating waste gas is 60 ~ 97 % by weight, preferably 60 ~ 96 % by weight, and the more preferably scope of 75 ~ 90 % by weight.
If the content of (i) titanium oxide based micropowder in catalyst for treating waste gas is few, then the clearance of the performance of catalyst for treating waste gas, the NOx of specifically selective reduction type NOx catalyst becomes not enough sometimes.
If the content of (i) titanium oxide based micropowder in catalyst for treating waste gas is too much, then aftermentioned other reinforcing material, filler, active component precursors use amount limited, the compressive strength, resistance to anti-thread breakage and NOx clearance etc. of catalyst for treating waste gas become not enough sometimes.
The content of the titanium oxide based oxide (or composition) containing titanium oxide catalyst for treating waste gas that deriving from (i) titanium oxide based micropowder in catalyst for treating waste gas uses is 8.5 ~ 90 % by weight, preferably 10 ~ 90 % by weight, further preferably 25 ~ 50 % by weight scope.In addition, also other compositions not removed such as active component are contained in (i) titanium oxide based micropowder.
(ii) reinforcing materialthe content of (ii) reinforcing material in catalyst for treating waste gas is 3 ~ 15 % by weight, further preferably 3 ~ 10 % by weight scope.
If the content of reinforcing material is few, then the be full of cracks that contraction time dry after sometimes there is extrusion molding causes; If the content of reinforcing material is too much, then during extrusion molding sometimes, reinforcing material blocks in mold for forming, hinders mouldability.
(iii) active component
Further, catalyst for treating waste gas is preferably containing the above-mentioned active component as active component.
The content of the active component in catalyst for treating waste gas is 0.001 ~ 15 % by weight with oxide basis, further preferably 0.3 ~ 12 % by weight scope.If the content of active component is few, then as selective reduction type NO
xwhen catalyst uses, NO sometimes
xclearance not enough.If the content of active component is too much, then compressive strength, the resistance to anti-thread breakage deficiency of formed body.
Herein, the total deriving from the active component of active component precursors compound (A) and (B) that uses for active component contained in the catalyst for treating waste gas that uses, above-mentioned operation (d) and/or above-mentioned operation (i) of active component.
filler
Catalyst for treating waste gas can contain filler.If containing filler, then compressive strength, abrasion resistance are excellent.
Catalyst for treating waste gas can contain above-mentioned filler.
The content of the filler in catalyst for treating waste gas is 0.5 ~ 15 % by weight, further preferably 3 ~ 10 % by weight scope.
If the content of the filler in catalyst for treating waste gas at least intensity is low; In addition, if the content of filler is too much, then catalyst performance becomes not enough sometimes.
The shape of catalyst for treating waste gas of the present invention can adopt the known shapes such as particle, bead, ring-type, honeycomb.
Owing to using above-mentioned formed body composition in the present invention, therefore mouldability is high, and catalyst strength, the abrasion resistance of the cellular exhaust-gas treatment obtained are excellent.In addition, by suitably selecting kind, use amount, the using method of above-mentioned organic additive, the formed body that mouldability improves further, thin-walled property, hole count are many can be obtained.
The longitudinal and transverse size of cellular catalyst for treating waste gas or external diameter are preferably in the scope of 30 ~ 400mm.
Here, the face shaping of honeycomb is the polygonal of more than quadrangle, hexagon, octagonal, circular, and Elliptical is circular, is not particularly limited, suitably can selects according to purposes, usage.
If the longitudinal and transverse size of cellular catalyst for treating waste gas or external diameter are less than 30mm, then when cellular catalyst for treating waste gas uses as selective reduction type NOx catalyst, only can increase production radical, thus uneconomical.If the longitudinal and transverse size of cellular catalyst for treating waste gas or external diameter are more than 400mm, then do not have to carry out shaping extrusion molding apparatus to the cellular catalyst for treating waste gas of this size.
In addition, the length of cellular catalyst for treating waste gas is 3 ~ 1500mm, further the scope of preferred 50 ~ 1300mm.
When the length of cellular catalyst for treating waste gas is less than 3mm, manufactures and become difficulty.
If the length of cellular catalyst for treating waste gas is more than 1500mm, then purposes is few.
The hole density of cellular catalyst for treating waste gas is 6 ~ 500cpsi, further the scope of preferred 15 ~ 200cpsi.
When the hole density of cellular catalyst for treating waste gas is less than 6cpsi, aperture is large, conformality is deteriorated, and manufactures and becomes difficulty.
If the hole density of cellular catalyst for treating waste gas is more than 500cpsi, then time shaping, the pressure loss becomes large, sometimes shapingly becomes difficulty.
The thickness of cellular catalyst for treating waste gas is 0.1 ~ 1.9mm, further the scope of preferred 0.1 ~ 1.5mm.
Be difficult to obtain the catalyst of thickness lower than 0.1mm of cellular catalyst for treating waste gas.
If the thickness of cellular catalyst for treating waste gas is more than 1.9mm, then contributes to the ratio step-down of the active surface of the honeycomb of catalyst performance, sometimes can not obtain enough performances.
[embodiment]
Be described by the following examples, but the present invention is not limited to these embodiments.
[embodiment 1]
the preparation of catalyst for treating waste gas (1)
Titanium oxide catalyst for treating waste gas (honeycomb shape: honeycomb hole count 20 × 20 order, length 1000mm, composition: TiO is contained by what use
2=79.65 % by weight, WO
3=8.0 % by weight, V
2o
5=0.90 % by weight, impurity: Na
2o=0.35 % by weight, K
2o=0.30 % by weight, CaO=1.5 % by weight, SO
4=6.13 % by weight) pulverize with pulverizer (Ya Liya machinery production institute (ヤ リ ヤ Machine tool System does institute) makes: Ya Liya pulverizer).
Then, titanium oxide catalyst for treating waste gas sieve (mesh size=0.5mm (Japanese Industrial Standards (JIS) regulation)) that contains used through pulverizing being sieved, obtaining the pulverized product (1) of the catalyst used.
operation (a)
Measure the average grain diameter of the pulverized product (1) of the catalyst used, result is shown in table.
By metatitanic acid slurry, (Ishihara Sangyo Kaisha, Ltd.'s (stone originates in industry (strain)) makes: MT-A, TiO
2concentration 30 % by weight, pH1.18) 37.5kg puts into the tank diameter of band heating return channel, and add pulverized product (1) 17.4kg of catalyst used, stir 6 hours at 30 DEG C, make mixed slurry.
work sequence (b)
The pH of cooled mixed slurry is 1.42.
Then, mixed slurry vacuum filter is carried out filtering, dewatering.
operation (c)
Na is carried out to filtrate
2o, K
2o, CaO, V
2o
5analyze, the clearance that the pulverized product (1) from the catalyst used removes these compositions is shown in table.
In filtration, dewatered cake (solid component concentration 51.7 % by weight) 48.4kg, after interpolation ammonium paratungstate (Japan New Metals Co., Ltd.'s (new metal (strain) of Japan) system) 1.42kg also mixes, the ammoniacal liquor 20kg adding concentration 15 % by weight neutralizes.Now, in and the pH of slurry be 9.5.Then, carry out stirring slaking in 3 hours at 95 DEG C.
operation (d)
Afterwards, this neutralization, slaking slurry are cooled to 40 DEG C, then carry out filtering, watering, prepare the cleaning filter cake of solid component concentration 49 % by weight.
operation (e)
Filter cake will be cleaned at 110 DEG C dry 20 hours, after burning till 5 hours further at 550 DEG C, pulverize with pulverizer (Ya Liya machinery production is made: Ya Liya pulverizer), obtain the titanium oxide based micropowder (1) containing the catalyst used.
operation (f), operation (g), operation (h)
Analyze the composition of the titanium oxide based micropowder (1) obtained, in addition, measure average grain diameter, result is shown in table.
Add at titanium oxide based micropowder (1) 24.1kg and ammonium metavanadate 0.082kg is dissolved in MEA 0.250kg and the solution obtained and water 3.5kg, then ammoniacal liquor is added, make the pH of mixed slurry be 7.9, be heated to be 120 DEG C with kneader and knead 0.5 hour.
Afterwards, the glass fibre added in this mixed slurry as reinforcing material (below, is sometimes referred to as " GF ".) 1.39kg, the Emathlite 0.26kg as filler, the PEO 0.500kg as organic additive, mediate 3 hours at 60 DEG C with kneader, prepare formed body composition (1).
operation (i), operation (j)
The content (use amount benchmark) of each composition in formed body composition (1) is shown in table.In addition, by infrared moisture measuring instrument, (Kate Science Institute (ケ Star ト chemistry institute) makes water content: FD-610) measure.
With vacuum extruding form machine (ironworker Co., Ltd. of Miyazaki (the rugged iron work (strain) of Palace) system), extrusion molding is carried out to formed body composition (1), obtain outside dimension and be plane one edge lengths 75m, run through the honeycomb structure (1) that direction length is about 500mm, aperture (dimetric through aperture) 6.4mm, septal wall thickness 1.0mm, aperture opening ratio 72%.
operation (k)
Then, by the honeycomb structure (1) that obtains at 60 DEG C dry 48 hours, then at 600 DEG C, burn till 3 hours, prepare cellular catalyst for treating waste gas (1).
operation (l), operation (m)
Measure each size of cellular catalyst for treating waste gas (1), result is shown in table.In addition, the content (use amount benchmark) of each composition in cellular catalyst for treating waste gas (1) is shown in table.
In addition, measure the specific area of cellular catalyst for treating waste gas (1), pore volume, compressive strength, tear strength and denitrating catalyst performance by following method, result is shown in table.
< specific area >
Based on using the mist of 30% nitrogen-70% helium as the BET method of adsorbed gas, obtained the specific area of cellular catalyst for treating waste gas (1) by specific area measuring device.
< pore volume >
Total pore volume of cellular catalyst for treating waste gas (1) is obtained by mercury injection method.
With reference to determination method: with mercury injection method pore distribution measurement device, (Kang Ta company (QANTA CROME society) makes the assay method of pore volume: PM-33GT1LP) measure.(pressure limit: 32 ~ 32200psi)
< compressive strength >
For using compressive strength machine, (Tokyo testing machine makes institute's (East capital Try test Machine System does institute) system: model AL/B30P) cellular catalyst for treating waste gas (1) is cut into cube or cuboid and the sample that obtains, honeycomb hole to run through direction and the direction vertical with this direction (following, referred to as " vertical direction ") on certain speed apply compression load, read the maximum loading (N) till sample is destroyed, obtain compressive strength by following (4) formula.
Compressive strength (N/cm
2)=W (N)/{ a (cm) × c (cm) } (4)
Here, a (cm) and c (cm) represents the size on 2 limits of the pressurized plane of sample.W (N) represents the slowly maximum loading of applying load to sample is completely destroyed.
< tear strength >
Using honeycomb hole count 9 × 9 order, run through the cellular catalyst for treating waste gas (1) of direction length 100mm (carrying out cutting adjustment to the catalyst of size in addition) as test sample, this test sample is filled in flow through reactors.In flow through reactors, the gas containing sand is circulated with following condition, measure wear rate by the reduction of catalyst weight based on following (5) formula.In flow through reactors the logical sand amount of the sand of circulation by arranging cyclone separator at the back segment of flow through reactors, after wear test terminate, measure the weight of the sand collected by this cyclone separator obtain.
experimental condition
Catalyst shape: honeycomb hole count 9 × 9 order, length 100mm
Gas flow rate: (16.5 ± 2) m/s (catalyst section)
Gas temperature: room temperature 25 DEG C
The gas currency: 3 hours
Sand concentration: (40 ± 5) g/Nm
3
Sand: silica sand average grain diameter 500 μm
Wear rate (%/kg)=(wear test start before catalyst weight (g)-wear test terminate after catalyst weight (g))/wear test start before catalyst weight (g) × 100/ logical sand amount (kg) (5)
< denitrating catalyst performance test >
Using the cellular catalyst for treating waste gas (1) that formed by honeycomb hole count 3 × 3 order, the honeycomb molded body that runs through direction length 300mm (carrying out cutting adjustment to the catalyst of size in addition) as test sample, this test sample is filled in flow through reactors.The model gas of following composition is circulated in this flow through reactors, measures denitration rate.Nitrogen oxide (NO in gas before and after catalyst exposure
x) denitration rate obtained by following (6) formula.Now NO
xconcentration chemiluminescent NOx analysis meter (arna Tyke Ya Nake Co., Ltd. (Co., Ltd. ア Na テ ッ Network ヤ Na コ) make: ECL-88AO) measure.
Denitration rate (%)={ (do not contact the NO in gas
xnO in gas after (quality ppm)-contact
x(quality ppm))/do not contact NO in gas
x(quality ppm) } × 100 (6)
experimental condition
Catalyst shape: honeycomb hole count 3 × 3 order, length 300mm
Reaction temperature: 380 DEG C, superficial linear velocity in a column (SV)=20,000hr
-1
Model gas forms: NO
x=180 quality ppm, NH
3=180 quality ppm, SO
2=500
Quality ppm, O
2=2 % by weight, H
2o=10 % by weight, N
2=balance
[embodiment 2]
the preparation of catalyst for treating waste gas (2)
In the same manner as example 1 titanium oxide catalyst for treating waste gas sieve (mesh size=0.3mm (Japanese Industrial Standards (JIS) regulation)) that contains used through pulverizing being sieved, obtaining the pulverized product (2) of the catalyst used.
operation (a)
Measure the average grain diameter of the pulverized product (2) of the catalyst used, result is shown in table.
Below, except utilizing the pulverized product (2) of the catalyst used, cellular catalyst for treating waste gas (2) is prepared in an identical manner.
Measure each size of cellular catalyst for treating waste gas (2), result is shown in table.In addition, the content (use amount benchmark) of each composition in cellular catalyst for treating waste gas (2) is shown in table.
In addition, measure the specific area of cellular catalyst for treating waste gas (2), pore volume, compressive strength, tear strength and denitrating catalyst performance by following method, result is shown in table.
[embodiment 3]
the preparation of catalyst for treating waste gas (3)
In the same manner as example 1 titanium oxide catalyst for treating waste gas sieve (mesh size=0.7mm (Japanese Industrial Standards (JIS) regulation)) that contains used through pulverizing being sieved, obtaining the pulverized product (3) of the catalyst used.
operation (a)
Measure the average grain diameter of the pulverized product (3) of the catalyst used, result is shown in table.
Below, except utilizing the pulverized product (3) of the catalyst used, cellular catalyst for treating waste gas (3) is prepared in an identical manner.
Measure each size of cellular catalyst for treating waste gas (3), result is shown in table.In addition, the content (use amount benchmark) of each composition in cellular catalyst for treating waste gas (3) is shown in table.
In addition, measure the specific area of cellular catalyst for treating waste gas (3), pore volume, compressive strength, tear strength and denitrating catalyst performance by following method, result is shown in table.
[embodiment 4]
the preparation of catalyst for treating waste gas (4)
Except adding metatitanic acid slurry (Ishihara Sangyo Kaisha, Ltd.'s system: MT-A, TiO in the operation (b) of embodiment 1
2concentration 30 % by weight) 7.5kg, to add beyond pulverized product (1) 31.3kg of catalyst that uses, make mixed slurry in an identical manner
.Operation (b)
Then, mixed slurry vacuum filter is carried out filtering, dewatering.
operation (c)
Na is carried out to filtrate
2o, K
2o, CaO, V
2o
5analyze, these compositions are measured from the disengaging (wash-out) of the pulverized product (1) of the catalyst used, depart from (wash-out) rate and be shown in table.
Then, in filtration, add ammonium paratungstate (Japan New Metals Co., Ltd.'s system) 0.32kg in dewatered cake (solid component concentration 51.8 % by weight) 48.3kg and after mixing, the ammoniacal liquor 18kg adding concentration 15 % by weight neutralizes.Now, in and the pH of slurry be 9.53.Then, carry out stirring slaking in 3 hours at 95 DEG C.
operation (d)
Below, in the same manner as example 1, cellular catalyst for treating waste gas (4) is prepared.
Measure each size of cellular catalyst for treating waste gas (4), result is shown in table.In addition, the content (use amount benchmark) of each composition in cellular catalyst for treating waste gas (4) is shown in table.
In addition, measure the specific area of cellular catalyst for treating waste gas (4), pore volume, compressive strength, tear strength and denitrating catalyst performance by following method, result is shown in table.
[embodiment 5]
the preparation of catalyst for treating waste gas (5)
Except adding metatitanic acid slurry (Ishihara Sangyo Kaisha, Ltd.'s system: MT-A, TiO in the operation (b) of embodiment 1
2concentration 30 % by weight) 67.5kg, to add beyond pulverized product (1) 3.48kg of catalyst that uses, make mixed slurry in an identical manner.
operation (b)
Then, mixed slurry vacuum filter is carried out filtering, dewatering.
operation (c)
Na is carried out to filtrate
2o, K
2o, CaO, V
2o
5analyze, these compositions are measured from the disengaging (wash-out) of the pulverized product (1) of the catalyst used, depart from (wash-out) rate and be shown in table.
Then, in filtration, add ammonium paratungstate (Japan New Metals Co., Ltd.'s system) 2.52kg in dewatered cake (solid component concentration 50.5 % by weight) 49.5kg and after mixing, the ammoniacal liquor 28kg adding concentration 15 % by weight neutralizes.Now, in and the pH of slurry be 9.5.Then, carry out stirring slaking in 3 hours at 95 DEG C.
operation (d)
Below, in the same manner as example 1, cellular catalyst for treating waste gas (5) is prepared.
Measure each size of cellular catalyst for treating waste gas (5), result is shown in table.In addition, the content (use amount benchmark) of each composition in cellular catalyst for treating waste gas (5) is shown in table.
In addition, measure the specific area of cellular catalyst for treating waste gas (5), pore volume, compressive strength, tear strength and denitrating catalyst performance by following method, result is shown in table.
[embodiment 6]
the preparation of catalyst for treating waste gas (6)
In the operation (d) of embodiment 1, do not add ammonium paratungstate (Japan New Metals Co., Ltd.'s system) 1.42kg, the ammoniacal liquor 18kg adding concentration 15 % by weight neutralizes.Now, in and the pH of slurry be 9.55.Then, carry out stirring slaking in 3 hours at 95 DEG C.
operation (d)
Below, in the same manner as example 1, cellular catalyst for treating waste gas (6) is prepared.
Measure each size of cellular catalyst for treating waste gas (6), result is shown in table.In addition, the content (use amount benchmark) of each composition in cellular catalyst for treating waste gas (6) is shown in table.
In addition, measure the specific area of cellular catalyst for treating waste gas (6), pore volume, compressive strength, tear strength and denitrating catalyst performance by following method, result is shown in table.
[embodiment 7]
the preparation of catalyst for treating waste gas (7)
Except adding titanyl sulfate in the operation (b) of embodiment 1, (Tayca Corp. (テ イ カ (strain)) makes: TM crystallization, TiO
2concentration 30 % by weight) 37.5kg replaces, beyond metatitanic acid slurry, making mixed slurry in an identical manner.
operation (b)
The pH of cooled mixed slurry is 9.54.
Below, in the same manner as example 1, cellular catalyst for treating waste gas (7) is prepared.
Measure each size of cellular catalyst for treating waste gas (7), result is shown in table.In addition, the content (use amount benchmark) of each composition in cellular catalyst for treating waste gas (7) is shown in table.
In addition, measure the specific area of cellular catalyst for treating waste gas (7), pore volume, compressive strength, tear strength and denitrating catalyst performance by following method, result is shown in table.
[comparative example 1]
the preparation of catalyst for treating waste gas (R1)
Metatitanic acid slurry (Ishihara Sangyo Kaisha, Ltd.'s system) 75.0kg is put into the tank diameter of band heating return channel, add again ammonium paratungstate 2.79kg and mixing after, pH is adjusted to 9.5 by the ammoniacal liquor 23kg adding concentration 15 % by weight, stirs slaking in 1 hour at 95 DEG C.Afterwards, this mixed slurry is cooled to 40 DEG C, then by filtering, watering and clean, prepares solid component concentration (TiO
2, WO
3) 49 % by weight cleaning filter cake.
Then, filter cake will be cleaned at 110 DEG C dry 20 hours, after burning till 5 hours further at 550 DEG C, pulverize with pulverizer (Ya Liya machinery production is made: Ya Liya pulverizer), obtain not containing the titanium oxide based micropowder (R1) of the catalyst used.
operation (f), operation (g), operation (h)
Analyze the composition of the titanium oxide based micropowder (R1) obtained, in addition, measure average grain diameter, result is shown in table.Then, add at titanium oxide based micropowder (1) 24.0kg and ammonium metavanadate 0.273kg is dissolved in MEA 0.250kg and the solution obtained and water 3.5kg, then add ammoniacal liquor, make the pH of mixed slurry be 7.8, be heated to be 120 DEG C with kneader and knead 0.5 hour.
Afterwards, the glass fibre added in this mixed slurry as reinforcing material (below, is sometimes referred to as " GF ".) 1.39kg, the Emathlite 0.26kg as filler, the PEO 0.500kg as organic additive, mediate 3 hours at 60 DEG C with kneader, prepare formed body composition (R1).
work sequence (i), operation (j)
Below, in the same manner as example 1, cellular catalyst for treating waste gas (R1) is prepared.
Measure each size of cellular catalyst for treating waste gas (R1), result is shown in table.In addition, the content (use amount benchmark) of each composition in cellular catalyst for treating waste gas (R1) is shown in table.
In addition, measure the specific area of cellular catalyst for treating waste gas (R1), pore volume, compressive strength, tear strength and denitrating catalyst performance by following method, result is shown in table.
[comparative example 2]
the preparation of catalyst for treating waste gas (R2)
In the same manner as example 1 titanium oxide catalyst for treating waste gas sieve (mesh size=1.0mm (Japanese Industrial Standards (JIS) regulation)) that contains used through pulverizing being sieved, obtaining the pulverized product (R2) of the catalyst used.
operation (a)
Measure the average grain diameter of the pulverized product (R2) of the catalyst used, result is shown in table.
Below, except utilizing the pulverized product (R2) of the catalyst used, cellular catalyst for treating waste gas (R2) is prepared in an identical manner.
Measure each size of cellular catalyst for treating waste gas (R2), result is shown in table.In addition, the content (use amount benchmark) of each composition in cellular catalyst for treating waste gas (R2) is shown in table.
In addition, measure the specific area of cellular catalyst for treating waste gas (R2), pore volume, compressive strength, tear strength and denitrating catalyst performance by following method, result is shown in table.
[comparative example 3]
the preparation of catalyst for treating waste gas (R3)
Except adding metatitanic acid slurry (Ishihara Sangyo Kaisha, Ltd.'s system: MT-A, TiO in the operation (b) of embodiment 1
2concentration 30 % by weight) 0.4kg, to add beyond pulverized product (1) 34.7kg of catalyst that uses, make mixed slurry in an identical manner.
operation (b)
Then, mixed slurry vacuum filter is carried out filtering, dewatering.
operation (c)
Na is carried out to filtrate
2o, K
2o, CaO, V
2o
5analyze, these compositions are measured from the disengaging (wash-out) of the pulverized product (1) of the catalyst used, depart from that (eluting rate is shown in table.
Then, in filtration, add ammonium paratungstate (Japan New Metals Co., Ltd.'s system) 0.06kg in dewatered cake (solid component concentration 52.0 % by weight) 48.1kg and after mixing, the ammoniacal liquor 16kg adding concentration 15 % by weight neutralizes.Now, in and the pH of slurry be 9.52.Then, carry out stirring slaking in 3 hours at 95 DEG C.
operation (d)
Below, in the same manner as example 1, cellular catalyst for treating waste gas (R3) is prepared.
Measure each size of cellular catalyst for treating waste gas (R3), result is shown in table.In addition, the content (use amount benchmark) of each composition in cellular catalyst for treating waste gas (R3) is shown in table.
In addition, measure the specific area of cellular catalyst for treating waste gas (R3), pore volume, compressive strength, tear strength and denitrating catalyst performance by following method, result is shown in table.
[comparative example 4]
the preparation of catalyst for treating waste gas (R4)
Except adding metatitanic acid slurry (Ishihara Sangyo Kaisha, Ltd.'s system: MT-A, TiO in the operation (b) of embodiment 1
2concentration 30 % by weight) 69.0kg, to add beyond pulverized product (1) 2.79kg of catalyst that uses, make mixed slurry in an identical manner.
operation (b)
Then, mixed slurry vacuum filter is carried out filtering, dewatering.
operation (c)
Na is carried out to filtrate
2o, K
2o, CaO, V
2o
5analyze, these compositions are measured from the disengaging (wash-out) of the pulverized product (1) of the catalyst used, depart from (wash-out) rate and be shown in table.
Then, in filtration, add ammonium paratungstate (Japan New Metals Co., Ltd.'s system) 0.06kg in dewatered cake (solid component concentration 51 % by weight) 49.0kg and after mixing, the ammoniacal liquor 16kg adding concentration 15 % by weight neutralizes.Now, in and the pH of slurry be 9.54.Then, carry out stirring slaking in 3 hours at 95 DEG C.
operation (d)
Below, in the same manner as example 1, cellular catalyst for treating waste gas (R4) is prepared.
Measure each size of cellular catalyst for treating waste gas (R4), result is shown in table.In addition, the content (use amount benchmark) of each composition in cellular catalyst for treating waste gas (R4) is shown in table.
In addition, measure the specific area of cellular catalyst for treating waste gas (R4), pore volume, compressive strength, tear strength and denitrating catalyst performance by following method, result is shown in table.
[comparative example 5]
the preparation of catalyst for treating waste gas (R5)
Titanium oxide catalyst for treating waste gas (honeycomb shape: honeycomb hole count 20 × 20 order, length 1000mm, composition: TiO is contained by what use
2=79.65 % by weight, WO
3=8.0 % by weight, V
2o
5=0.90 % by weight, impurity: Na
2o=0.35 % by weight, K
2o=0.30 % by weight, CaO=1.5 % by weight, SO
4=6.13 % by weight) use as cellular catalyst for treating waste gas (R5).
Measure the specific area of cellular catalyst for treating waste gas (R5), pore volume, compressive strength, tear strength, result is shown in table.
Cellular catalyst for treating waste gas (R5) cutting is adjusted to honeycomb hole count 3 × 3 order, runs through the length 300mm in direction, and measure denitrating catalyst performance in the same manner as example 1, result is shown in table.
[table 1]
Other compositions are mainly (WO
3, Al
2o
3, SiO
2).
[table 2]
[table 3]
[table 4]
* the content of titanium oxide based micropowder is to deduct V from original amount
2o
5, WO
3numeric representation.
Claims (10)
1. a manufacture method for catalyst for treating waste gas, is characterized in that,
After by pulverizing containing titanium oxide catalyst for treating waste gas of using, to make average grain diameter be the powder of 0.1 ~ 15 μm,
What aqueous solution of titanyle sulfate and/or metatitanic acid slurry and this are used mixes containing titanium oxide catalyst for treating waste gas powder, makes mixed slurry, make aqueous solution of titanyle sulfate and/or metatitanic acid slurry with TiO
2concentration (the C of meter
t) and the concentration (C of solid constituent containing titanium oxide catalyst for treating waste gas used through pulverizing
rC) concentration ratio (C
t)/(C
rC) reach 0.1 ~ 9.0 scope,
After filtering this mixed slurry, add alkali compounds and titanyl sulfate and/or metatitanic acid neutralized, the titanium oxide gel of preparation pH in the scope of 7 ~ 12,
This gel is burnt till, then pulverizes, preparation titanium oxide based micropowder,
Mix this titanium oxide fine powder end and reinforcing material,
To mixture carry out shaping after burn till.
2. the manufacture method of catalyst for treating waste gas as claimed in claim 1, is characterized in that, with front in being undertaken by alkali compounds, and mixed active component precursor compound.
3. the manufacture method of catalyst for treating waste gas as claimed in claim 1 or 2, is characterized in that, be mixed together active component precursors compound with reinforcing material.
4. the manufacture method of catalyst for treating waste gas as claimed in claim 2 or claim 3, it is characterized in that, active component precursors compound is the compound of at least a kind of element being selected from V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, Ir, comprises this metal element and the compound that can generate metal oxide.
5. a catalyst for treating waste gas, is characterized in that,
Obtained by method according to claim 1,
Containing (i) titanium oxide based micropowder and (i i) reinforcing material, i the content of () titanium oxide based micropowder is in the scope of 60 ~ 97 % by weight, the content of (i i) reinforcing material is in the scope of 3 ~ 15 % by weight.
6. catalyst for treating waste gas as claimed in claim 5, is characterized in that, also containing (i i i) active component, should the content of (i i i) active component with oxide basis in the scope of 0.001 ~ 15 % by weight.
7. the catalyst for treating waste gas as described in claim 4 or 5, it is characterized in that, deriving from described (i) titanium oxide based micropowder use containing the titanium oxide based oxide of titanium oxide catalyst for treating waste gas or the content of composition in the scope of 8.5 ~ 90 % by weight.
8. the catalyst for treating waste gas according to any one of claim 5 ~ 7, is characterized in that, also containing filler, the content of this filler is in the scope of 0.5 ~ 15 % by weight.
9. the catalyst for treating waste gas according to any one of claim 5 ~ 8, it is characterized in that, described catalyst for treating waste gas is honeycomb formed article, the longitudinal and transverse size of this honeycomb or external diameter are in the scope of 30 ~ 400mm, length is in the scope of 3 ~ 1500mm, hole density is in the scope of 6 ~ 500cpsi, and thickness is in the scope of 0.1 ~ 1.9mm.
10. the catalyst for treating waste gas according to any one of claim 5 ~ 9, it is characterized in that, described active component is metal or the metal oxide of at least a kind of element being selected from V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, Ir.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-068571 | 2014-03-28 | ||
| JP2014068571 | 2014-03-28 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106944039A (en) * | 2017-02-21 | 2017-07-14 | 安徽迪诺环保新材料科技有限公司 | The production method of 40 hole above honeycomb denitration catalyst carrier materials |
| CN111974378A (en) * | 2020-09-23 | 2020-11-24 | 国家能源投资集团有限责任公司 | Denitration catalyst and preparation method thereof |
| CN116060425A (en) * | 2023-03-08 | 2023-05-05 | 国能龙源环保有限公司 | Method for removing Hg on surface of waste denitration catalyst |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3052687A1 (en) * | 2016-06-21 | 2017-12-22 | Lab Sa | PROCESS FOR PRODUCING A CATALYST |
| CN112316937B (en) * | 2020-11-16 | 2023-05-12 | 陆叶梓 | Cement rotary kiln waste gas treatment catalyst and preparation method thereof |
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| US20020058586A1 (en) * | 2000-09-27 | 2002-05-16 | Kyung-Il Choi | Method for preparing a catalyst for selective catalytic reduction of nitrogen oxides |
| CN101878066A (en) * | 2008-02-29 | 2010-11-03 | 三菱重工业株式会社 | Method of regenerating catalyst for discharge gas treatment and catalyst for discharge gas treatment obtained by the method |
| JP2011251245A (en) * | 2010-06-02 | 2011-12-15 | Mitsubishi Heavy Ind Ltd | Method for regeneration of exhaust gas treatment catalyst, and exhaust gas treatment catalyst produced using the method |
| CN104023840A (en) * | 2011-12-27 | 2014-09-03 | 日挥触媒化成株式会社 | Titanium-containing granular powder and method for production thereof, and exhaust gas treatment catalyst using same and method for production thereof |
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| DE19617081C2 (en) * | 1996-04-29 | 2003-02-06 | Kerr Mcgee Pigments Gmbh & Co | Process for the production of mixed oxide powders from deactivated DENOX catalysts |
| JP4005291B2 (en) * | 2000-02-14 | 2007-11-07 | バブコック日立株式会社 | Regeneration method of used denitration catalyst |
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2015
- 2015-03-20 JP JP2015057718A patent/JP6441140B2/en active Active
- 2015-03-27 CN CN201510140096.6A patent/CN104941628B/en not_active Expired - Fee Related
Patent Citations (4)
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| US20020058586A1 (en) * | 2000-09-27 | 2002-05-16 | Kyung-Il Choi | Method for preparing a catalyst for selective catalytic reduction of nitrogen oxides |
| CN101878066A (en) * | 2008-02-29 | 2010-11-03 | 三菱重工业株式会社 | Method of regenerating catalyst for discharge gas treatment and catalyst for discharge gas treatment obtained by the method |
| JP2011251245A (en) * | 2010-06-02 | 2011-12-15 | Mitsubishi Heavy Ind Ltd | Method for regeneration of exhaust gas treatment catalyst, and exhaust gas treatment catalyst produced using the method |
| CN104023840A (en) * | 2011-12-27 | 2014-09-03 | 日挥触媒化成株式会社 | Titanium-containing granular powder and method for production thereof, and exhaust gas treatment catalyst using same and method for production thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106944039A (en) * | 2017-02-21 | 2017-07-14 | 安徽迪诺环保新材料科技有限公司 | The production method of 40 hole above honeycomb denitration catalyst carrier materials |
| CN111974378A (en) * | 2020-09-23 | 2020-11-24 | 国家能源投资集团有限责任公司 | Denitration catalyst and preparation method thereof |
| CN116060425A (en) * | 2023-03-08 | 2023-05-05 | 国能龙源环保有限公司 | Method for removing Hg on surface of waste denitration catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104941628B (en) | 2018-12-18 |
| JP6441140B2 (en) | 2018-12-19 |
| JP2015192999A (en) | 2015-11-05 |
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