CN108218454A - A kind of low temperature rare earth composite honeycomb ceramic body for having both denitration heat accumulation function - Google Patents

A kind of low temperature rare earth composite honeycomb ceramic body for having both denitration heat accumulation function Download PDF

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CN108218454A
CN108218454A CN201711483086.8A CN201711483086A CN108218454A CN 108218454 A CN108218454 A CN 108218454A CN 201711483086 A CN201711483086 A CN 201711483086A CN 108218454 A CN108218454 A CN 108218454A
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parts
pug
drying
temperature
low temperature
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李军营
周守洪
杨晓波
徐志鹏
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Hubei Shenwu Thermal Energy Technology Co Ltd
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Hubei Shenwu Thermal Energy Technology Co Ltd
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Abstract

The invention discloses a kind of low temperature rare earth composite honeycomb ceramic bodies for having both denitration heat accumulation function, belong to catalysis technical field；The denitrating catalyst is mainly by following components：TiC35~40 part, 25~35 parts of plate diamond spar aggregate, 5~10 parts of tungstic acid, SiO25~8 parts, 8~12 parts of chrome oxide green micro mist, 2~3 parts of glass fibre, 2~4 parts of silicon nitride, 3~6 parts of haloflex, methyl methacrylate -3~5 parts of butadiene-styrene copolymer, 10~12 parts of hydroxypropyl methyl cellulose, 2~3 parts of phthalic acid ester, 2~3 parts of monoethanolamine, 1~3 part of stearic acid mediate by pug, aging, extrusion molding, drying and calcining, impregnation catalyst slurry, drying is prepared with calcination process again.

Description

A kind of low temperature rare earth composite honeycomb ceramic body for having both denitration heat accumulation function
Technical field
The present invention relates to a kind of low temperature rare earth composite honeycomb ceramic body for having both denitration heat accumulation function, the present invention is prepared de- Denox catalyst has good mechanical strength, antiacid corrosive power, thermal shock resistance, is adaptable to coal-burning boiler, fired power generating unit Air preheater in, the original paper that exchanges heat in air preheater to be replaced to examine and step on steel, have both good heat exchange property, denitration activity and wider temperature Spend window.
Background technology
In recent years, the energy and associated environment become the hot spot that whole world various countries are paid close attention to the most.China is due to per capita Energy resources shortage, environmental carrying capacity is limited, ecology fragility, by the great sustainable development for restricting China.Domestic GDP is annual High speed development, the hurried increase of energy consumption, environment, ecology are worsening.It is energy-saving to become the big master for solving energy problem Offense to.According to statistics, domestic industrial department energy-output ratio accounts for the 70% of national energy total amount.Wherein Industrial Stoves are China Big power consumer accounts for about the 25% of national total energy consumption, and low energy utilization rate is that industrial furnace is caused to consume energy one of the main reason for big.
Compared with the industrial furnace of developed country, the domestic Industrial Stoves thermal efficiency that is averaged wants low 20% or so, the energy of waste Source is equivalent to 200,000,000 tons of standard coals, it is seen that Industrial Stoves energy-saving potential is very huge.
The original paper material that exchanges heat used in the air preheater in Industrial Stoves at present steps on steel to examine, and examines and steps on steel with machinery The advantages that intensity is high, cracky, heat exchange rate be not fast, thermal capacitance is big, but in use, examine step on steel surface enamel it is easily de- It falls, the sulfuric acid corrosion formed by ammonium hydrogen sulfate or moisture condensation is very easy to after the naked leakage of steel, especially national coal-burning power plant is complete Implement after minimum discharge in face.For the nitrous oxides concentration after denitration process is made to reach minimum discharge standard, at present, the drop of mainstream Low NOx drainage method is to increase by one layer of catalyst, system resistance, air preheater resistance can be caused to improve in this way, SO2To SO3 Conversion ratio rise, aerosol discharge increase, cause the escaping of ammonia increase, corrosion and clogging increase etc..
In use, heat exchange element slowly rotates air preheater, and the higher flue gas of temperature and cold air alternately flow Through heat exchange element, periodically exchanged heat.In a heat-exchange periodic, the Temperature cycling variation of heat exchange element is selected dilute Earth elements Ce, La have wider denitration activity temperature range as active component.
Traditional vanadium titanium system denitrating catalyst, active temperature windows are relatively narrow（320~400 DEG C）, easily by SO in operational process2 Poisoning, activity is relatively low under low temperature, and is also easy to produce sulphur ammonium, and blocking catalyst hole and air preheater and upstream device cause system pressure drop It is larger, increase the unfavorable factors such as the electric cost of air-introduced machine.
And existing rare-earth-based catalyst does not have heat accumulation function, and wears no resistance, and active temperature low value is high, intensity Low, service life is short；So that application range is greatly limited to, therefore, we there is an urgent need to study a kind of new catalyst, with Substitute the said goods.
Invention content
The present invention provides a kind of low temperature rare earth composite honeycomb ceramic body for having both denitration heat accumulation function, to solve above-mentioned technology Problem.
In order to solve the above technical problems, the present invention program the technical solution adopted is that：A kind of denitration heat accumulation function of having both Low temperature rare earth composite honeycomb ceramic body, it is characterised in that the denitrating catalyst is mainly by following components：TiC35~40 part, plate 25~35 parts of corundum aggregate, 5~10 parts of tungstic acid, SiO25~8 parts, 8~12 parts of chrome oxide green micro mist, glass fibre 2~3 Part, 2~4 parts of silicon nitride, 3~6 parts of haloflex, methyl methacrylate-butadiene-styrene copolymer 3~5 Part, 10~12 parts of hydroxypropyl methyl cellulose, 2~3 parts of monoethanolamine, 1~3 part of stearic acid are mediated by pug, aging, are squeezed out It is molded, dry and calcining, impregnation catalyst slurry, drying is prepared with calcination process again.
The catalysis slurry is composed of the following components：12~15 parts of ferric nitrate, 12~15 parts of manganese nitrate, niobium pentaoxide 8 ~12 parts, methyl methacrylate -5~10 parts of butadiene-styrene copolymer, dimethyl silicone polymer 0.5~2 Part, 6~10 parts of carbon fiber；3~5 parts of alumina powder, 3~6 parts of silica flour, 3~4 parts of zinc oxide, 5~8 parts of cerous nitrate, lanthanum nitrate 5~6 parts, 3 parts of titanate coupling agent.
A kind of low temperature rare earth composite honeycomb ceramic body for having both denitration heat accumulation function, preparation method include the following steps：
（1）Pug is mediated：
i）Weigh TiC, plate diamond spar aggregate, tungstic acid, SiO2, chrome oxide green micro mist, stearic acid, monoethanolamine, methyl-prop E pioic acid methyl ester-butadiene-styrene copolymer powder mixing, adds in deionized water and 20% ammonium hydroxide, wherein deionization Water：Powder weight ratio is 1：（0.4~0.6）, 20min or so is mediated in stirring, by deionized water, the ammonia of mediating and adjust addition Water adjusts pug index, and pug is mediated（i）Pug moisture target value 38~45%, pH desired values 7.8~9.4；
ii）It adds 0.5~1.5 part of 20% ammonium hydroxide, cover stirring machine cap, be heated to 95 DEG C or more while stirring, then beat Head cover is opened, pug moisture to pug is concentrated by evaporation and is in granular form, the pug moisture target value 25~28%, pH desired values 7.8~ 8.5；
iii）Add glass fibre successively while stirring, silicon nitride adds 20% ammonium hydroxide, stirring 15min or so, the pug water Subhead scale value 29~34%, pH desired values 8.1~9.2；
iv）Haloflex, hydroxypropyl methyl cellulose are added successively, stir more than 10min, the pug moisture target value 28 ~32%, pH desired value 8.1~9.0；
（2）It is aging：The pug that will be kneaded, is sealed with preservative film, aging, aging 3-4h；
（3）Pre-filtering squeezes out：By aging good pug, on pre-filtering extruder, extrusion force 1700~2200N of plasticity is filtered It is extruded into mud item；
（4）Molding squeezes out：Extrusion molding is carried out on vacuum-extruder of the front end equipped with SCR molding dies, it is wet to obtain catalyst Base；
（5）Drying-calcining：By step（4）The obtained wet base of catalyst, is transferred on aluminium alloy pallet, with the glass with heat-preservation cotton The box cover of glass steel material packages, drying temperature be 90 DEG C, arid cycle 5h；Dried catalyst blank is sent into calcining furnace It is calcined, 1380 DEG C of calcination temperature, in calcination process, control temperature is incremented by by 100 DEG C/h of gradients, forged from 100 DEG C The burning time is 18~22h, obtains ceramic honey comb green body, with 30% nitric acid cleaning ceramic green body of volumetric concentration, is dried for standby；
（6）Starching：It is common to weigh ferric nitrate, manganese nitrate, niobium pentaoxide, methyl methacrylate-butadiene-polystyrene ternary Polymers, dimethyl silicone polymer, carbon fiber, alumina powder, silica flour, zinc oxide, cerous nitrate, lanthanum nitrate, titanate coupling agent, The aqueous solution containing 1.2~3.5 parts of oxalic acid is dissolved at 70~95 DEG C, slurries are than 1:3, add and be warming up to 80 DEG C and keep the temperature, with ultrasound Wave concussion stirring 1~2 hour, is made catalysis slurry；Step 5 gained ceramic honey comb green body is put into catalysis slurry pool, is wrapped Drying oven is put into after catalysis slurry, drying temperature is 70 DEG C, 20~30 minutes arid cycles, is struck off on the outside of ceramic honey comb green body Catalysis slurry and after cleaning out, is reentered into drying oven, and drying temperature is 90 DEG C, arid cycle 1h；
（7）Drying-calcining：By step（6）Obtained ceramic honey comb green body is sent into calcining furnace and is calcined, calcination temperature 550 DEG C, in calcination process, control temperature is incremented by from 100 DEG C by 100 DEG C/h of gradients, and calcination time is 7~9h, obtains low temperature Honeycomb ceramic body.
Preferably, the step（3）Pre-filtering squeezes out, and strainer uses mesh specification as 1.0x4mm's or 0.8x3mm Stainless steel filtering net.
Preferably, the step（4）Molding squeezes out, and extruder control condition is extrusion pressure 7MPa, extrusion temperature ＜ 35 DEG C, vacuum degree -0.094MPa or so.
The invention has the advantages that：Denitration rate of the present invention in the environment of low temperature is high, and reaction condition is mild, to ring Border is without any pollution.The present invention first passes through 1380 DEG C of high-temperature firing ceramic honey comb idiosomes, then by ceramic honey comb green body starching, finally It is fired by 500~600 DEG C.The present invention improves the anti-caking power of catalyst, is conducive to improve catalyst thermal stability；It can Be adapted to coal-burning boiler, fired power generating unit air preheater in；Plate diamond spar aggregate can obviously reduce the cost of catalyst, meanwhile, by It is axial heat conduction in integral catalyzer, using the heat accumulation function of plate diamond spar aggregate honeycomb ceramic carrier, improves catalyst The uniformity of temperature improves catalytic performance.
Specific embodiment
For the ease of understanding the present invention, the present invention is described more fully in embodiment below.But the present invention can To realize in different forms, however it is not limited to embodiment described herein.Opposite, the purpose for providing these embodiments is Make to the disclosure more thorough and comprehensive.
Embodiment 1
A kind of low temperature rare earth composite honeycomb ceramic body for having both denitration heat accumulation function is mainly by following components：TiC35 parts, plate it is firm Beautiful 25 parts of aggregate, 5 parts of tungstic acid, SiO28 parts, 8 parts of chrome oxide green micro mist, 2 parts of glass fibre, 4 parts of silicon nitride, chlorinated polyethylene 3 parts of alkene, methyl methacrylate -5 parts of butadiene-styrene copolymer, 10 parts of hydroxypropyl methyl cellulose, monoethanol 2 parts of amine, 3 parts of stearic acid are mediated by pugs, aging, extrusion molding, drying and calcining, impregnation catalyst slurry, again it is dry with Calcination process is prepared.
The catalysis slurry is made of following components：12 parts of ferric nitrate, 15 parts of manganese nitrate, 8 parts of niobium pentaoxide, methyl-prop E pioic acid methyl ester -5 parts of butadiene-styrene copolymer, 2 parts of dimethyl silicone polymer, 10 parts of carbon fiber, alumina powder 5 parts, 3 parts of silica flour, 3 parts of zinc oxide, 5 parts of cerous nitrate, 5 parts of lanthanum nitrate, 5 parts of titanate coupling agent.
Preparation method includes the following steps：
（1）Pug is mediated：
i）Weigh TiC, plate diamond spar aggregate, tungstic acid, SiO2, chrome oxide green micro mist, stearic acid, monoethanolamine, methyl-prop E pioic acid methyl ester-butadiene-styrene copolymer powder mixing, adds in deionized water and 20% ammonium hydroxide, wherein deionization Water：Powder weight ratio is 1：（0.4~0.6）, 20min or so is mediated in stirring, by deionized water, the ammonia of mediating and adjust addition Water adjusts pug index, and pug is mediated（i）Pug moisture target value 38~45%, pH desired values 7.8~9.4；
ii）It adds 0.5 part of 20% ammonium hydroxide, cover stirring machine cap, be heated to 95 DEG C or more while stirring, then open top Lid is concentrated by evaporation pug moisture to pug and is in granular form, the pug moisture target value 25~28%, pH desired values 7.8~8.5；
iii）Add glass fibre successively while stirring, silicon nitride adds 20% ammonium hydroxide, stirring 15min or so, the pug water Subhead scale value 29~34%, pH desired values 8.1~9.2；
iv）Haloflex, hydroxypropyl methyl cellulose are added successively, stir more than 10min, the pug moisture target value 28 ~32%, pH desired value 8.1~9.0；
（2）It is aging：The pug that will be kneaded, is sealed with preservative film, aging, aging 4h；
（3）Pre-filtering squeezes out：By aging good pug, on pre-filtering extruder, extrusion force 1700~2200N of plasticity, strainer Stainless steel filtering net of the mesh specification for 1.0x4mm or 0.8x3mm is used, filtering is extruded into mud item；
（4）Molding squeezes out：Extrusion molding, extruder control strip are carried out on vacuum-extruder of the front end equipped with SCR molding dies Part is extrusion pressure 7MPa, and 35 DEG C, vacuum degree -0.094MPa or so of extrusion temperature ＜ obtains the wet base of catalyst；
（5）Drying-calcining：By step（4）The obtained wet base of catalyst, is transferred on aluminium alloy pallet, with the glass with heat-preservation cotton The box cover of glass steel material packages, drying temperature be 90 DEG C, arid cycle 5h；Dried catalyst blank is sent into calcining furnace It is calcined, 1380 DEG C of calcination temperature, in calcination process, control temperature is incremented by by 100 DEG C/h of gradients, forged from 100 DEG C The burning time is 18h, obtains ceramic honey comb green body, with 30% nitric acid cleaning ceramic green body of volumetric concentration, is dried for standby；
（6）Starching：It is common to weigh ferric nitrate, manganese nitrate, niobium pentaoxide, methyl methacrylate-butadiene-polystyrene ternary Polymers, dimethyl silicone polymer, carbon fiber, alumina powder, silica flour, zinc oxide, cerous nitrate, lanthanum nitrate, titanate coupling agent, The aqueous solution containing 1.2 parts of oxalic acid is dissolved at 70 DEG C, slurries are than 1:3, add and be warming up to 80 DEG C and keep the temperature, stirred with ultrasonic oscillation 1 hour, catalysis slurry is made；Step 5 gained ceramic honey comb green body is put into catalysis slurry pool, is put into after wrapping catalysis slurry Drying oven, drying temperature are 70 DEG C, strike off the catalysis slurry on the outside of ceramic honey comb green body and clear up 20~30 minutes arid cycles After clean, be reentered into drying oven, drying temperature is 90 DEG C, arid cycle 1h；
（7）Drying-calcining：By step（6）Obtained ceramic honey comb green body is sent into calcining furnace and is calcined, calcination temperature 550 DEG C, in calcination process, control temperature is incremented by, calcination time 9h obtains low temperature bee from 100 DEG C by 100 DEG C/h of gradients Nest ceramic body.Products obtained therefrom geometric dimension is 150x150x（500~1250）Mm, aperture be 5~8mm, interior wall thickness 0.7~ 1.2mm, geometry specific surface area are 360~700m2/m3。
Embodiment 2
A kind of low temperature rare earth composite honeycomb ceramic body for having both denitration heat accumulation function is mainly by following components：TiC38 parts, plate it is firm Beautiful 30 parts of aggregate, 7 parts of tungstic acid, SiO26 parts, 10 parts of chrome oxide green micro mist, 3 parts of glass fibre, 3 parts of silicon nitride, chlorination gather 5 parts of ethylene, methyl methacrylate -4 parts of butadiene-styrene copolymer, 11 parts of hydroxypropyl methyl cellulose, Dan Yi 3 parts of hydramine, 2 parts of stearic acid are mediated by pug, and aging, extrusion molding, drying and calcining, are dried impregnation catalyst slurry again It is prepared with calcination process.
The catalysis slurry consists of the following compositions：14 parts of ferric nitrate, 14 parts of manganese nitrate, 10 parts of niobium pentaoxide, methyl Methyl acrylate -8 parts of butadiene-styrene copolymer, 1.3 parts of dimethyl silicone polymer, 7 parts of carbon fiber, aluminium oxide 4 parts of micro mist, 5 parts of silica flour, 4 parts of zinc oxide, 6 parts of cerous nitrate, 5 parts of lanthanum nitrate, 5 parts of titanate coupling agent.
Preparation method includes the following steps：
（1）Pug is mediated：
i）Weigh TiC, plate diamond spar aggregate, tungstic acid, SiO2, chrome oxide green micro mist, stearic acid, monoethanolamine, methyl-prop E pioic acid methyl ester-butadiene-styrene copolymer powder mixing, adds in deionized water and 20% ammonium hydroxide, wherein deionization Water：Powder weight ratio is 1：（0.4~0.6）, 20min or so is mediated in stirring, by deionized water, the ammonia of mediating and adjust addition Water adjusts pug index, and pug is mediated（i）Pug moisture target value 38~45%, pH desired values 7.8~9.4；
ii）It adds 1 part of 20% ammonium hydroxide, cover stirring machine cap, be heated to 95 DEG C or more while stirring, then open head cover, It is concentrated by evaporation pug moisture to pug to be in granular form, the pug moisture target value 25~28%, pH desired values 7.8~8.5；
iii）Add glass fibre, silicon nitride, 20% ammonium hydroxide of addition, stirring 15min or so, the pug water successively while stirring Subhead scale value 29~34%, pH desired values 8.1~9.2；
iv）Haloflex, hydroxypropyl methyl cellulose, stirring more than 10min, the pug moisture target value 28 are added successively ~32%, pH desired value 8.1~9.0；
（2）It is aging：The pug that will be kneaded, is sealed with preservative film, aging, aging 3h；
（3）Pre-filtering squeezes out：By aging good pug, on pre-filtering extruder, extrusion force 1700~2200N of plasticity, strainer Stainless steel filtering net of the mesh specification for 1.0x4mm or 0.8x3mm is used, filtering is extruded into mud item；
（4）Molding squeezes out：Extrusion molding, extruder control strip are carried out on vacuum-extruder of the front end equipped with SCR molding dies Part is extrusion pressure 7MPa, and 35 DEG C, vacuum degree -0.094MPa or so of extrusion temperature ＜ obtains the wet base of catalyst；
（5）Drying-calcining：By step（4）The obtained wet base of catalyst, is transferred on aluminium alloy pallet, with the glass with heat-preservation cotton The box cover of glass steel material packages, drying temperature be 90 DEG C, arid cycle 5h；Dried catalyst blank is sent into calcining furnace It is calcined, 1380 DEG C of calcination temperature, in calcination process, control temperature is incremented by by 100 DEG C/h of gradients, forged from 100 DEG C The burning time is 21h, obtains ceramic honey comb green body, with 30% nitric acid cleaning ceramic green body of volumetric concentration, is dried for standby；
（6）Starching：It is common to weigh ferric nitrate, manganese nitrate, niobium pentaoxide, methyl methacrylate-butadiene-polystyrene ternary Polymers, dimethyl silicone polymer, carbon fiber, alumina powder, silica flour, zinc oxide, cerous nitrate, lanthanum nitrate, titanate coupling agent, The aqueous solution containing 2.2 parts of oxalic acid is dissolved at 85 DEG C, slurries are than 1:3, add and be warming up to 80 DEG C and keep the temperature, stirred with ultrasonic oscillation 1.5 hours, catalysis slurry is made；Step 5 gained ceramic honey comb green body is put into catalysis slurry pool, is put after wrapping catalysis slurry Enter drying oven, drying temperature is 70 DEG C, 20~30 minutes arid cycles, strikes off catalysis slurry on the outside of ceramic honey comb green body and clear After reason is clean, be reentered into drying oven, drying temperature is 90 DEG C, arid cycle 1h；
（7）Drying-calcining：By step（6）Obtained ceramic honey comb green body is sent into calcining furnace and is calcined, calcination temperature 550 DEG C, in calcination process, control temperature is incremented by, calcination time 8h obtains low temperature bee from 100 DEG C by 100 DEG C/h of gradients Nest ceramic body.Products obtained therefrom geometric dimension is 150x150x（500~1250）Mm, aperture be 5~8mm, interior wall thickness 0.7~ 1.2mm, geometry specific surface area are 360~700m2/m3。
Embodiment 3
A kind of low temperature rare earth composite honeycomb ceramic body for having both denitration heat accumulation function is mainly by following components：TiC40 parts, plate it is firm Beautiful 35 parts of aggregate, 10 parts of tungstic acid, SiO25 parts, 12 parts of chrome oxide green micro mist, 3 parts of glass fibre, 2 parts of silicon nitride, chlorination gather 6 parts of ethylene, methyl methacrylate -3 parts of butadiene-styrene copolymer, 12 parts of hydroxypropyl methyl cellulose, Dan Yi 2 parts of hydramine, 1 part of stearic acid are mediated by pug, and aging, extrusion molding, drying and calcining, are dried impregnation catalyst slurry again It is prepared with calcination process.
The catalysis slurry consists of the following compositions：15 parts of ferric nitrate, 15 parts of manganese nitrate, 12 parts of niobium pentaoxide, methyl Methyl acrylate -10 parts of butadiene-styrene copolymer, 0.5 part of dimethyl silicone polymer, 6 parts of carbon fiber, aluminium oxide 3 parts of micro mist, 6 parts of silica flour, 3 parts of zinc oxide, 8 parts of cerous nitrate, 6 parts of lanthanum nitrate, 5 parts of titanate coupling agent.
（1）Pug is mediated：
i）Weigh TiC4, plate diamond spar aggregate, tungstic acid 1, SiO2, chrome oxide green micro mist 1, stearic acid, monoethanolamine, methyl Methyl acrylate-butadiene-styrene copolymer powder mixing, adds in deionized water and 20% ammonium hydroxide, wherein deionization Water：Powder weight ratio is 1：（0.4~0.6）, 20min or so is mediated in stirring, by deionized water, the ammonia of mediating and adjust addition Water adjusts pug index, and pug is mediated（i）Pug moisture target value 38~45%, pH desired values 7.8~9.4；
ii）It adds 1.5 parts of 20% ammonium hydroxide, cover stirring machine cap, be heated to 95 DEG C or more while stirring, then open top Lid is concentrated by evaporation pug moisture to pug and is in granular form, the pug moisture target value 25~28%, pH desired values 7.8~8.5；
iii）Add glass fibre, silicon nitride, 20% ammonium hydroxide of addition, stirring 15min or so, the pug water successively while stirring Subhead scale value 29~34%, pH desired values 8.1~9.2；
iv）Haloflex, hydroxypropyl methyl cellulose, stirring more than 10min, the pug moisture target value 28 are added successively ~32%, pH desired value 8.1~9.0；
（2）It is aging：The pug that will be kneaded, is sealed with preservative film, aging, aging 3h；
（3）Pre-filtering squeezes out：By aging good pug, on pre-filtering extruder, extrusion force 1700~2200N of plasticity, strainer Stainless steel filtering net of the mesh specification for 1.0x4mm or 0.8x3mm is used, filtering is extruded into mud item；
（4）Molding squeezes out：Extrusion molding, extruder control strip are carried out on vacuum-extruder of the front end equipped with SCR molding dies Part is extrusion pressure 7MPa, and 35 DEG C, vacuum degree -0.094MPa or so of extrusion temperature ＜ obtains the wet base of catalyst；
（5）Drying-calcining：By step（4）The obtained wet base of catalyst, is transferred on aluminium alloy pallet, with the glass with heat-preservation cotton The box cover of glass steel material packages, drying temperature be 90 DEG C, arid cycle 5h；Dried catalyst blank is sent into calcining furnace It is calcined, 1380 DEG C of calcination temperature, in calcination process, control temperature is incremented by by 100 DEG C/h of gradients, forged from 100 DEG C The burning time is 22h, obtains ceramic honey comb green body, with 30% nitric acid cleaning ceramic green body of volumetric concentration, is dried for standby；
（6）Starching：It is common to weigh ferric nitrate, manganese nitrate, niobium pentaoxide, methyl methacrylate-butadiene-polystyrene ternary Polymers, dimethyl silicone polymer, carbon fiber, alumina powder, silica flour, zinc oxide, cerous nitrate, lanthanum nitrate, titanate coupling agent, The aqueous solution containing 1.2~3.5 parts of oxalic acid is dissolved at 95 DEG C, slurries are than 1:3, add and be warming up to 80 DEG C and keep the temperature, shaken with ultrasonic wave Stirring 2 hours is swung, catalysis slurry is made；Step 5 gained ceramic honey comb green body is put into catalysis slurry pool, wraps catalysis slurry After be put into drying oven, drying temperature is 70 DEG C, strikes off the catalysis slurry on the outside of ceramic honey comb green body 20~30 minutes arid cycles And after cleaning out, be reentered into drying oven, drying temperature is 90 DEG C, arid cycle 1h；
（7）Drying-calcining：By step（6）Obtained ceramic honey comb green body is sent into calcining furnace and is calcined, calcination temperature 550 DEG C, in calcination process, control temperature is incremented by, calcination time 7h obtains low temperature bee from 100 DEG C by 100 DEG C/h of gradients Nest ceramic body.Products obtained therefrom geometric dimension is 150x150x（500~1250）Mm, aperture be 5~8mm, interior wall thickness 0.7~ 1.2mm, geometry specific surface area are 360~700m2/m3。
1-3 of embodiment of the present invention products obtained therefroms and other Products commercially are compared, obtain with Lower Testing index：
After tested, the compression strength of catalyst of the present invention is axially 70~76MPa, wear-resistant 3.8~4.0cm3, catalyst Service life had higher intensity and thermal conductivity factor, therefore with extensive society and economic value in 7 ~ 8 years.
Embodiment of the present invention is only the description carried out to the preferred embodiment of the present invention, not to the present invention Conception and scope is defined, and under the premise of not departing from the present invention relates to thought, engineers and technicians are to this hair in this field The various modifications and improvement that bright technical solution is made, should all fall into protection scope of the present invention.

Claims (4)

1. a kind of low temperature rare earth composite honeycomb ceramic body for having both denitration heat accumulation function, it is characterised in that the denitrating catalyst is main By following components：The denitrating catalyst is mainly by following components：TiC35~40 part, 25~35 parts of plate diamond spar aggregate, three oxidations 5~10 parts of tungsten, SiO25~8 parts, 8~12 parts of chrome oxide green micro mist, 2~3 parts of glass fibre, 2~4 parts of silicon nitride, chlorinated polyethylene 3~6 parts of alkene, methyl methacrylate -3~5 parts of butadiene-styrene copolymer, hydroxypropyl methyl cellulose 10~ 12 parts, 2~3 parts of monoethanolamine, 1~3 part of stearic acid mediated by pug, aging, extrusion molding, drying and calcining, dipping are urged Slurrying material, drying is prepared with calcination process again；
The catalysis slurry is composed of the following components：12~15 parts of ferric nitrate, 12~15 parts of manganese nitrate, niobium pentaoxide 8~12 Part, methyl methacrylate -5~10 parts of butadiene-styrene copolymer, 0.5~2 part of dimethyl silicone polymer, carbon 6~10 parts of fiber；3~5 parts of alumina powder, 3~6 parts of silica flour, 3~4 parts of zinc oxide, 5~8 parts of cerous nitrate, lanthanum nitrate 5~6 Part, 4~5 parts of titanate coupling agent.
2. a kind of low temperature rare earth composite honeycomb ceramic body for having both denitration heat accumulation function according to claim 1, feature It is that preparation method includes the following steps：
（1）Pug is mediated：
i）Weigh TiC, plate diamond spar aggregate, tungstic acid, SiO2, chrome oxide green micro mist, stearic acid, monoethanolamine, metering system Sour methyl esters-butadiene-styrene copolymer powder mixing, adds in deionized water and 20% ammonium hydroxide, wherein deionized water： Powder weight ratio is 1：（0.4~0.6）, 20min or so is mediated in stirring, by deionized water, the ammonium hydroxide of mediating and adjust addition Pug index is adjusted, pug is mediated（i）Pug moisture target value 38~45%, pH desired values 7.8~9.4；
ii）It adds 0.5~1.5 part of 20% ammonium hydroxide, cover stirring machine cap, be heated to 95 DEG C or more while stirring, then beat Head cover is opened, pug moisture to pug is concentrated by evaporation and is in granular form, the pug moisture target value 25~28%, pH desired values 7.8~ 8.5；
iii）Add glass fibre successively while stirring, silicon nitride adds 20% ammonium hydroxide, stirring 15min or so, the pug water Subhead scale value 29~34%, pH desired values 8.1~9.2；
iv）Haloflex, hydroxypropyl methyl cellulose are added successively, stir more than 10min, the pug moisture target value 28 ~32%, pH desired value 8.1~9.0；
（2）It is aging：The pug that will be kneaded, is sealed with preservative film, aging, aging 3-4h；
（3）Pre-filtering squeezes out：By aging good pug, on pre-filtering extruder, extrusion force 1700~2200N of plasticity is filtered It is extruded into mud item；
（4）Molding squeezes out：Extrusion molding is carried out on vacuum-extruder of the front end equipped with SCR molding dies, it is wet to obtain catalyst Base；
（5）Drying-calcining：By step（4）The obtained wet base of catalyst, is transferred on aluminium alloy pallet, with the glass with heat-preservation cotton The box cover of glass steel material packages, drying temperature be 90 DEG C, arid cycle 5h；Dried catalyst blank is sent into calcining furnace It is calcined, 1380 DEG C of calcination temperature, in calcination process, control temperature is incremented by by 100 DEG C/h of gradients, forged from 100 DEG C The burning time is 18~22h, obtains ceramic honey comb green body, with 30% nitric acid cleaning ceramic green body of volumetric concentration, is dried for standby；
（6）Starching：It is common to weigh ferric nitrate, manganese nitrate, niobium pentaoxide, methyl methacrylate-butadiene-polystyrene ternary Polymers, dimethyl silicone polymer, carbon fiber, alumina powder, silica flour, zinc oxide, cerous nitrate, lanthanum nitrate, titanate coupling agent, The aqueous solution containing 1.2~3.5 parts of oxalic acid is dissolved at 70~95 DEG C, slurries are than 1:3, add and be warming up to 80 DEG C and keep the temperature, with ultrasound Wave concussion stirring 1~2 hour, is made catalysis slurry；Step 5 gained ceramic honey comb green body is put into catalysis slurry pool, is wrapped Drying oven is put into after catalysis slurry, drying temperature is 70 DEG C, 20~30 minutes arid cycles, is struck off on the outside of ceramic honey comb green body Catalysis slurry and after cleaning out, is reentered into drying oven, and drying temperature is 90 DEG C, arid cycle 1h；
（7）Drying-calcining：By step（6）Obtained ceramic honey comb green body is sent into calcining furnace and is calcined, calcination temperature 550 DEG C, in calcination process, control temperature is incremented by from 100 DEG C by 100 DEG C/h of gradients, and calcination time is 7~9h, obtains low temperature Honeycomb ceramic body.
3. a kind of low temperature rare earth composite honeycomb ceramic body for having both denitration heat accumulation function according to claim 2, feature It is：Step（3）Pre-filtering squeezes out, and strainer uses stainless steel filtering net of the mesh specification for 1.0x4mm or 0.8x3mm.
4. a kind of low temperature rare earth composite honeycomb ceramic body for having both denitration heat accumulation function according to claim 2, feature It is：Step（4）Molding squeezes out, and extruder control condition is extrusion pressure 7MPa, 35 DEG C of extrusion temperature ＜, and vacuum degree- 0.094MPa or so.
CN201711483086.8A 2017-12-29 2017-12-29 A kind of low temperature rare earth composite honeycomb ceramic body for having both denitration heat accumulation function Withdrawn CN108218454A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110022622A (en) * 2019-05-16 2019-07-16 厦门蜂涛陶瓷有限公司 A kind of cellular alumina ceramic heating element and preparation method thereof
CN112121816A (en) * 2020-10-23 2020-12-25 湖北群有长物环保科技有限公司 Low-temperature catalyst special for waste incineration
CN112958127A (en) * 2021-02-26 2021-06-15 上海大学材料基因组工程(萍乡)研究院 Method for loading catalyst on ceramic fiber
CN113045334A (en) * 2021-04-14 2021-06-29 乌鲁木齐胜达天利建材科技有限公司 Preparation method of fly ash and slag foamed ceramic

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110022622A (en) * 2019-05-16 2019-07-16 厦门蜂涛陶瓷有限公司 A kind of cellular alumina ceramic heating element and preparation method thereof
CN112121816A (en) * 2020-10-23 2020-12-25 湖北群有长物环保科技有限公司 Low-temperature catalyst special for waste incineration
CN112958127A (en) * 2021-02-26 2021-06-15 上海大学材料基因组工程(萍乡)研究院 Method for loading catalyst on ceramic fiber
CN113045334A (en) * 2021-04-14 2021-06-29 乌鲁木齐胜达天利建材科技有限公司 Preparation method of fly ash and slag foamed ceramic

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