CN104941628B - Utilize the manufacturing method and catalyst for treating waste gas of the catalyst for treating waste gas of the catalyst used - Google Patents
Utilize the manufacturing method and catalyst for treating waste gas of the catalyst for treating waste gas of the catalyst used Download PDFInfo
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- CN104941628B CN104941628B CN201510140096.6A CN201510140096A CN104941628B CN 104941628 B CN104941628 B CN 104941628B CN 201510140096 A CN201510140096 A CN 201510140096A CN 104941628 B CN104941628 B CN 104941628B
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- catalyst
- waste gas
- treating waste
- titanium oxide
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229960002969 oleic acid Drugs 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 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
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 235000021081 unsaturated fats Nutrition 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 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
- 239000002023 wood Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
- Exhaust Gas After Treatment (AREA)
Abstract
The present invention provides a kind of catalyst for treating waste gas containing titanium oxide that utilization has used, the manufacturing method of the catalyst for treating waste gas of catalyst for treating waste gas function admirable while mouldability, intensity, abrasion resistance etc. are excellent.The manufacturing method of the catalyst for treating waste gas is: crushing the catalyst for treating waste gas containing titanium oxide used and is made after the powder that average grain diameter is 0.1~15 μm, by aqueous solution of titanyle sulfate and/or metatitanic acid slurry and this mixed using the complete powder of catalyst for treating waste gas containing titanium oxide, mixed slurry is made so that aqueous solution of titanyle sulfate and/or metatitanic acid slurry with TiO2Concentration (the C of meterT) and the catalyst for treating waste gas containing titanium oxide used through crushing the concentration (C in terms of solid componentRC) concentration ratio (CT)/(CRC) reach 0.1~9.0 range, alkali compounds is added after being filtered to the mixed slurry, neutralisation of sulphuric acid oxygen titanium and/or metatitanic acid, prepare titanium oxide gel of pH in the range of 7~12, the gel is burnt into, is then crushed, titanium oxide micropowder is prepared, titanium oxide fine powder end and reinforcing material are mixed, is burnt into after being formed to mixture.
Description
Technical field
The manufacturing method and exhaust-gas treatment that the present invention relates to the use of the catalyst for treating waste gas of the catalyst used are urged
Agent.
Background technique
In the past, to polluter, the especially NO being discharged from mobile generating sources such as the fixed generating source such as power station, automobilesx
Use honeycomb catalyst alternatively reduced form NOxCatalyst (hereinafter referred to as SCR catalyst) is handled.
Although coal, mink cell focus, timber etc. are used as fuel in the case where the fixed generating source such as known power station, example
Such as in the case where coal, containing V, Ni, Fe, Hg, As, Si, Ca, Mg, S ingredient, ash content etc. in burning waste gas, these are in exhaust gas
Deposition in catalyst, accumulation are handled, catalyst physical, chemical property is made to be deteriorated.Then, it is reached a certain level in performance deterioration
In the case of, the catalyst for treating waste gas more renewed is run.
Here, environmental problem can be caused if directly discarding the catalyst of taking-up used, in addition, used
Largely containing the useful ingredient such as titanium oxide, Mo, W, V, active metal components in catalyst, therefore research is regenerated, is sharp again
Method.Japanese Patent Laid-Open 2005-185928 bulletin (patent document 1), Japanese Patent Laid-Open 2011-251245 public affairs
It reports (patent document 2)
For example, disclosing complete exhaust gas used below in Japanese Patent Laid-Open 2005-185928 bulletin (patent document 1)
It handles the regeneration method of catalyst: heating in the catalyst for treating waste gas to the burning waste gas for surpassing mink cell focus
Afterwards, denitration performance and SO can be made by carrying out cleaning with oxalic acid aqueous solution2Oxidability is restored.
In addition, disclosing complete exhaust gas used below in Japanese Patent Laid-Open 2011-251245 bulletin (patent document 2)
Handle catalyst regeneration method: the catalyst for treating waste gas used is crushed, is miniaturize, be made into matrix at
In addition new catalyst for treating waste gas is crushed, is made into slurry liquid, which is coated in matrix formed body by type body
Surface on.
Existing technical literature
Patent document
Patent document 1: Japanese Patent Laid-Open 2005-185928 bulletin
Patent document 2: Japanese Patent Laid-Open 2011-251245 bulletin
Summary of the invention
The technical problems to be solved by the invention
But in method described in Patent Document 1, denitration performance and SO2The recovery of oxidability is not necessarily abundant,
And need to handle a large amount of cleaning waste liquids of the oxalic acid containing impurity such as vanadium, sulfate ions and for processing, in economy
There are problems in property.
In addition, in the method for patent document 2, using the catalyst for treating waste gas of crushing used formed body at
Type is difficult to shape the honeycomb more than heavy caliber, thin-walled or hole count than the insufficient formability of common catalyst for treating waste gas sometimes
Formed body, and attachment material cannot be sufficiently removed by being burnt into step for regeneration, compared with common catalyst for treating waste gas just
Phase exhaust-gas treatment performance and catalyst life are insufficient.
Technical problem of the invention is provided in mouldability, by force using the catalyst for treating waste gas containing titanium oxide used
The manufacturing method of the catalyst for treating waste gas of catalyst for treating waste gas function admirable and useless while degree, abrasion resistance etc. are excellent
Gas disposal catalyst.
Technical scheme applied to solve the technical problem
Then, the present inventor find after conscientiously studying, if in the preparation for preparing previous catalyst for treating waste gas
Used in process when titanium oxide micropowder, mixed in the titanyl sulfate or metatitanic acid slurry used usually as raw material
The catalyst for treating waste gas containing titanium oxide used through crushing simultaneously is filtered, then can remove as leading to catalyst degradation
The alkali metal such as Na, K, Ca of ingredient, alkaline-earth metal, mouldability is excellent if as main material use, and what is obtained is useless
Intensity, abrasion resistance, the exhaust-gas treatment performance of gas disposal catalyst etc. are excellent, so as to complete the present invention.
The manufacturing method of catalyst for treating waste gas of the invention is characterized in that,
It is crushed in the catalyst for treating waste gas containing titanium oxide that will have been used and the powder that average grain diameter is 0.1~15 μm is made
Afterwards,
By aqueous solution of titanyle sulfate and/or metatitanic acid slurry and the catalyst for treating waste gas containing titanium oxide used powder
Mixed, prepare mixed slurry so that aqueous solution of titanyle sulfate and/or metatitanic acid slurry with TiO2Concentration (the C of meterT) and
Concentration (the C of the solid component of the catalyst for treating waste gas containing titanium oxide used through crushingRC) concentration ratio (CT)/(CRC) reach
To 0.1~9.0 range,
After filtering the mixed slurry, addition alkali compounds neutralizes titanyl sulfate and/or metatitanic acid, and preparation pH exists
Titanium oxide gel in the range of 7~12,
The gel is burnt into, is then crushed, titanium oxide micropowder is prepared,
Titanium oxide fine powder end and reinforcing material are mixed,
It is burnt into after being formed to mixture.
Can by alkali compounds carry out in and before mixed active component precursor compound, can also be with strengthening material
Material is mixed together active component precursors compound.
Active component precursors compound is selected from V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, Ir
At least one kind of element compound, the compound including the metal element and producible oxide.
Catalyst for treating waste gas of the invention is obtained by the above method, which is characterized in that
Containing (i) titanium oxide micropowder and (ii) reinforcing material, (i) content of titanium oxide micropowder is in 60~97 weights
In the range of measuring %, the content of (ii) reinforcing material is in the range of 3~15 weight %.
Further, preferably comprise (iii) active constituent, should (iii) active constituent content in terms of oxide 0.001~
In the range of 15 weight %.
The titanium oxide from the catalyst for treating waste gas containing titanium oxide used in above-mentioned (i) titanium oxide micropowder
The content of type oxide (or ingredient) is preferably in the range of 8.5~90 weight %.
Further, filler is preferably comprised, the content of the filler is in the range of 0.5~15 weight %.
Above-mentioned catalyst for treating waste gas is honeycomb formed article, which preferably in the range of 30~400mm, grows
Degree is preferably in the range of 3~1500mm, and hole density is preferably in the range of 6~500cpsi, and thickness is preferably in 0.1~1.9mm
In the range of.
Above-mentioned active constituent is preferably selected from V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, Ir extremely
The metal or metal oxide of few a kind of element.
The content of above-mentioned active constituent is in terms of oxide preferably in the range of 0.001~15 weight %.
The effect of invention
If it is excellent to can provide mouldability, intensity, abrasion resistance and catalyst for treating waste gas performance using the present invention
It is good, and the also manufacturing method and catalyst for treating waste gas of excellent catalyst for treating waste gas in economy.
Specific embodiment
Firstly, being illustrated to the manufacturing method of catalyst for treating waste gas of the invention.
[manufacturing method of catalyst for treating waste gas]
The manufacturing method of catalyst for treating waste gas of the invention includes the catalyst for treating waste gas containing titanium oxide that will have been used
Crush the process (process (a)) that the powder that average grain diameter is 0.1~15 μm is made.
Process (a)
The catalyst for treating waste gas containing titanium oxide used is crushed.
As the catalyst for treating waste gas containing titanium oxide used, mainly can be used above-mentioned from the fixed generation such as power station
The polluter of the mobile generating source discharge such as source, automobile, in particular for NOxThe catalyst of the selective reduction processing of gas.
In addition to aftermentioned ash content etc., the catalyst for treating waste gas containing titanium oxide used is with TiO2Meter preferably comprises 50 weights
Measure % or more titanium oxide.
It is suitble to use for handling the fixed generating source institute such as power station for using coal, mink cell focus, timber etc. as fuel
The cellular catalyst for treating waste gas containing titanium oxide used of the exhaust gas of generation.
Especially in the case where using coal as fuel, in burning waste gas containing V, Ni, Fe, Hg, As, Si, Ca, Mg, Na,
K, S ingredient, ash content etc., these ingredients are deposited in the catalyst for treating waste gas containing titanium oxide used, are accumulated, if using this
The manufacturing method of invention, then optionally reduce or remove contained in finally obtained catalyst for treating waste gas these at
Point.
As the breaking method of the catalyst for treating waste gas containing titanium oxide used, as long as can crush as desired size
It is then not particularly limited, known method can be used.For example, atomizer, Henschel mixer, pulverizer, Asia can be used
Power Asia pulverizer (ヤ リ ヤ Fen crushed machine) etc. is crushed.
The size of the catalyst for treating waste gas containing titanium oxide used through the crushing energy, equipment required for crushing etc.
Funds, the rate of recovery of pulverizing process, filterability and removal inside particles impurity etc. consider that average grain diameter is 0.1~15 μ
M, more preferable 0.5~10.0 μm of range.
If the average grain diameter of the catalyst for treating waste gas containing titanium oxide used through crushing is lower than under above range
Limit, then the funds such as the energy, equipment required for crushing improve sometimes, and the rate of recovery decline of pulverizing process, sometimes slurry
Filterability decline, the removal of impurity become inadequate；If average grain diameter is excessive, although filterability improves, sometimes due to
The impurity of the inside particles of the catalyst for treating waste gas containing titanium oxide used through crushing cannot be removed and cleaning effect does not fill
Point.
In the present invention, in the catalyst for treating waste gas containing titanium oxide used and aftermentioned process (h) through crushing
The average grain diameter of titanium oxide micropowder by laser diffraction formula particle size distribution analyzer (hole field make it is made: LA-300) into
Row measurement.
It then, will be at aqueous solution of titanyle sulfate and/or metatitanic acid slurry and the exhaust gas containing titanium oxide used through crushing
Manage catalyst mixing, mixed slurry be made so that aqueous solution of titanyle sulfate and/or metatitanic acid slurry with TiO2The concentration of meter
(CT) and the catalyst for treating waste gas containing titanium oxide used through crushing solid component concentration (CRC) concentration ratio (CT)/
(CRC) reach 0.1~9.0 range (process (b) and (c)).
Process (b)
Aqueous solution of titanyle sulfate and/or metatitanic acid slurry and the exhaust-gas treatment containing titanium oxide used through crushing are urged
Agent mixing, is made mixed slurry.
Here, metatitanic acid slurry refers to the slurry containing titanium hydroxide after having hydrolyzed titanium sulfate.
Aqueous solution of titanyle sulfate and/or metatitanic acid slurry in mixed slurry with TiO2Concentration (the C of meterT) it is 5~40 weights
Measure %, the further preferably range of 10~30 weight %.If the above-mentioned concentration (C in mixed slurryT) low, then under economy
Drop；If the above-mentioned concentration (C in mixed slurryT) excessively high, then the viscosity of slurry is got higher in process (b) and process (d), is had
When stirring become difficult.
If the catalyst for treating waste gas containing titanium oxide of crushing used is dispersed in titanyl sulfate and/or metatitanic acid
In, then pH becomes acid, especially becomes the salt centered on alkali composition and dissolves.In addition, sulphur ingredient becomes sulfate ion.It will
These pass through filtering, dehydration procedure removal.In addition, (alkalinity) is neutralized by the addition of aftermentioned alkali compounds, by
Titanyl sulfate and/or metatitanic acid generate titanium oxide gel.It is useless containing titanium oxide through having used of crushing to cover due to the gel
The form generating of gas disposal catalyst, thus with prepare after gel in advance again with the exhaust gas containing titanium oxide used through crushing
The case where processing catalyst is mixed is compared, and can make the mouldability height of catalyst for treating waste gas and intensity etc. is excellent.
In addition, the concentration in terms of solid component of the catalyst for treating waste gas containing titanium oxide used in mixed slurry
(CRC) it is 3~55 weight %, further preferably contained with the range of 9~25 weight %.
If above-mentioned concentration (CRC) low, then from the aspect of the catalyst for treating waste gas containing titanium oxide that recycling has used
Low efficiency.If above-mentioned concentration (CRC) excessively high, then the viscosity of mixed slurry is got higher, and stirring becomes difficult sometimes.
At this point, above-mentioned concentration (CT) and above-mentioned concentration (CRC) concentration ratio (CT)/(CRC) it is 0.1~9.0, further preferably
1.0~5.0 range.
If concentration ratio (CT)/(CRC) too low, then in the catalyst for treating waste gas containing titanium oxide used through crushing
Impurity removal it is insufficient while sometimes mouldability be deteriorated, in addition, the denitration of finally obtained catalyst for treating waste gas sometimes
Performance is insufficient.If concentration ratio (CT)/(CRC) excessively high, then due to the usage amount of the catalyst for treating waste gas containing titanium oxide used
It is few, therefore the low efficiency from the aspect of recycling the gas disposal catalyst of waste discharge containing titanium oxide that has used.
The all solids constituent concentration of mixed slurry is 8~60 weight %, the range of further preferred 19~39 weight %.
If all solids constituent concentration of mixed slurry is low, the filtrate in process (c) becomes more, a large amount of due to needing
The low filtrate of impurity concentration is handled, sometimes treatment effeciency and economy decline.If all solids ingredient of mixed slurry is dense
Height is spent, then the viscosity of mixed slurry is got higher, and is caused obstacle to stirring or filtering, is difficult to carry out subsequent handling sometimes.In addition,
In the case that all solids constituent concentration of mixed slurry is excessively high, dilution water can be added as needed.
In addition, usually mixed slurry pH in the range of 0.5~4, further preferred 1.0~3.0 range.It is mixing
In the case that the pH of slurry is lower than 0.5, due to going for the impurity such as alkali, alkaline-earth metal when being filtered in aftermentioned process (c)
Except rate will not further be got higher, for the more therefore uneconomical using quantitative change of the alkali compounds of neutralization in process (d).
If the pH of mixed slurry is more than 4, the removal of the impurity such as alkali, alkaline-earth metal is become inadequate sometimes.
In addition, the pH of mixed slurry not within the above range in the case where, can add acid or alkali pH is adjusted to above-mentioned
Range.
As acid, the organic acids such as inorganic acids or oxalic acid such as hydrochloric acid, nitric acid, sulfuric acid can be used.In addition, can be used as alkali
Sodium hydroxide, potassium hydroxide, sodium carbonate, NH4OH etc..
In addition, mixed slurry can be heated as needed.
As heating condition, it is as long as the impurity such as Ca, K, Na can be removed efficiently in the filtering of process (c) then
Can, it is not particularly limited, substantially preferably 40~60 DEG C of range, at this point it is possible to not stir, but is preferably stirred.
By heating mixed slurry, can promote with the neutralization reaction of the impurity such as Ca, K, Na, by the way that impurity is become soluble
Salt can efficiently remove impurity.
Process (c)
Mixed slurry produced above is filtered, is dehydrated.It is not particularly limited, can adopt as filtering, dewatering
By a conventionally known method.
For example, vacuum filtration process, compression filtration, weight filtration method, centrifuge separation etc. can be enumerated.
Due to by filtering, being dehydrated Ca, K, Na, S (SO dissolved out in removable filtrate4) etc. or ash content etc. lead to catalyst
The ingredient of deterioration, therefore the catalyst for treating waste gas of good activity can be finally obtained.
Filtering, dewatered filter cake solid content a degree of variation is had according to the size of particle, but in 30 weights
% or more is measured, preferably in the range of 45~55 weight %.
If filtering, the solid component concentration of dewatered filter cake are low, it is dehydrated insufficient, impurity is largely remaining, sometimes
The performance of obtained catalyst for treating waste gas is insufficient.
In filtering, during addition alkali compounds carries out titanyl sulfate and/or metatitanic acid in dewatered filter cake and, preparation
Titanium oxide gel (process (d)) of pH in the range of 7~12.
Process (d)
In filtering, during addition alkali compounds carries out titanyl sulfate and/or metatitanic acid in dewatered filter cake and, preparation
Titanium oxide gel.
As alkali compounds, as long as titanium oxide gel can be made for titanyl sulfate and/or metatitanic acid by neutralizing,
NH can be enumerated4OH, sodium hydroxide, potassium hydroxide etc..
In the present invention, from the aspect of not containing alkali metal, it is suitble to use NH4OH。
The pH of titanium oxide gel after neutralization is 7~12, further preferred 8~10 range.
In the case that the pH of titanium oxide gel after the neutralization is lower than 7, sulfate ion is largely remaining sometimes, and mouldability is sometimes
It becomes inadequate.In addition, the specific surface area of the raw material after firing in process (g) becomes smaller, the exhaust-gas treatment catalysis obtained sometimes
The performance of agent is insufficient.
If the pH of the titanium oxide gel after neutralizing is more than 12, alkali compounds uses quantitative change more, sometimes economy
Decline.
It, can be before addition alkali compounds neutralisation of sulphuric acid oxygen titanium and/or metatitanic acid before mixed active ingredient in the present invention
Body compound (A).
As active component precursors compound (A), using selected from V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y,
The compound of at least one kind of element of Ce, Nd, In, Ir.
Specifically, can enumerate 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..
It is preferred that active component precursors compound (A) is used as solution, although different according to the type of compound,
It is preferably dissolved in the acid such as the alkali such as water, monoethanolamine, oxalic acid and uses.
For the combined amount of active component precursors compound (A), it is contemplated that at the above-mentioned exhaust gas containing titanium oxide used
Manage the content of the active constituent in catalyst, the content in finally obtained catalyst for treating waste gas in terms of the oxide of element
It is used for the range of 0.001~15 weight %, further preferred 0.3~12 weight %.If the content of active constituent is few, example
Such as alternatively reduced form NOxIn the case where catalyst use, the NO of catalyst for treating waste gas sometimesxRemoval rate it is insufficient.If
The content of active constituent is excessive, then the compressive strength of formed body, resistance to anti-thread breakage deficiency.
Then, it neutralizes preferably to be heated, being cured after above-mentioned defined pH range.
At this point, curing temperature is 40~95 DEG C, further preferred 50~75 DEG C of range, the curing time is according to curing temperature
And it is different, but substantially 1~24 hour.
If curing temperature is within the above range, gel homogenizes, and mouldability in process (k) improves, obtain at
The crackle of type body is suppressed, and the excellent catalyst for treating waste gas such as intensity, abrasion resistance can be obtained.
Process (e)
Then, the titanium oxide gel after neutralization is cleaned.In addition, it is not necessary to be cleaned, but as cleaning side
Method, as long as can reduce, remove Ca, K, Na, SO4Equal impurity are then not particularly limited, and known method can be used.
For example, using device identical with above-mentioned operation (c), after the titanium oxide gel after neutralization is filtered, is dehydrated,
It can be cleaned by watering, preferably pouring warm water.
At this point, the anion such as sulfate ion can be efficiently removed if using weak aqua ammonia in water.
Process (f)
Gel obtained in process (e) is dried.
As drying means, as long as can by the gel powderization as long as be not particularly limited, known method can be used.
Drying temperature is different according to drying time, but substantially 70~120 DEG C of range.
The gel of powdered as above is burnt into, is then crushed, preparation titanium oxide micropowder (process (g) with
And (h)).
Process (g)
Firing temperature is 450~700 DEG C, further preferred 500~650 DEG C of range.
If firing temperature is low, the mixing in process (i) is set to be difficult to carry out since the crystallization of titanium oxide is insufficient,
And make mouldability insufficient sometimes due to the bleeding (Japanese: from water) when easily causing extrusion forming.
If firing temperature is excessively high, the crystallization of titanium oxide is promoted, specific surface area becomes smaller, at exhaust gas obtained by it
Managing catalyst, performance is insufficient sometimes.
Firing time is different according to firing temperature, but substantially 1~24 hour.
Process (h)
After firing, the average grain diameter of titanium oxide micropowder obtained by crushing be 0.1~15 μm, further preferred 0.5~5
μm range.
The funds such as the energy, equipment as required for the above range lower limit crushing below to titanium oxide micropowder mention
Height, and mouldability will not further increase, it is thus not preferred.If average grain diameter is excessive, under the mouldability in process (k)
The deficiencies of drop, the formed body obtained sometimes crack, intensity, abrasion resistance is without preferred.
As long as average grain diameter is not particularly limited within the above range in breaking method at this time, can be used previous
Well known method, for example, can be used and the identical method, apparatus of above-mentioned operation (a).
Later, the titanium oxide fine powder end and reinforcing material are mixed, after forming the mixture into, is dried, is burnt into (process
(i)~(m)).
Process (i)
Preparation is mixed with mixture (the hereinafter referred to as formed body group of reinforcing material in above-mentioned titanium oxide micropowder
Close object).The content of titanium oxide micropowder in the composition is calculated as 33~80 weight % with solid component, and further preferred 40
The range of~75 weight %.If the content of the titanium oxide micropowder in formed body composition is few, in difficult forming
Meanwhile catalyst performance, such as selective reduction type NO sometimesxThe NO of catalystxRemoval rate it is insufficient.
Reinforcing material
As reinforcing material, the fibrous reinforcements such as glass fibre, ceramic fibre can be used.
If containing such reinforcing material, the hair of cracking caused by contraction when can inhibit dry after extrusion molding
It is raw, the excellent catalyst for treating waste gas of compressive strength, abrasion resistance can be prepared.
Formed body with the content of the reinforcing material in composition with solid component be calculated as 1.8~12.8 weight %, further
It is preferred that the range of 3~10 weight %.
The receipts if content of the reinforcing material in formed body composition is few, when dry after generation extrusion molding sometimes
Cracking caused by contracting.If the content of the reinforcing material in formed body composition is excessive, enhance when extrusion molding sometimes
Material blocks in mold for forming, hinders mouldability.
Filler
In the present invention, filler can be contained in formed body composition.If containing filler, can be carried out continuously it is crowded
Compressive strength, abrasion resistance excellent formed body are made while molding out.
As filler, the ceramic powders such as cordierite, aluminium oxide, zirconium oxide, silicon nitride, silicon carbide, clay mineral can be used.
Formed body is calculated as 0.42~12.8 weight % with the content of the filler in composition with solid component, further preferably
The range of 1~10 weight %.
If the content of the filler in formed body composition is few, continuous extrusion decline has duration size
The molding of honeycomb formed article of formed body, especially long size becomes difficult, in addition, the cleaning or replacement of mold for forming sometimes
Become frequently, productivity, economy decline.If the content of the filler in formed body composition is excessive, sometimes catalyst
Performance becomes insufficient.
Organic additive
In the present invention, it can further contain organic additive in formed body composition.
As organic additive, fatty acid, aliphatic ester etc. can be used.
Unsaturated fat represented by saturated fatty acid represented by the above-mentioned preferred following formula of fatty acid (1) and/or following formula (2)
Acid.
CnH2n-CO2H················(1)
(wherein, the integer that n is 4~23)
Cn'H2n'-2m+1-CO2H······(2)
(wherein, the integer that n' is 13~23, m indicate the quantity of double bond, are 1~6 integer)
As saturated fatty acid, specifically, stearic acid, lauric acid, myristic acid, behenic acid, arachidic acid, wood can be enumerated
Cerinic acid, palmitinic acid etc. and their mixture.
In addition, oleic acid, arachidonic acid, linoleic acid, linolenic acid, eicosapentaenoic can be enumerated as unsaturated fatty acid
Acid, docosahexaenoic acid etc. and their mixture.
In addition, being also suitable for using the aliphatic esters such as fatty acid glyceride, carboxymethyl cellulose, methylcellulose, hydroxypropyl
Cellulose, hydroxymethyl cellulose, avicel cellulose, polyethylene glycol, polypropylene glycol, polyethylene oxide etc..
If the fissility from mold for forming, mouldability and other effects can be improved containing such organic added material.
Formed body is calculated as 0.03~4.3 weight % with the content of the organic additive in composition with solid component, into one
The step preferably range of 0.5~2 weight %.
If the content of the organic additive in formed body composition is few, mouldability becomes insufficient；If excessive,
The pore volume of obtained molding body catalyst becomes larger, and becomes except deficiency in compressive strength, produces sometimes when formed body is burnt into
Raw cracking.
Active component precursors compound (B)
Moreover, in this process (i), it can mixed active component precursor compound (B).
As active component precursors compound (B), can be used and the identical chemical combination of above-mentioned active component precursors compound (A)
Object.
For the combined amount of active component precursors compound (B), it is contemplated that at the above-mentioned exhaust gas containing titanium oxide used
The content of the active constituent in catalyst and the content of active component precursors compound (A) are managed, at finally obtained exhaust gas
Managing the content in catalyst in terms of the oxide of element is 0.001~15 weight %, the model of further preferred 0.3~12 weight %
Enclose use.
If the content of active constituent is few, such as alternatively reduced form NOxIn the case where catalyst use, give up sometimes
The NO of gas disposal catalystxRemoval rate it is insufficient.If the content of active constituent is excessive, compressive strength, the anti-cracking of formed body
Line is insufficient.
Solvent
Formed body composition can contain solvent other than mentioned component.It, can be according to using purpose and molding as solvent
Method is suitably selected.
Specifically, the volatile solvents such as water, methanol, ethyl alcohol, propyl alcohol, methyl ethyl ketone, preferably water can be enumerated.
The concentration of solvent in such formed body composition is 15~40 weight %, the preferably model of 25~35 weight
It encloses, all solids constituent concentration is 60~85 weight %, the range of further preferred 65~75 weight %.
Formed body if all solids constituent concentration of formed body composition is too low, after extrusion molding, before drying
Conformality it is poor, deform sometimes.
If all solids constituent concentration of formed body composition is excessive, fluency when sometimes through molding die
Difference, mouldability, especially continuously shaped property decline.
Process (j)
Formed body produced above is kneaded with composition, is kneaded.As being kneaded, kneading method, as long as can be uniform
Above-mentioned each material is mixed, is not particularly limited, known mixed method can be used.
Usually using kneader, but continuous kneader, mixing machine also can be used etc..
It is kneaded and kneading preferably carries out under heating.Substantially 80~140 DEG C of temperature at this time, further preferred 90~
130 DEG C of range.By being kneaded and being kneaded within the scope of such temperature, it can be prepared into the excellent formed body of type and use
Composition.
In addition, incorporation time is different according to temperature, but substantially 0.25~5 hour.
Process (k)
It is kneaded and well known molding machine can be used in the forming method of pug mill, it can shape, type according to formed body
It is equal suitably to be selected, extrusion shaping machine usually can be used, to constructed as honeycomb type formed body complicated formed body into
Applicable vacuum extruding form machine in the molding situation of row.
Process (l)
As the drying means in drying process (l), as long as can not be bent, do not generate deformation, furthermore not crack ground
Evenly drying is carried out, is not particularly limited, known method can be used.
For example, in the case where article formed into honeycomb is dried, although according to outer diameter, length, hole, thickness etc. without
Together, but substantially preferably 30~65 DEG C of temperature of range, drying time substantially preferably 24~72 hours ranges.
Process (m)
It is burnt into later, firing temperature is 450~700 DEG C, further preferred 480~600 DEG C of range.If firing
Temperature is low, then leads to organic substance residues due to organic compound for using etc., hinder catalyst performance sometimes.If firing
Temperature is excessively high, then the crystallization of titanium oxide excessively carries out, and the specific surface area and pore volume of obtained catalyst for treating waste gas have
Shi Bian little, catalyst performance becomes insufficient sometimes.
Firing time is different according to firing temperature, but substantially 1~24 hour.
Catalyst for treating waste gas of the invention can be manufactured by the above each process.
[catalyst for treating waste gas]
Catalyst for treating waste gas of the invention is characterized in that, is manufactured by the above method, and (i) titanium oxide micro mist is contained
End and (ii) reinforcing material, (i) content of titanium oxide micropowder in the range of 60~97 weight %, (ii) reinforcing material
Content is in the range of 3~15 weight %.
(i) titanium oxide micropowder
The content of (i) titanium oxide micropowder in catalyst for treating waste gas is 60~97 weight %, preferably 60~96 weights
Measure %, the range of more preferable 75~90 weight %.
If the content of (i) titanium oxide micropowder in catalyst for treating waste gas is few, sometimes catalyst for treating waste gas
Performance, specifically the removal rate of the NOx of selective reduction type NOx catalyst becomes insufficient.
If the content of (i) titanium oxide micropowder in catalyst for treating waste gas is excessive, aftermentioned others strengthening material
Material, filler, the usage amount of active component precursors are limited, sometimes the compressive strength of catalyst for treating waste gas, resistance to anti-thread breakage and NOx
Removal rate etc. becomes insufficient.
In (i) titanium oxide micropowder in catalyst for treating waste gas from the exhaust-gas treatment containing titanium oxide used
The content of the titanium oxide oxide (or ingredient) of catalyst be 8.5~90 weight %, preferably 10~90 weight %, further
It is preferred that the range of 25~50 weight %.In addition, other not being removed containing active constituent etc. also in titanium oxide micropowder (i)
Ingredient.
(ii) reinforcing materialThe content of (ii) reinforcing material in catalyst for treating waste gas is 3~15 weight %, further
It is preferred that the range of 3~10 weight %.
If the content of reinforcing material is few, cracking caused by contraction when dry after generation extrusion molding sometimes；Such as
The content of fruit reinforcing material is excessive, then reinforcing material blocks in mold for forming when extrusion molding sometimes, hinders mouldability.
(iii) active constituent
Further, catalyst for treating waste gas preferably comprises the above-mentioned active constituent as active constituent.
The content of active constituent in catalyst for treating waste gas is calculated as 0.001~15 weight % with oxide, further excellent
Select the range of 0.3~12 weight %.If the content of active constituent is few, in alternatively reduced form NOxWhat catalyst used
In the case of, NO sometimesxRemoval rate it is insufficient.It is the compressive strength of formed body, resistance to anti-thread breakage if the content of active constituent is excessive
It is insufficient.
Herein, active constituent be active constituent contained in the catalyst for treating waste gas that has used, above-mentioned operation (d) and/
Or the total of the active constituent of active component precursors compound (A) and (B) is derived from used in above-mentioned operation (i).
Filler
Catalyst for treating waste gas can contain filler.If compressive strength, abrasion resistance are excellent containing filler.
Catalyst for treating waste gas can contain above-mentioned filler.
The content of filler in catalyst for treating waste gas is 0.5~15 weight %, the model of further preferred 3~10 weight %
It encloses.
Intensity is low if the content of the filler in catalyst for treating waste gas is few；In addition, if the content of filler is excessive, then
Sometimes catalyst performance becomes insufficient.
The known shape such as particle, bead, ring-type, honeycomb can be used in the shape of catalyst for treating waste gas of the invention
Shape.
Due to using above-mentioned formed body composition in the present invention, mouldability is high, obtained honeycomb exhaust-gas treatment
Catalyst strength, abrasion resistance it is excellent.In addition, by proper choice of the type, usage amount, use of above-mentioned organic additive
Method, can be obtained mouldability further increase, be thinning, the formed body more than hole count.
The longitudinal and transverse size or outer diameter of honeycomb catalyst for treating waste gas are preferably in the range of 30~400mm.
Here, cellular face shaping is quadrangle, hexagon, polygonal more than octagonal, circle, oval etc.,
Be not particularly limited, can depending on the application, usage suitably selected.
If the longitudinal and transverse size or outer diameter of honeycomb catalyst for treating waste gas are less than 30mm, honeycomb exhaust-gas treatment is urged
Agent alternatively in the case where the use of reduced form NOx catalyst, only will increase production radical, thus uneconomical.If honeycomb
The longitudinal and transverse size or outer diameter of shape catalyst for treating waste gas are more than 400mm, then being capable of honeycomb exhaust-gas treatment to the size
Catalyst carries out molding extrusion molding apparatus.
In addition, the length of honeycomb catalyst for treating waste gas is 3~1500mm, the model of further preferred 50~1300mm
It encloses.
In the case where the length of honeycomb catalyst for treating waste gas is less than 3mm, manufacture is become difficult.
If the length of honeycomb catalyst for treating waste gas is more than 1500mm, purposes is few.
The hole density of honeycomb catalyst for treating waste gas is 6~500cpsi, the range of further preferred 15~200cpsi.
In the case where the hole density of honeycomb catalyst for treating waste gas is less than 6cpsi, aperture is big, conformality is deteriorated, system
It makes and becomes difficult.
If the hole density of honeycomb catalyst for treating waste gas is more than 500cpsi, the pressure loss becomes larger when forming, sometimes
Molding becomes difficult.
Honeycomb catalyst for treating waste gas with a thickness of 0.1~1.9mm, the range of further preferred 0.1~1.5mm.
It is difficult to obtain catalyst of the thickness lower than 0.1mm of honeycomb catalyst for treating waste gas.
If the thickness of honeycomb catalyst for treating waste gas is more than 1.9mm, facilitating the cellular of catalyst performance has
The ratio on effect surface is lower, and cannot obtain enough performances sometimes.
[embodiment]
It is illustrated by the following examples, however, the present invention is not limited to these examples.
[embodiment 1]
The preparation of catalyst for treating waste gas (1)
By the catalyst for treating waste gas containing titanium oxide used (honeycomb shape: 20 × 20 mesh of honeycomb hole count, length
1000mm, composition: TiO2=79.65 weight %, WO3=8.0 weight %, V2O5=0.90 weight %, impurity: Na2O=0.35 weight
Measure %, K2O=0.30 weight %, CaO=1.5 weight %, SO4=6.13 weight %) use pulverizer (Ya Liya machinery production institute
(ヤ リ ヤ machinery production institute) system: Ya Liya pulverizer) it crushes.
Then, the catalyst for treating waste gas containing titanium oxide used through crushing is sieved into (mesh size=0.5mm (day
This industrial standard (JIS) regulation)) it is sieved, obtain the pulverized product (1) using complete catalyst.
Process (a)
The average grain diameter for measuring the pulverized product (1) of the catalyst used, is as a result shown in table.
By metatitanic acid slurry (Ishihara Sangyo Kaisha, Ltd.'s (stone originates in industry (strain)) system: MT-A, TiO230 weight % of concentration,
PH1.18) 37.5kg is put into band and is heated to reflux in the stirred tank of device, adds pulverized product (1) 17.4kg of the catalyst used,
It is stirred 6 hours at 30 DEG C, mixed slurry is made.Process (b)
The pH of mixed slurry after cooling is 1.42.
Then, mixed slurry is filtered with vacuum filter, is dehydrated.Process (c)
Na is carried out to filtrate2O、K2O、CaO、V2O5Analysis, will remove these from the pulverized product of the catalyst used (1)
The removal rate of ingredient is shown in table.
In filtering, dewatered cake (51.7 weight % of solid component concentration) 48.4kg, addition ammonium paratungstate (the new gold of Japan
Belong to Co., Ltd. (Japan new metal (strain)) system) 1.42kg and after mixing, the ammonium hydroxide 20kg that 15 weight % of concentration is added carries out
With.At this point, the pH for neutralizing slurry is 9.5.Then, it is cured while carrying out stirring in 3 hours at 95 DEG C.Process (d)
Later, the neutralization, curing slurry are cooled to 40 DEG C, are then filtered, water, prepares solid component concentration 49
The cleaning filter cake of weight %.Process (e)
It is 20 hours dry at 110 DEG C that filter cake will be cleaned, it is (sub- with pulverizer after being further burnt into 5 hours at 550 DEG C
Power Asia machinery production is made: Ya Liya pulverizer) it crushes, obtain the titanium oxide micropowder (1) containing the catalyst used.Process (f), process (g), process (h)
The composition of obtained titanium oxide micropowder (1) is analyzed, in addition, measurement average grain diameter, is as a result shown in table
In.
Titanium oxide micropowder (1) 24.1kg be added ammonium metavanadate 0.082kg is dissolved in monoethanolamine 0.250kg and
The solution and water 3.5kg obtained, is subsequently added into ammonium hydroxide, makes the pH 7.9 of mixed slurry, be heated to be 120 DEG C one on one side with kneader
Knead 0.5 hour on side.
Later, the glass fibre as reinforcing material is added in the mixed slurry (hereinafter, sometimes referred to as " GF ".)
1.39kg, the Emathlite 0.26kg as filler, the polyethylene oxide 0.500kg as organic additive, are existed with kneader
It is mediated 3 hours at 60 DEG C, prepares formed body composition (1).Process (i), process (j)
The content (usage amount benchmark) of each ingredient of the formed body in composition (1) is shown in table.In addition, water content passes through
Infrared moisture measuring instrument (Kate Science Institute (ケ Star ト chemistry institute) system: FD-610) is measured.
With vacuum extruding form machine (ironworker Co., Ltd. of Miyazaki (Miyazaki's iron work (strain)) system) to formed body composition (1)
Extrusion molding is carried out, it is (dimetric for one edge lengths 75m of plane, through direction length about 500mm, aperture to obtain outer diameter
Penetrate through aperture) 6.4mm, septal wall thickness 1.0mm, aperture opening ratio 72% honeycomb structure (1).Process (k)
Then, obtained honeycomb structure (1) is 48 hours dry at 60 DEG C, then it is burnt into 3 hours at 600 DEG C,
It prepares honeycomb catalyst for treating waste gas (1).Process (l), process (m)
Each size for measuring honeycomb catalyst for treating waste gas (1), is as a result shown in table.In addition, honeycomb exhaust-gas treatment
The content (usage amount benchmark) of each ingredient in catalyst (1) is shown in table.
In addition, with specific surface area, the pore volume, compression of the following method measurement honeycomb catalyst for treating waste gas (1)
Intensity, tear strength and denitrating catalyst performance, are as a result shown in table.
<specific surface area>
Based on using the mixed gas of -70% helium of 30% nitrogen as the BET method of adsorbed gas, filled by specific area measuring
Set the specific surface area for finding out honeycomb catalyst for treating waste gas (1).
<pore volume>
Total pore volume of honeycomb catalyst for treating waste gas (1) is found out by mercury injection method.
With reference to measuring method: the measuring method of pore volume is with mercury injection method broad pore distribution measurement device (Kang Ta company (QANTA
CROME society) system: PM-33GT1LP) it is measured.(pressure limit: 32~32200psi)
<compressive strength>
For using compressive strength machine (Tokyo testing machine makes institute (Dong Jing Shi test mechanism makees institute) system: model AL/B30P)
Honeycomb catalyst for treating waste gas (1) is cut into sample obtained by cube or cuboid, honeycomb hole through direction and
Compression load is applied with certain speed on the direction (hreinafter referred to as " vertical direction ") vertical with the direction, reads sample quilt
Maximum loading (N) until destruction finds out compressive strength by (4) formula below.
Compressive strength (N/cm2)=W (N)/{ a (cm) × c (cm) } (4)
Here, the size on 2 sides of a (cm) and the pressurized plane of c (cm) representing sample.W (N) indicate slowly apply load to
Sample be destroyed completely until maximum loading.
<tear strength>
9 × 9 mesh of honeycomb hole count, through direction length 100mm (are subjected to cutting tune to the catalyst of size in addition to this
It is whole) honeycomb catalyst for treating waste gas (1) be used as test sample, which is filled in flow through reactors.?
In flow through reactors, the gas containing sand is made to circulate with following conditions, following (5) formula is based on by the reduction amount of catalyst weight
Measure wear rate.Cyclonic separation is arranged by the back segment in flow through reactors in the logical sand amount of the sand to circulate in flow through reactors
Device measures the weight of sand collected by the cyclone separator after wear test to find out.
Experimental condition
Catalyst shape: 9 × 9 mesh of honeycomb hole count, length 100mm
Gas flow rate: (16.5 ± 2) m/s (catalyst section)
Gas temperature: 25 DEG C of room temperature
The gas currency: 3 hours
Sand concentration: (40 ± 5) g/Nm3
Sand: 500 μm of silica sand average grain diameter
Wear rate (%/kg)=(wear test start before catalyst weight (g)-wear test after catalyst
Weight (g))/wear test start before catalyst weight (g) × 100/ logical sand amount (kg) (5)
<denitrating catalyst performance test>
Cutting tune (will be carried out to the catalyst of size in addition to this by 3 × 3 mesh of honeycomb hole count, through direction length 300mm
It is whole) honeycomb molded body formed honeycomb catalyst for treating waste gas (1) be used as test sample, which is filled in
In flow through reactors.So that the model gas of following compositions is circulated in the flow through reactors, measures denitrification rate.Catalyst connects
Touch the nitrogen oxides (NO in the gas of front and backX) denitrification rate found out by following (6) formula.NO at this timeXConcentration chemiluminescence
Formula analysis of nitrogen oxide meter (arna Tyke Ya Nake Co., Ltd. (Co., Ltd. ア Na テ ッ Network ヤ Na U) system: ECL-
88AO) it is measured.
Denitrification rate (%)={ (not in contact with the NO in gasXThe NO in gas after (quality ppm)-contactX(quality
Ppm))/not in contact with the NO in gasX(quality ppm) } × 100 (6)
Experimental condition
Catalyst shape: 3 × 3 mesh of honeycomb hole count, length 300mm
Reaction temperature: 380 DEG C, superficial linear velocity in a column (SV)=20,000hr-1
Model gas composition: NOX=180 mass ppm, NH3=180 mass ppm, SO2=500
Quality ppm, O2=2 weight %, H2O=10 weight %, N2=balance
[embodiment 2]
The preparation of catalyst for treating waste gas (2)
In the same manner as example 1 by the sieve (sieve of catalyst for treating waste gas containing titanium oxide used through crushing
Mesh size=0.3mm (Japanese Industrial Standards (JIS) regulation)) it is sieved, obtain the pulverized product (2) using complete catalyst.Process (a)
The average grain diameter for measuring the pulverized product (2) of the catalyst used, is as a result shown in table.
Hereinafter, preparing honeycomb exhaust gas in an identical manner other than using the pulverized product (2) of the catalyst used
It handles catalyst (2).
Each size for measuring honeycomb catalyst for treating waste gas (2), is as a result shown in table.In addition, honeycomb exhaust-gas treatment
The content (usage amount benchmark) of each ingredient in catalyst (2) is shown in table.
In addition, with specific surface area, the pore volume, compression of the following method measurement honeycomb catalyst for treating waste gas (2)
Intensity, tear strength and denitrating catalyst performance, are as a result shown in table.
[embodiment 3]
The preparation of catalyst for treating waste gas (3)
In the same manner as example 1 by the sieve (sieve of catalyst for treating waste gas containing titanium oxide used through crushing
Mesh size=0.7mm (Japanese Industrial Standards (JIS) regulation)) it is sieved, obtain the pulverized product (3) using complete catalyst.Process (a)
The average grain diameter for measuring the pulverized product (3) of the catalyst used, is as a result shown in table.
Hereinafter, preparing honeycomb exhaust gas in an identical manner other than using the pulverized product (3) of the catalyst used
It handles catalyst (3).
Each size for measuring honeycomb catalyst for treating waste gas (3), is as a result shown in table.In addition, honeycomb exhaust-gas treatment
The content (usage amount benchmark) of each ingredient in catalyst (3) is shown in table.
In addition, with specific surface area, the pore volume, compression of the following method measurement honeycomb catalyst for treating waste gas (3)
Intensity, tear strength and denitrating catalyst performance, are as a result shown in table.
[embodiment 4]
The preparation of catalyst for treating waste gas (4)
In addition to metatitanic acid slurry (Ishihara Sangyo Kaisha, Ltd.'s system: MT-A, TiO is added in the process (b) of embodiment 12It is dense
Spend 30 weight %) other than pulverized product (1) 31.3kg of catalyst for having used of 7.5kg, addition, mixing is made in an identical manner
Slurry.Process (b)
Then, mixed slurry is filtered with vacuum filter, is dehydrated.Process (c)
Na is carried out to filtrate2O、K2O、CaO、V2O5Analysis, by these ingredients from the pulverized product (1) of the catalyst used
Disengaging (elution) amount, be detached from (elution) rate be shown in table.
Then, ammonium paratungstate (Japan is added in filtering, dewatered cake (51.8 weight % of solid component concentration) 48.3kg
New metal Co. Ltd. system) 0.32kg and after mixing, the ammonium hydroxide 18kg that 15 weight % of concentration is added is neutralized.At this point, neutralizing
The pH of slurry is 9.53.Then, it is cured while carrying out stirring in 3 hours at 95 DEG C.Process (d)
Hereinafter, in the same manner as example 1, preparing honeycomb catalyst for treating waste gas (4).
Each size for measuring honeycomb catalyst for treating waste gas (4), is as a result shown in table.In addition, honeycomb exhaust-gas treatment
The content (usage amount benchmark) of each ingredient in catalyst (4) is shown in table.
In addition, with specific surface area, the pore volume, compression of the following method measurement honeycomb catalyst for treating waste gas (4)
Intensity, tear strength and denitrating catalyst performance, are as a result shown in table.
[embodiment 5]
The preparation of catalyst for treating waste gas (5)
In addition to metatitanic acid slurry (Ishihara Sangyo Kaisha, Ltd.'s system: MT-A, TiO is added in the process (b) of embodiment 12It is dense
Spend 30 weight %) other than pulverized product (1) 3.48kg of catalyst for having used of 67.5kg, addition, it is made in an identical manner mixed
Close slurry.Process (b)
Then, mixed slurry is filtered with vacuum filter, is dehydrated.Process (c)
Na is carried out to filtrate2O、K2O、CaO、V2O5Analysis, by these ingredients from the pulverized product (1) of the catalyst used
Disengaging (elution) amount, be detached from (elution) rate be shown in table.
Then, ammonium paratungstate (Japan is added in filtering, dewatered cake (50.5 weight % of solid component concentration) 49.5kg
New metal Co. Ltd. system) 2.52kg and after mixing, the ammonium hydroxide 28kg that 15 weight % of concentration is added is neutralized.At this point, neutralizing
The pH of slurry is 9.5.Then, it is cured while carrying out stirring in 3 hours at 95 DEG C.Process (d)
Hereinafter, in the same manner as example 1, preparing honeycomb catalyst for treating waste gas (5).
Each size for measuring honeycomb catalyst for treating waste gas (5), is as a result shown in table.In addition, honeycomb exhaust-gas treatment
The content (usage amount benchmark) of each ingredient in catalyst (5) is shown in table.
In addition, with specific surface area, the pore volume, compression of the following method measurement honeycomb catalyst for treating waste gas (5)
Intensity, tear strength and denitrating catalyst performance, are as a result shown in table.
[embodiment 6]
The preparation of catalyst for treating waste gas (6)
In the process (d) of embodiment 1, ammonium paratungstate (Japan New Metals Co., Ltd.'s system) 1.42kg is not added, is added
The ammonium hydroxide 18kg of 15 weight % of concentration is neutralized.At this point, the pH for neutralizing slurry is 9.55.Then, 3 are carried out on one side at 95 DEG C
Hour stirring cures on one side.Process (d)
Hereinafter, in the same manner as example 1, preparing honeycomb catalyst for treating waste gas (6).
Each size for measuring honeycomb catalyst for treating waste gas (6), is as a result shown in table.In addition, honeycomb exhaust-gas treatment
The content (usage amount benchmark) of each ingredient in catalyst (6) is shown in table.
In addition, with specific surface area, the pore volume, compression of the following method measurement honeycomb catalyst for treating waste gas (6)
Intensity, tear strength and denitrating catalyst performance, are as a result shown in table.
[embodiment 7]
The preparation of catalyst for treating waste gas (7)
In addition to titanyl sulfate (Tayca Corp. (テ イ カ (strain)) system: TM knot is added in the process (b) of embodiment 1
Crystalline substance, TiO230 weight % of concentration) 37.5kg replaces mixed slurry is made in an identical manner other than metatitanic acid slurry.Process (b)
The pH of mixed slurry after cooling is 9.54.
Hereinafter, in the same manner as example 1, preparing honeycomb catalyst for treating waste gas (7).
Each size for measuring honeycomb catalyst for treating waste gas (7), is as a result shown in table.In addition, honeycomb exhaust-gas treatment
The content (usage amount benchmark) of each ingredient in catalyst (7) is shown in table.
In addition, with specific surface area, the pore volume, compression of the following method measurement honeycomb catalyst for treating waste gas (7)
Intensity, tear strength and denitrating catalyst performance, are as a result shown in table.
[comparative example 1]
The preparation of catalyst for treating waste gas (R1)
By metatitanic acid slurry (Ishihara Sangyo Kaisha, Ltd.'s system), 75.0kg is put into band and is heated to reflux in the stirred tank of device, then adds
After adding ammonium paratungstate 2.79kg and mixing, pH is adjusted to 9.5 by the ammonium hydroxide 23kg that 15 weight % of concentration is added, at 95 DEG C on one side
Stirring cures for 1 hour on one side.Later, which is cooled to 40 DEG C, is then cleaned, is prepared by filtering, watering
Solid component concentration (TiO2、WO3) 49 weight % cleaning filter cake.
Then, cleaning filter cake is 20 hours dry at 110 DEG C, after being further burnt into 5 hours at 550 DEG C, with crushing
Machine (Ya Liya machinery production is made: Ya Liya pulverizer) crushes, and obtains the titanium oxide micro mist without the catalyst used
Last (R1).Process (f), process (g), process (h)
The composition of obtained titanium oxide micropowder (R1) is analyzed, in addition, measurement average grain diameter, is as a result shown in table
In.Then, titanium oxide micropowder (1) 24.0kg be added ammonium metavanadate 0.273kg is dissolved in monoethanolamine 0.250kg and
The solution and water 3.5kg obtained, is subsequently added into ammonium hydroxide, makes the pH 7.8 of mixed slurry, be heated to be 120 DEG C one on one side with kneader
Knead 0.5 hour on side.
Later, the glass fibre as reinforcing material is added in the mixed slurry (hereinafter, sometimes referred to as " GF ".)
1.39kg, the Emathlite 0.26kg as filler, the polyethylene oxide 0.500kg as organic additive, are existed with kneader
It is mediated 3 hours at 60 DEG C, prepares formed body composition (R1).Process (i), process (j)
Hereinafter, in the same manner as example 1, preparing honeycomb catalyst for treating waste gas (R1).
Each size for measuring honeycomb catalyst for treating waste gas (R1), is as a result shown in table.In addition, honeycomb exhaust-gas treatment
The content (usage amount benchmark) of each ingredient in catalyst (R1) is shown in table.
In addition, with specific surface area, the pore volume, compression of the following method measurement honeycomb catalyst for treating waste gas (R1)
Intensity, tear strength and denitrating catalyst performance, are as a result shown in table.
[comparative example 2]
The preparation of catalyst for treating waste gas (R2)
In the same manner as example 1 by the sieve (sieve of catalyst for treating waste gas containing titanium oxide used through crushing
Mesh size=1.0mm (Japanese Industrial Standards (JIS) regulation)) it is sieved, obtain the pulverized product (R2) using complete catalyst.Process (a)
The average grain diameter for measuring the pulverized product (R2) of the catalyst used, is as a result shown in table.
Hereinafter, it is useless to prepare honeycomb in an identical manner other than using the pulverized product (R2) of the catalyst used
Gas disposal catalyst (R2).
Each size for measuring honeycomb catalyst for treating waste gas (R2), is as a result shown in table.In addition, honeycomb exhaust-gas treatment
The content (usage amount benchmark) of each ingredient in catalyst (R2) is shown in table.
In addition, with specific surface area, the pore volume, compression of the following method measurement honeycomb catalyst for treating waste gas (R2)
Intensity, tear strength and denitrating catalyst performance, are as a result shown in table.
[comparative example 3]
The preparation of catalyst for treating waste gas (R3)
In addition to metatitanic acid slurry (Ishihara Sangyo Kaisha, Ltd.'s system: MT-A, TiO is added in the process (b) of embodiment 12It is dense
Spend 30 weight %) other than pulverized product (1) 34.7kg of catalyst for having used of 0.4kg, addition, mixing is made in an identical manner
Slurry.Process (b)
Then, mixed slurry is filtered with vacuum filter, is dehydrated.Process (c)
Na is carried out to filtrate2O、K2O、CaO、V2O5Analysis, by these ingredients from the pulverized product (1) of the catalyst used
Disengaging (elution) amount, be detached from (eluting rate is shown in table.
Then, ammonium paratungstate (Japan is added in filtering, dewatered cake (52.0 weight % of solid component concentration) 48.1kg
New metal Co. Ltd. system) 0.06kg and after mixing, the ammonium hydroxide 16kg that 15 weight % of concentration is added is neutralized.At this point, neutralizing
The pH of slurry is 9.52.Then, it is cured while carrying out stirring in 3 hours at 95 DEG C.Process (d)
Hereinafter, in the same manner as example 1, preparing honeycomb catalyst for treating waste gas (R3).
Each size for measuring honeycomb catalyst for treating waste gas (R3), is as a result shown in table.In addition, honeycomb exhaust-gas treatment
The content (usage amount benchmark) of each ingredient in catalyst (R3) is shown in table.
In addition, with specific surface area, the pore volume, compression of the following method measurement honeycomb catalyst for treating waste gas (R3)
Intensity, tear strength and denitrating catalyst performance, are as a result shown in table.
[comparative example 4]
The preparation of catalyst for treating waste gas (R4)
In addition to metatitanic acid slurry (Ishihara Sangyo Kaisha, Ltd.'s system: MT-A, TiO is added in the process (b) of embodiment 12It is dense
Spend 30 weight %) other than pulverized product (1) 2.79kg of catalyst for having used of 69.0kg, addition, it is made in an identical manner mixed
Close slurry.Process (b)
Then, mixed slurry is filtered with vacuum filter, is dehydrated.Process (c)
Na is carried out to filtrate2O、K2O、CaO、V2O5Analysis, by these ingredients from the pulverized product (1) of the catalyst used
Disengaging (elution) amount, be detached from (elution) rate be shown in table.
Then, ammonium paratungstate is added in filtering, dewatered cake (51 weight % of solid component concentration) 49.0kg, and (Japan is newly
Metal Co. Ltd. system) 0.06kg and mix after, be added 15 weight % of concentration ammonium hydroxide 16kg neutralized.At this point, neutralizing slurry
The pH of material is 9.54.Then, it is cured while carrying out stirring in 3 hours at 95 DEG C.Process (d)
Hereinafter, in the same manner as example 1, preparing honeycomb catalyst for treating waste gas (R4).
Each size for measuring honeycomb catalyst for treating waste gas (R4), is as a result shown in table.In addition, honeycomb exhaust-gas treatment
The content (usage amount benchmark) of each ingredient in catalyst (R4) is shown in table.
In addition, with specific surface area, the pore volume, compression of the following method measurement honeycomb catalyst for treating waste gas (R4)
Intensity, tear strength and denitrating catalyst performance, are as a result shown in table.
[comparative example 5]
The preparation of catalyst for treating waste gas (R5)
By the catalyst for treating waste gas containing titanium oxide used (honeycomb shape: 20 × 20 mesh of honeycomb hole count, length
1000mm, composition: TiO2=79.65 weight %, WO3=8.0 weight %, V2O5=0.90 weight %, impurity: Na2O=0.35 weight
Measure %, K2O=0.30 weight %, CaO=1.5 weight %, SO4=6.13 weight %) it is used as honeycomb catalyst for treating waste gas
(R5) it uses.
Measure specific surface area, pore volume, the compressive strength, tear strength of honeycomb catalyst for treating waste gas (R5), knot
Fruit is shown in table.
Honeycomb catalyst for treating waste gas (R5) cutting is adjusted to the length of 3 × 3 mesh of honeycomb hole count, through direction
300mm measures denitrating catalyst performance in the same manner as example 1, is as a result shown in table.
[table 1]
Other compositions are mainly (WO3、Al2O3、SiO2)。
[table 2]
[table 3]
[table 4]
* the content of titanium oxide micropowder is to subtract V from original amount2O5, WO3Numerical value indicate.
Claims (9)
1. a kind of manufacturing method of catalyst for treating waste gas, which is characterized in that
After the catalyst for treating waste gas containing titanium oxide that will have been used crushes and the powder that average grain diameter is 0.1~15 μm is made,
By aqueous solution of titanyle sulfate and/or metatitanic acid slurry and the catalyst for treating waste gas containing titanium oxide used the powder into
Row mixing, is made mixed slurry so that aqueous solution of titanyle sulfate and/or metatitanic acid slurry with TiO2The concentration C of meterTWith through powder
The concentration C of the solid component of the broken catalyst for treating waste gas containing titanium oxide usedRCConcentration ratio CT/CRCReach 0.1~9.0
Range,
After filtering the mixed slurry, addition alkali compounds neutralizes titanyl sulfate and/or metatitanic acid, preparation pH 7~
Titanium oxide gel in the range of 12,
The gel is burnt into, is then crushed, titanium oxide micropowder is prepared,
The titanium oxide micropowder and reinforcing material are mixed,
It is burnt into after being formed to mixture.
2. the manufacturing method of catalyst for treating waste gas as described in claim 1, which is characterized in that by alkali compounds into
Before row neutralizes, mixed active component precursor compound.
3. the manufacturing method of catalyst for treating waste gas as described in claim 1, which is characterized in that be mixed together with reinforcing material
Active component precursors compound.
4. the manufacturing method of catalyst for treating waste gas as claimed in claim 2 or claim 3, which is characterized in that active component precursors
The compound that object is at least one kind of element selected from V, W, Mo, Cr, Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, Ir is closed,
Compound including the metal element and producible metal oxide.
5. a kind of catalyst for treating waste gas, which is characterized in that
It is obtained by method described in claim 1,
Containing (i) titanium oxide micropowder and (ii) reinforcing material, (i) content of titanium oxide micropowder is in 60~97 weight %
In the range of, the content of (ii) reinforcing material is in the range of 3~15 weight %.
6. catalyst for treating waste gas as claimed in claim 5, which is characterized in that also contain (iii) active constituent, be somebody's turn to do (iii)
The content of active constituent in terms of oxide in the range of 0.001~15 weight %, the content of (i) titanium oxide micropowder
For 60~96 weight %.
7. catalyst for treating waste gas as claimed in claim 5, which is characterized in that also contain filler, the content of the filler is 0.5
In the range of~15 weight %, the content of (i) titanium oxide micropowder is 60~96 weight %.
8. catalyst for treating waste gas as claimed in claim 5, which is characterized in that the catalyst for treating waste gas is honeycomb moulding
Body, in the range of 30~400mm, length is in the range of 3~1500mm, hole density for the cellular longitudinal and transverse size or outer diameter
In the range of 6~500cpsi, thickness is in the range of 0.1~1.9mm.
9. catalyst for treating waste gas as claimed in claim 6, which is characterized in that the active constituent be selected from V, W, Mo, Cr,
The metal or metal oxide of at least one kind of element of Mn, Fe, Ni, Cu, Ag, Au, Pd, Y, Ce, Nd, In, Ir.
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| CN106944039B (en) * | 2017-02-21 | 2020-10-16 | 安徽迪诺环保新材料科技有限公司 | Production method of honeycomb denitration catalyst carrier material with more than 40 holes |
| CN111974378B (en) * | 2020-09-23 | 2023-06-09 | 国家能源投资集团有限责任公司 | Denitration catalyst and preparation method thereof |
| CN112316937B (en) * | 2020-11-16 | 2023-05-12 | 陆叶梓 | Cement rotary kiln waste gas treatment catalyst and preparation method thereof |
| CN116060425B (en) * | 2023-03-08 | 2023-06-02 | 国能龙源环保有限公司 | Method for removing Hg on surface of waste denitration catalyst |
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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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| JPS5829143B2 (en) * | 1979-04-27 | 1983-06-21 | 石原産業株式会社 | A new method for producing a denitrification catalyst that reuses waste catalyst as a raw material |
| JPS61153139A (en) * | 1984-12-27 | 1986-07-11 | Babcock Hitachi Kk | Regeneration method of denitrating catalyst |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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