CN107308991A - A kind of wall drift tube type SCR denitration and preparation method thereof - Google Patents
A kind of wall drift tube type SCR denitration and preparation method thereof Download PDFInfo
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- CN107308991A CN107308991A CN201710445216.2A CN201710445216A CN107308991A CN 107308991 A CN107308991 A CN 107308991A CN 201710445216 A CN201710445216 A CN 201710445216A CN 107308991 A CN107308991 A CN 107308991A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0219—Coating the coating containing organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Abstract
The present invention relates to catalyst preparation technical field, a kind of wall drift tube type SCR denitration, including catalyst coat material and catalyst activity component are disclosed, the catalyst coat material includes the raw material of following parts by weight：100 parts of titanium dioxide, 5 20 parts of bentonite；The catalyst activity component includes the raw material of following parts by weight：0.2 3 parts of manganese acetate, 1 10 parts of rare-earth oxide.The method for preparing catalyst of the present invention be able to can be just molded on the basis of catalyst load fastness and its catalytic effect is ensured by primary coating, calcining, with short production cycle, and improve the accuracy of product compositions content, lift catalyst performance.
Description
Technical field
The present invention relates to catalyst preparation technical field, more particularly to a kind of wall drift tube type SCR denitration and its system
Preparation Method.
Background technology
Nitrogen oxides is one of major pollutants in air, and nitrogen oxides is mainly by nitric oxide and nitrogen dioxide structure
Into.Nitric oxide is originally nontoxic, and after being converted into nitrogen dioxide when reacting, great pollution is caused to environment, and
Seriously endanger healthy.A large amount of discharges of nitrogen oxides, one is, in the case where the sun shines, to occur photochemical reaction, result in city
The composite air pollution such as city or region gray haze, photochemical fog is aggravated；Two are the increase in the pollution level of acid rain, with the whole nation
The construction of each desulfurization equipment, the regulation effect of sulfur dioxide shows, and nitrogen oxides is increasingly becoming the first acid pollution gas
Body.；Three be the effect by dry, wet deposition, has aggravated the influence of body eutrophication.China clearly arranges NOx discharge
One of pollutant of priority control during entering, and correspondingly discharge rich and influential family such as Thermal Power Generation Industry and motor vehicle industry have been promulgated accordingly
Nitrogen oxides control policy.
NOx two aspects of discharge main source, one is stationary source such as coal-burning power plant, cement plant, glass furnace etc., and two are
Moving source such as motor vehicle, large-scale diesel engine etc..For the low of monoblock type can be used in the high flue gas denitrification system of dust content
Hole density cellular catalyst, for fuel oil, the generating set of combustion gas, large-scale diesel engine and motor vehicle, due to containing in flue gas
Dust quantity is very low, therefore the catalysis of hole density bigger (pitch is smaller) can be used in the SCR denitration in flue gas denitrification system
Agent, to improve the disposal ability of catalyst unit volume, so as to greatly reduce the usage amount of catalyst.And be less than for pitch
3mm integral honeycomb SCR denitration, it is difficult to prepared with the method for conventional integrated extrusion molding, therefore in the type
Catalyst prod prepare when, use cordierite carrier using apply carry method obtain fine pith integral honeycomb SCR denitration
Catalyst turns into a selection well.At present, the specification of common cordierite carrier has 200/400/600 mesh, equivalent to section
Away from for 1.8mm, 1.3mm and 1.0mm.In this case, load formula honeycombed SCR denitration either unit price or phase are applied
Use volume with treatment effeciency is all far superior to squash type product.
For the atomic flue gas of dustiness (dust removal process was predominantly carried out in advance, country discharge standard is reached
Flue gas) denitrating system can be integrated with cleaner, and perforated tubular is made based on this denitrating catalyst, integrated with dust-removal cloth-bag
Wall flow type ceramic pipe catalyst is formed, the preparation of the type denitrating catalyst applies load formula SCR denitration using foamed ceramics pipe and is catalyzed
Agent, because active component all bears the coating surface in carrier, therefore is to apply the effect carried and product compositions the problem of most critical
The control of content；It is how convenient, succinct to obtain component and designing value deviation very small product, apply load as preparing
The key of formula integral wall drift tube type SCR denitration.
Patent CNl01185886A discloses a kind of preparation method of SCR denitration, is to employ first to prepare Al2O3-
SiO2-TiO2Complex sol, carries out painting load in carrier surface afterwards；Its proofing is being contained into nitric acid after drying, roasting
In lanthanum, ammonium metavanadate, secondary and oxalic acid mixed liquor, the obtained method after drying and roasting.Patent CN 102614890A are disclosed
A kind of nitric acid, the honeycomb monolith SCR catalyst of nitrate tail gas denitration, are used first with cordierite powder and other auxiliary materials
Powder the carrier of netted honeycomb hole is made through steps such as ball milling, kneading, shaping, sizing, firings, prepare oxygen with aluminum oxide afterwards
Change aluminium and apply material containing slurry, be coated on carrier, then by the method for proofing by vanadium, tungsten, key, manganese, chromium, copper, iron isoreactivity
Composition and co-catalyst are supported on the carrier applied after carrying, are made after drying, roasting.Prepared by the method carried at present using applying
It is required for by two the main preparations of preparation process, i.e. coating and supporting for catalyst activity component.
Active component is carried out again support, still first carry out active component and support to be made to urge after either first carrying out coating preparation
Feed liquid is prepared after agent powder again and carries out painting load, is required for carrying out calcination process twice, so not only causes the wave on the energy
Take, and preparation process is long, in its preparation process, applies the control of carrying capacity and deviation easily occurs in the control of activity component load quantity
Accumulation is so as to cause each component content and design load deviation of final products larger.And catalyst preparation research is 10 points of essences
Carefully and practicality very strong technology, accurate control parameters and condition are highly important.In summary, find a kind of new
Denitrating catalyst preparation method, so as to reduce the production cycle, and improve the accuracy of product compositions content, lifted
Catalyst performance, tool is of great significance.
The content of the invention
In order to solve the above-mentioned technical problem, the invention provides a kind of wall drift tube type SCR denitration and its preparation side
Method.The method for preparing catalyst of the present invention can pass through on the basis of catalyst load fastness and its catalytic effect is ensured
Primary coating, calcining can be just molded, with short production cycle, and improve the accuracy of product compositions content, lift catalyst performance.
The present invention concrete technical scheme be：A kind of wall drift tube type SCR denitration, including catalyst coat material and
Catalyst activity component, the catalyst coat material includes the raw material of following parts by weight：100 parts of titanium dioxide, bentonite 5-
20 parts；The catalyst activity component includes the raw material of following parts by weight：0.2-3 parts of manganese acetate, rare-earth oxide 1-10
Part.
Preferably, the rare-earth oxide is at least one of lanthanoid metal, cerium, oxide of yttrium.
Preferably, the titanium dioxide crystal form is anatase titanium dioxide, and it is made by sulfuric acid process.
Preferably, the bentonite is the bentonite containing montmorillonite mineral more than 80%.
Preferably, the particle diameter of the titanium dioxide, bentonite and rare-earth oxide is in D50 ＜ 2mm, D90 ＜ 5mm
In the range of.
A kind of preparation method of wall drift tube type SCR denitration, is added directly into catalyst by catalytic active component and applies
In layer material, the composite mortar containing catalytic active component is formed, composite mortar is then coated in wall drift tube type foamed ceramics
Wall drift tube type SCR denitration is obtained after pipe internal surface, drying and roasting.
Preferably, the preparation method of above-mentioned wall drift tube type SCR denitration, is comprised the following steps that：
A), manganese acetate is dissolved in the deionized water of its 50-100 times of quality, acetic acid manganese solution is obtained, it is standby；
B), by the effective deionized water dipping of wall drift tube type foamed ceramics, washing, 105-115 DEG C of dry 1.5-2.5h is standby；
C), by titanium dioxide, bentonite and rare-earth oxide by proportioning mix, add appropriate amount of deionized water, ammoniacal liquor and
Cmc carries out kneading plasticizing, adjusts material acid-base value, old to put 10-14h, obtains plasticity material；
D) the acetic acid manganese solution and appropriate amount of deionized water, are added into the plasticity material, in high-speed emulsifying machine emulsify 30~
Ammonification water is with the sulfate radical in neutralisation of sulphuric acid method anatase titanium dioxide during 60min, emulsification, and adjusts pH value 7-9, Ran Houjia
It is 1000~6000mPaS to enter PEO regulation viscosity, and composite mortar is made；
E), the compound slurry is applied directly to the wall stream after step b) processing by the method purged using negative-pressure adsorption, malleation
On tubular type foamed ceramics pipe internal surface；
F), by step e) prepare coated catalyst at 105-115 DEG C dry 3.5-4.5h, be subsequently placed in Muffle furnace with
1.8-2.2 DEG C/Min speed, which is warming up to after 290-310 DEG C, calcines 3.5-4.5h, then is heated up with 4.8-5.2 DEG C/Min speed
1.5-2.5h is calcined after to 610-630 DEG C, finished product is obtained, coating load amount is 10-40%.
The advantage of this technology invention is：In foam type carrier inner surfaces of pores there is high capacity efficiency to urge there is provided one kind
Agent preparation technology, without needing to carry out pre-acidified processing to carrier, while being catalyzed compared to traditional first prepares coating back loading
Active component and coating material can be prepared by mixing into support materials by the technique of agent attribute component, this technology, and a step completes coating
In carrier surface, the load-carrying efficiency of active component and coating material is not only increased, the distribution bias of catalytic component is reduced,
The activity of catalyst is improved, and substantially reduces the preparation time of catalyst, the energy has been saved, has been more suitable for scale system
It is standby；
This technology has invented a kind of preparation method of the support materials with function admirable：Due in irregular foam pore structure
The carrier of distribution is not only difficult to control to load due to out-of-flatness surface of the inner surfaces of pores for macroscopic view during supported catalytic materials
Amount, and easily change the pore size distribution$ of carrier, or even block the hole path of carrier, therefore stickiness for support materials,
Rheological property has higher requirement.
Present invention employs control diameter of particle, the method that slurrying is emulsified at a high speed can make slurry adhesion, good fluidity,
Property is more stable, and coating load amount is bigger, with reference to stronger advantage.
Catalyst prepared by the catalyst support materials and its preparation method of load foamed ceramics invented using this technology
Active height, the wide characteristic of active temperature windows after testing；
The inventive method active component can be substantially adhered to coat powder surface so that by controlling the painting carrying capacity of slurry, reach
To the purpose of accurate control catalytic active component content；
Preferably, the wall drift tube type foamed ceramics pipe is cordierite foamed ceramics pipe.
Preferably, the alkali metal oxide content of the cordierite foamed ceramics pipe is less than 100ppm, macroscopical pore volume
For 50~80%.
Preferably, the addition of deionized water is the 24-40% of solid matter mass, the addition of ammoniacal liquor in step c)
For the 0.08-0.2wt% of solid matter mass, the addition of carboxymethyl cellulose is the 0.1- of solid matter mass
0.5wt%., the ammoniacal liquor initial concentration is 15wt%.
Preferably, in the step d) composite mortar slurry solid content be 20-50wt%, size distribution be 1~
20um。
It is compared with the prior art, the beneficial effects of the invention are as follows：
The present invention prepares coating and active component is supported on same step and completed, and not only increases active component and coating material
Load-carrying efficiency, reduce the distribution bias of catalytic component, improve the activity of catalyst, and substantially reduce catalyst
Preparation time, saved the energy, be more suitable for prepare with scale.
The catalyst active height after testing prepared, activity are constituted and preparation method thereof using catalytic component of the present invention
The wide characteristic of temperature window.
Meanwhile, the inventive method active component can be substantially adhered to coat powder surface so that by controlling slurry
Carrying capacity is applied, the purpose of accurate control catalytic active component content is reached.
Present invention employs control diameter of particle, the method that slurrying is emulsified at a high speed can make slurry adhesion, good fluidity,
Property is more stable, and coating load amount is bigger, with reference to more firm.
Embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1
A kind of wall drift tube type SCR denitration, including catalyst coat material and catalyst activity component.
The catalyst coat material includes the raw material of following parts by weight：(anatase titanium dioxide passes through sulfuric acid legal system to titanium dioxide
) 100 parts, 12.5 parts of bentonite (containing montmorillonite mineral more than 80%).
The catalyst activity component includes the raw material of following parts by weight：1.6 parts of manganese acetate, rare-earth oxide (oxygen
Change cerium) 5.5 parts.
A kind of preparation method of wall drift tube type SCR denitration, is comprised the following steps that：
A), manganese acetate is dissolved in the deionized water of its 100 times of quality, acetic acid manganese solution is obtained, it is standby.
B), by φ 50mm × L300mm × δ 8mm two wall drift tube type foamed ceramics pipes (cordierite, alkali metal oxidation
Thing content is less than 100ppm, and macroscopical pore volume washs 65%) to use deionized water dipping, and 110 DEG C of dry 2h are standby.
C), titanium dioxide, bentonite and rare-earth oxide are mixed by proportioning, above material diameter of particle should be selected
In the range of D50 ＜ 2mm, D90 ＜ 5mm, it is 15wt% ammoniacal liquor and 0.2 part to add 40 parts of deionized waters, 0.1 part of concentration
Cmc carries out kneading plasticizing, old to put 12h, obtains plasticity material.
D) the acetic acid manganese solution and appropriate amount of deionized water, are added into the plasticity material, is emulsified in high-speed emulsifying machine
Ammonification water adjusts pH value 8 during 60min, emulsification, and it is 2000mPaS then to add PEO regulation viscosity, and composite mortar, slurry is made
Solid content is 36wt%, and size distribution is 1~20um.
E), the compound slurry is applied directly to after step b) processing by the method purged using negative-pressure adsorption, malleation
On wall drift tube type foamed ceramics pipe internal surface.
F), by step e) prepare coated catalyst at 110 DEG C dry 4h, be subsequently placed in Muffle furnace with 2 DEG C/
Min speed, which is warming up to after 300 DEG C, calcines 4h, then calcines 2h after being warming up to 620 DEG C with 5 DEG C/Min speed, obtains finished product, applies
Layer load capacity is 18.6%.
Embodiment 2
A kind of wall drift tube type SCR denitration, including catalyst coat material and catalyst activity component.
The catalyst coat material includes the raw material of following parts by weight：(anatase titanium dioxide passes through sulfuric acid legal system to titanium dioxide
) 100 parts, 5 parts of bentonite (containing montmorillonite mineral more than 80%).
The catalyst activity component includes the raw material of following parts by weight：0.2 part of manganese acetate, rare-earth oxide (oxygen
Change lanthanum) 10 parts.
A kind of preparation method of wall drift tube type SCR denitration, is comprised the following steps that：
A), manganese acetate is dissolved in the deionized water of its 100 times of quality, acetic acid manganese solution is obtained, it is standby.
B), by φ 50mm × L300mm × δ 8mm two wall drift tube type foamed ceramics pipes (cordierite, alkali metal oxidation
Thing content is less than 100ppm, and macroscopical pore volume washs 50%) to use deionized water dipping, and 105 DEG C of dry 2.5h are standby.
C), titanium dioxide, bentonite and rare-earth oxide are mixed by proportioning, above material diameter of particle should be selected
In the range of D50 ＜ 2mm, D90 ＜ 5mm, it is 15wt% ammoniacal liquor and 0.2 part to add 40 parts of deionized waters, 0.1 part of concentration
Cmc carries out kneading plasticizing, old to put 11h, obtains plasticity material.
D) the acetic acid manganese solution and appropriate amount of deionized water, are added into the plasticity material, is emulsified in high-speed emulsifying machine
Ammonification water adjusts pH value 8 during 30min, emulsification, and it is 1200mPaS then to add PEO regulation viscosity, and composite mortar, slurry is made
Solid content is 30wt%, and size distribution is 1~20um.
E), the compound slurry is applied directly to after step b) processing by the method purged using negative-pressure adsorption, malleation
On wall drift tube type foamed ceramics pipe internal surface.
F) step e), is prepared into coated catalyst 4.5h is dried at 105 DEG C, be subsequently placed in Muffle furnace with 1.8
DEG C/Min speed is warming up to after 290 DEG C and calcines 4.5h, then 2.5h is calcined after being warming up to 610 DEG C with 4.8 DEG C/Min speed, obtain
To finished product, coating load amount is 10.8%.
Embodiment 3
A kind of wall drift tube type SCR denitration, including catalyst coat material and catalyst activity component.
The catalyst coat material includes the raw material of following parts by weight：(anatase titanium dioxide passes through sulfuric acid legal system to titanium dioxide
) 100 parts, 20 parts of bentonite (containing montmorillonite mineral more than 80%).
The catalyst activity component includes the raw material of following parts by weight：3 parts of manganese acetate, rare-earth oxide (oxidation
Cerium) 1 part.
A kind of preparation method of wall drift tube type SCR denitration, is comprised the following steps that：
A), manganese acetate is dissolved in the deionized water of its 100 times of quality, acetic acid manganese solution is obtained, it is standby.
B), by φ 50mm × L300mm × δ 8mm two wall drift tube type foamed ceramics pipes (cordierite, alkali metal oxidation
Thing content is less than 100ppm, and macroscopical pore volume washs 80%) to use deionized water dipping, and 115 DEG C of dry 2h are standby.
C), titanium dioxide, bentonite and rare-earth oxide are mixed by proportioning, above material diameter of particle should be selected
In the range of D50 ＜ 2mm, D90 ＜ 5mm, it is 15wt% ammoniacal liquor and 0.2 part to add 25 parts of deionized waters, 0.1 part of concentration
Cmc carries out kneading plasticizing, old to put 13h, obtains plasticity material.
D) the acetic acid manganese solution and appropriate amount of deionized water, are added into the plasticity material, is emulsified in high-speed emulsifying machine
Ammonification water adjusts pH value 8 during 90min, emulsification, and it is 3500mPaS then to add PEO regulation viscosity, and composite mortar, slurry is made
Solid content is 38wt%, and size distribution is 1~20um.
E), the compound slurry is applied directly to after step b) processing by the method purged using negative-pressure adsorption, malleation
On wall drift tube type foamed ceramics pipe internal surface.
F) step e), is prepared into coated catalyst 3.5h is dried at 115 DEG C, be subsequently placed in Muffle furnace with 2.2
DEG C/Min speed is warming up to after 310 DEG C and calcines 3.5h, then 1.5h is calcined after being warming up to 630 DEG C with 4.8 DEG C/Min speed, obtain
To finished product, coating load amount is 24.3%.
Embodiment 4
A kind of wall drift tube type SCR denitration, including catalyst coat material and catalyst activity component.
The catalyst coat material includes the raw material of following parts by weight：(anatase titanium dioxide passes through sulfuric acid legal system to titanium dioxide
) 100 parts, 8 parts of bentonite (containing montmorillonite mineral more than 80%).
The catalyst activity component includes the raw material of following parts by weight：1.5 parts of manganese acetate, rare-earth oxide (oxygen
Change yttrium) 4 parts.
A kind of preparation method of wall drift tube type SCR denitration, is comprised the following steps that：
A), manganese acetate is dissolved in the deionized water of its 50 times of quality, acetic acid manganese solution is obtained, it is standby.
B), by φ 50mm × L300mm × δ 8mm two wall drift tube type foamed ceramics pipes (cordierite, alkali metal oxidation
Thing content is less than 100ppm, and macroscopical pore volume washs 70%) to use deionized water dipping, and 105 DEG C of dry 2h are standby.
C), titanium dioxide, bentonite and rare-earth oxide are mixed by proportioning, above material diameter of particle should be selected
In the range of D50 ＜ 2mm, D90 ＜ 5mm, it is 15wt% ammoniacal liquor and 0.56 part to add 24 parts of deionized waters, 0.25 part of concentration
Cmc carry out kneading plasticizing, it is old to put 12h, obtain plasticity material.
D) the acetic acid manganese solution and appropriate amount of deionized water, are added into the plasticity material, is emulsified in high-speed emulsifying machine
Ammonification water adjusts pH value 8 during 70min, emulsification, and it is 6000mPaS then to add PEO regulation viscosity, and composite mortar, slurry is made
Solid content is 50wt%, and size distribution is 1~20um.
E), the compound slurry is applied directly to after step b) processing by the method purged using negative-pressure adsorption, malleation
On wall drift tube type foamed ceramics pipe internal surface.
F), by step e) prepare coated catalyst at 110 DEG C dry 4h, be subsequently placed in Muffle furnace with 2 DEG C/
Min speed, which is warming up to after 320 DEG C, calcines 4h, then calcines 2h after being warming up to 620 DEG C with 5 DEG C/Min speed, obtains finished product, applies
Layer load capacity is 25%.
Embodiment 5
A kind of wall drift tube type SCR denitration, including catalyst coat material and catalyst activity component.
The catalyst coat material includes the raw material of following parts by weight：(anatase titanium dioxide passes through sulfuric acid legal system to titanium dioxide
) 100 parts, 8 parts of bentonite (containing montmorillonite mineral more than 80%).
The catalyst activity component includes the raw material of following parts by weight：1.5 parts of manganese acetate, rare-earth oxide (oxygen
Change yttrium, cerium oxide) 6 parts.
A kind of preparation method of wall drift tube type SCR denitration, is comprised the following steps that：
A), manganese acetate is dissolved in the deionized water of its 75 times of quality, acetic acid manganese solution is obtained, it is standby.
B), by φ 50mm × L300mm × δ 8mm two wall drift tube type foamed ceramics pipes (cordierite, alkali metal oxidation
Thing content is less than 100ppm, and macroscopical pore volume washs 60%) to use deionized water dipping, and 105 DEG C of dry 2h are standby.
C), titanium dioxide, bentonite and rare-earth oxide are mixed by proportioning, above material diameter of particle should be selected
In the range of D50 ＜ 2mm, D90 ＜ 5mm, it is 15wt% ammoniacal liquor and 0.3 part to add 40 parts of deionized waters, 0.15 part of concentration
Cmc carry out kneading plasticizing, it is old to put 12h, obtain plasticity material.
D) the acetic acid manganese solution and appropriate amount of deionized water, are added into the plasticity material, is emulsified in high-speed emulsifying machine
Ammonification water adjusts pH value 8 during 50min, emulsification, and it is 1000mPaS then to add PEO regulation viscosity, and composite mortar, slurry is made
Solid content is 20wt%, and size distribution is 1~20um.
E), the compound slurry is applied directly to after step b) processing by the method purged using negative-pressure adsorption, malleation
On wall drift tube type foamed ceramics pipe internal surface.
F), by step e) prepare coated catalyst at 110 DEG C dry 4h, be subsequently placed in Muffle furnace with 2 DEG C/
Min speed, which is warming up to after 320 DEG C, calcines 4h, then calcines 2h after being warming up to 620 DEG C with 5 DEG C/Min speed, obtains finished product, applies
Layer load capacity is 40%.
Performance test
The measure of carrier loaded amount：With the net weight of the original foam of electronic balance weighing above example 1 to embodiment 3 ceramics,
W1 is designated as, after above step coating catalyst support materials, the foamed ceramics of catalyst has been loaded with electronic balance weighing
Weight, is designated as W2, with formula θ (%)=(W2-W1)/W2 computational load amounts, and above example is designated as θ 1, θ 2, θ 3 respectively, specific number
According to being shown in Table 1.
Table 1
The measure of the pressure loss：Measure is compared with resistance measurement pipe, gas flows to foamed pipe from the outer surface of foamed pipe
Inner surface, air speed is 5000/h, and the pressure differential inside and outside foamed pipe is measured with difference gauge, and original earthenware and load are measured respectively
The resistance of the earthenware of catalyst material, above-described embodiment is designated as Pa1 and Pb1, Pa2 and Pb2, Pa3 and Pb3 respectively, tests institute
Obtain data and be shown in Table 2.
Table 2
The adhesion test of support materials：The ceramics of catalysis material have been loaded with oscillation cleaning in ultrasonic washing instrument hot bath
Pipe, the weight before and after cleaning is weighed with electronic balance respectively, and the earthenware weight before cleaning is designated as W3, the earthenware weight after cleaning
Amount is designated as W4, and the loss late of the support materials after thermosonication vibration is calculated with formula δ (%)=(W3-W4)/W3, and the above is implemented
Example is denoted as δ 1 respectively, and δ 2, δ 2, specific data measured is shown in Table 3.
Table 3
The activity rating test of catalyst：With catalyst activity evaluating apparatus test catalyst activity index, set air speed as
1500/h, setting reaction temperature is respectively 160 DEG C and 380 DEG C, and entrance mixed gas NO concentration is 1000mg/Nm3, and rate of oxygen is
6%, moisture content is 10%, and reducing agent is made with ammonia.The efficiency of removing NO (denitration) at each temperature is measured respectively, and the above is implemented
Example measures denitration efficiency at 160 DEG C and is designated as η a1, η a2 and η a3 respectively, and denitration efficiency is not obtained at 380 DEG C and is designated as η b1 respectively,
η b2 and η b3, specific determination data are shown in Table 4.
Table 4
Implement the row test data above and illustrate have using the SCR denitration prepared by the technology of the present invention good
Activity and temperature stability.
Raw materials used in the present invention, equipment, is the conventional raw material, equipment of this area unless otherwise noted；In the present invention
Method therefor, is the conventional method of this area unless otherwise noted.
It is described above, only it is presently preferred embodiments of the present invention, not the present invention is imposed any restrictions, it is every according to the present invention
Any simple modification, change and equivalent transformation that technical spirit is made to above example, still fall within the technology of the present invention side
The protection domain of case.
Claims (10)
1. a kind of wall drift tube type SCR denitration, it is characterised in that including catalyst coat material and catalyst activity component,
The catalyst coat material includes the raw material of following parts by weight：100 parts of titanium dioxide, 5-20 parts of bentonite；The catalyst
Active component includes the raw material of following parts by weight：0.2-3 parts of manganese acetate, 1-10 parts of rare-earth oxide.
2. a kind of wall drift tube type SCR denitration as claimed in claim 1, it is characterised in that the rare earth metal oxidation
Thing is at least one of lanthanoid metal, cerium, oxide of yttrium.
3. a kind of wall drift tube type SCR denitration as claimed in claim 1, it is characterised in that the titanium dioxide crystal form
For anatase titanium dioxide, and it is made by sulfuric acid process.
4. a kind of wall drift tube type SCR denitration as claimed in claim 1, it is characterised in that the bentonite is containing illiteracy
The bentonite of de- stone ore thing more than 80%.
5. a kind of preparation method of wall drift tube type SCR denitration as claimed in claim 1, it is characterised in that：Described two
The particle diameter of titanium oxide, bentonite and rare-earth oxide is in D50<2mm, D90<In the range of 5mm.
6. a kind of preparation method of wall drift tube type SCR denitration as described in one of claim 1-5, it is characterised in that：
Catalytic active component is added directly into catalyst coat material, the composite mortar containing catalytic active component is formed, then
Wall drift tube type SCR denitration is obtained after composite mortar is coated in into wall drift tube type foamed ceramics pipe internal surface, drying and roasting.
7. a kind of preparation method of wall drift tube type SCR denitration as claimed in claim 6, it is characterised in that specific step
It is rapid as follows：
A), manganese acetate is dissolved in the deionized water of its 50-100 times of quality, acetic acid manganese solution is obtained, it is standby；
B), by the effective deionized water dipping of wall drift tube type foamed ceramics, washing, 105-115 DEG C of dry 1.5-2.5h is standby；
C), titanium dioxide, bentonite and rare-earth oxide are mixed by proportioning, deionized water, ammoniacal liquor and cmc is added and enters
Row kneading plasticizing, it is old to put 10-14h, obtain plasticity material；
D) the acetic acid manganese solution and deionized water, are added into the plasticity material, 30 ~ 60min is emulsified in high-speed emulsifying machine,
Ammonification water adjusts pH value 7-9 during emulsification, and it is 1000 ~ 6000mPaS then to add PEO regulation viscosity, and composite mortar is made；
E), the compound slurry is applied directly to the wall stream after step b) processing by the method purged using negative-pressure adsorption, malleation
On tubular type foamed ceramics pipe internal surface；
F), by step e) prepare coated catalyst at 105-115 DEG C dry 3.5-4.5h, be subsequently placed in Muffle furnace with
1.8-2.2 DEG C/Min speed, which is warming up to after 290-310 DEG C, calcines 3.5-4.5h, then is heated up with 4.8-5.2 DEG C/Min speed
1.5-2.5h is calcined after to 610-630 DEG C, finished product is obtained, coating load amount is 10-40%.
8. a kind of preparation method of wall drift tube type SCR denitration as claimed in claim 7, it is characterised in that：The wall
Drift tube type foamed ceramics pipe is cordierite foamed ceramics pipe；The alkali metal oxide content of the cordierite foamed ceramics pipe
Less than 100ppm, macroscopical pore volume is 50 ~ 80%.
9. a kind of preparation method of wall drift tube type SCR denitration as claimed in claim 7, it is characterised in that：Step c）
The addition of middle deionized water is the 20-40% of solid matter mass, and the addition of ammoniacal liquor is the 0.08- of solid matter mass
0.2wt%, the addition of carboxymethyl cellulose is the 0.1-0.5wt% of solid matter mass, and the ammoniacal liquor initial concentration is
15wt%。
10. a kind of preparation method of wall drift tube type SCR denitration as claimed in claim 7, it is characterised in that：Step d)
The composite mortar in slurry solid content be 20-50wt%, size distribution be 1 ~ 20um.
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| CN112058078A (en) * | 2020-07-27 | 2020-12-11 | 北京方信立华科技有限公司 | Ceramic tube with denitration and dust removal functions and preparation method thereof |
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