CN108191444A - A kind of medium temperature denitration, accumulation of heat integration rare earth composite ceramic material - Google Patents

A kind of medium temperature denitration, accumulation of heat integration rare earth composite ceramic material Download PDF

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Publication number
CN108191444A
CN108191444A CN201711492590.4A CN201711492590A CN108191444A CN 108191444 A CN108191444 A CN 108191444A CN 201711492590 A CN201711492590 A CN 201711492590A CN 108191444 A CN108191444 A CN 108191444A
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parts
pug
temperature
nitrate
drying
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CN201711492590.4A
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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 medium temperature denitration, accumulation of heat integration rare earth composite ceramic materials, belong to catalysis technical field；The denitrating catalyst is mainly by following components：Zirconium oxide fibre, anorthite, boron nitride, barium carbonate, montmorillonite, carbon fiber, titanium dioxide, haloflex part, methyl methacrylate-butadiene-styrene copolymer, cyanethyl cellulose, phthalic acid ester, monoethanolamine, stearic acid are mediated by pug, aging, extrusion molding, drying and calcining, impregnation catalyst slurry, drying is prepared with calcination process again.It the composite can be widely applied in the air preheater of coal-burning boiler, fired power generating unit etc., the energy can be saved, improve efficiency of energy utilization, reduce disposal of pollutants, actually a new technology benefited the nation and the people.

Description

A kind of medium temperature denitration, accumulation of heat integration rare earth composite ceramic material
Technical field
The present invention relates to a kind of composite ceramic material more particularly to a kind of medium temperature denitration, accumulation of heat integration rare earth composite ceramics Ceramic material.
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 range is narrow, 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 medium temperature denitration, accumulation of heat integration rare earth composite ceramic material, to solve above-mentioned technical problem.
In order to solve the above technical problems, the present invention program the technical solution adopted is that：A kind of medium temperature denitration, accumulation of heat integration Rare earth composite ceramic material, it is characterised in that the denitrating catalyst is mainly by following components：25~30 parts of Zirconium oxide fibre, calcium are long 70~80 parts of stone, 5~10 parts of boron nitride, 5~8 parts of barium carbonate, 10~15 parts of montmorillonite, 2~3 parts of carbon fiber, titanium dioxide 4~ 5 parts, 3~6 parts of haloflex, methyl methacrylate -3~5 parts of butadiene-styrene copolymer, cyanoethyl it is fine 3~6 parts of dimension element, 2~3 parts of phthalic acid ester, 2~3 parts of monoethanolamine, 1~3 part of stearic acid are mediated by pug, aging, are squeezed Go out molding, drying and calcining, impregnation catalyst slurry, again drying be prepared with calcination process.
The catalysis slurry is mainly composed of the following components：5~8 parts of aluminium oxide, 5~10 parts of ferric nitrate, manganese nitrate 5~15 Part, 5~10 parts of anorthite, 5~10 parts of ammonium dihydrogen phosphate, 0.5~2 part of dimethyl silicone polymer, 6~10 parts of carbon fiber；Nitric acid 3~5 parts of yttrium, 5~8 parts of ammonium metatungstate, 5~8 parts of cerous nitrate, 2~4 parts of lanthanum nitrate, 3 parts of titanate coupling agent.
A kind of medium temperature denitration, accumulation of heat integration rare earth composite ceramic material, preparation method include the following steps：
（1）Pug is mediated：
i）Zirconium oxide fibre, anorthite, boron nitride, barium carbonate, montmorillonite, titanium dioxide, carbon fiber, haloflex is weighed to mix It closes, adds in deionized water and 20% ammonium hydroxide, 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 20% ammonium hydroxide, cover stirring machine cap, be heated to 95 DEG C or more while stirring, then open head cover, steam Hair concentration pug moisture to pug is in granular form, the pug moisture target value 25~28%, pH desired values 7.8~8.5；
iii）Add methyl methacrylate-butadiene-styrene copolymer, cyanoethyl fiber successively while stirring Element adds 20% ammonium hydroxide, stirring 15min or so, the pug moisture target value 29~34%, pH desired values 8.1~9.2；
iv）Phthalic acid ester, monoethanolamine, stearic acid 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；By dried catalyst blank be sent into kiln into Row calcining, 1100~1200 DEG C of calcination temperature, in calcination process, control temperature is passed from 100 DEG C by 100 DEG C/h of gradients Increase, calcination time is 18~22h, obtains ceramic honey comb green body；
（6）Starching：Weigh aluminium oxide, ferric nitrate, manganese nitrate, anorthite, ammonium dihydrogen phosphate, dimethyl silicone polymer, carbon fiber, Yttrium nitrate, ammonium metatungstate, cerous nitrate, lanthanum nitrate, titanate coupling agent are dissolved at 70~95 DEG C containing 1.2~3.5 parts of oxalic acid Aqueous solution, slurries are than 1:3, add and be warming up to 80 DEG C and keep the temperature, stirred 1~2 hour with ultrasonic oscillation, catalysis slurry is made；It will Step 5 gained ceramic honey comb green body is put into catalysis slurry pool, and drying oven, drying temperature 70 are put into after wrapping catalysis slurry DEG C, after striking off the catalysis slurry on the outside of ceramic honey comb green body and cleaning out, it is reentered into drying 20~30 minutes arid cycles Stove, drying temperature be 90 DEG C, arid cycle 1h；
（7）Calcining：By step（6）Obtained ceramic honey comb green body is sent into kiln and is calcined, 550 DEG C of calcination temperature, calcining In the process, control temperature is incremented by from 100 DEG C by 100 DEG C/h of gradients, and calcination time is 7~9h, obtains medium temperature honeycomb pottery Porcelain.
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.
Preferably, the Extruded Monolithic Celluar Ceramics are column structure, Extruded Monolithic Celluar Ceramics are internally provided with multiple perforation cylinders Duct, the cross sectional shapes of the Extruded Monolithic Celluar Ceramics is polygon, semicircle, circle, arch, one kind of sector, the hole The cross sectional shape in road is one or more combinations of polygon, semicircle, circle, arch, sector, is made pottery in the duct with honeycomb The upper surface and lower face of ceramic material are compounded with resistant to corrosion layer, and the Extruded Monolithic Celluar Ceramics upper surface, lower face are respectively equipped with fixed Position groove is equipped with the positioning convex strip coordinated with positioning groove in Extruded Monolithic Celluar Ceramics upper surface or lower face.
Preferably, the positioning groove is cross, the positioning convex strip is cross.
Material property of the present invention is superior, has good mechanical strength, antiacid corrosive power, thermal shock resistance.And Denitration rate under medium temperature environment is high, and reaction condition is mild, to environment without any pollution.The present invention first passes through high-temperature firing honeycomb Ceramic idiosome, then by ceramic honey comb green body starching, finally fired by medium temperature.This technique can significantly improve catalyst Anti- caking power improves the uniformity of catalyst temperature, improves catalytic performance, is conducive to improve catalyst thermal stability, meanwhile, Due to ceramic honey comb idiosome high-temperature firing, structural strength is big, in use, honeycomb ceramic carrier can be greatly enhanced with laminated multi-layer Heat accumulation function.The design of cross positioning convex strip enables two heat storage installations more convenient, and two can be greatly decreased after installation Airflow hole inconsistent phenomenon between a honeycomb ceramics is very unimpeded along the channel of airflow direction.
Present invention storage exothermicity is good, and wear-resisting, corrosion resistance and good, thermal shock resistance is good, heat exchange efficiency is high, thus is It economizes on resources, environmentally protective novel product, can be widely applied in the air preheater of coal-burning boiler, fired power generating unit etc., Ke Yijie It saves the energy, improve efficiency of energy utilization, reduce disposal of pollutants, actually a new technology benefited the nation and the people.
Description of the drawings
Structure diagram when being perpendicular positioning of the present invention shown in Fig. 1；
Fig. 2 is the structure diagram of positioning convex strip in the present invention；
It is the structure diagram of the present invention shown in Fig. 3.
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 medium temperature denitration, accumulation of heat integration rare earth composite ceramic material are mainly by following components：25 parts of Zirconium oxide fibre, calcium are long 80 parts of stone, 5 parts of boron nitride, 8 parts of barium carbonate, 10 parts of montmorillonite, 2 parts of carbon fiber, 4 parts of titanium dioxide, 3 parts of haloflex, first Base methyl acrylate -5 parts of butadiene-styrene copolymer, 3 parts of cyanethyl cellulose, 3 parts of phthalic acid ester, list 2 parts of ethanol amine, 3 parts of stearic acid are mediated by pug, and aging, extrusion molding, drying and calcining, are done impregnation catalyst slurry again It is dry to be prepared with calcination process.
The catalysis slurry is mainly composed of the following components：5 parts of aluminium oxide, 10 parts of ferric nitrate, 15 parts of manganese nitrate, anorthite 5 parts, 5 parts of ammonium dihydrogen phosphate, 2 parts of dimethyl silicone polymer, 10 parts of carbon fiber, 5 parts of yttrium nitrate, 8 parts of ammonium metatungstate, cerous nitrate 5 Part, 4 parts of lanthanum nitrate, 3 parts of titanate coupling agent.
Preparation method includes the following steps：
（1）Pug is mediated：
i）Zirconium oxide fibre, anorthite, boron nitride, barium carbonate, montmorillonite, titanium dioxide, carbon fiber, haloflex is weighed to mix It closes, adds in deionized water and 20% ammonium hydroxide, 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 20% ammonium hydroxide, cover stirring machine cap, be heated to 95 DEG C or more while stirring, then open head cover, steam Hair concentration pug moisture to pug is in granular form, the pug moisture target value 25~28%, pH desired values 7.8~8.5；
iii）Add methyl methacrylate-butadiene-styrene copolymer, cyanoethyl fiber successively while stirring Element adds 20% ammonium hydroxide, stirring 15min or so, the pug moisture target value 29~34%, pH desired values 8.1~9.2；
iv）Phthalic acid ester, monoethanolamine, stearic acid 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；By dried catalyst blank be sent into kiln into Row calcining, 1100~1200 DEG C of calcination temperature, in calcination process, control temperature is passed from 100 DEG C by 100 DEG C/h of gradients Increase, calcination time 18h obtains ceramic honey comb green body.
（6）Starching：Weigh aluminium oxide, ferric nitrate, manganese nitrate, anorthite, ammonium dihydrogen phosphate, dimethyl silicone polymer, carbon Fiber, yttrium nitrate, ammonium metatungstate, cerous nitrate, lanthanum nitrate, titanate coupling agent are dissolved in water-soluble containing 1.2 parts of oxalic acid at 70 DEG C Liquid, slurries are than 1:3, add and be warming up to 80 DEG C and keep the temperature, stirred 1 hour with ultrasonic oscillation, catalysis slurry is made；By step 5 institute It obtains ceramic honey comb green body to be put into catalysis slurry pool, is put into drying oven after wrapping catalysis slurry, drying temperature is 70 DEG C, dry all 20 minutes phases after striking off the catalysis slurry on the outside of ceramic honey comb green body and cleaning out, were reentered into drying oven, drying temperature is 90 DEG C, arid cycle 1h；
（7）Calcining：By step（6）Obtained ceramic honey comb green body is sent into kiln and is calcined, 550 DEG C of calcination temperature, calcining In the process, control temperature is incremented by, calcination time 9h obtains medium temperature ceramic honey comb from 100 DEG C by 100 DEG C/h of gradients. Products obtained therefrom geometric dimension is 150x150x（500~1250）Mm, aperture are 5~8mm, interior 0.7~1.2mm of wall thickness.
Embodiment 2
A kind of medium temperature denitration, accumulation of heat integration rare earth composite ceramic material are mainly by following components：28 parts of Zirconium oxide fibre, calcium are long 75 parts of stone, 7 parts of boron nitride, 6 parts of barium carbonate, 14 parts of montmorillonite, 3 parts of carbon fiber, 5 parts of titanium dioxide, 5 parts of haloflex, first Base methyl acrylate -4 parts of butadiene-styrene copolymer, 5 parts of cyanethyl cellulose, 2 parts of phthalic acid ester, list 3 parts of ethanol amine, 2 parts of stearic acid are mediated by pug, and aging, extrusion molding, drying and calcining, are done impregnation catalyst slurry again It is dry to be prepared with calcination process.
The catalysis slurry is mainly composed of the following components：6 parts of aluminium oxide, 8 parts of ferric nitrate, 10 parts of manganese nitrate, anorthite 9 Part, 8 parts of ammonium dihydrogen phosphate, 1.3 parts of dimethyl silicone polymer, 7 parts of carbon fiber, 4 parts of yttrium nitrate, 7 parts of ammonium metatungstate, cerous nitrate 6 Part, 3 parts of lanthanum nitrate, 3 parts of titanate coupling agent.
Preparation method includes the following steps：
（1）Pug is mediated：
i）Zirconium oxide fibre, anorthite, boron nitride, barium carbonate, montmorillonite, titanium dioxide, carbon fiber, haloflex is weighed to mix It closes, adds in deionized water and 20% ammonium hydroxide, 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 20% ammonium hydroxide, cover stirring machine cap, be heated to 95 DEG C or more while stirring, then open head cover, steam Hair concentration pug moisture to pug is in granular form, the pug moisture target value 25~28%, pH desired values 7.8~8.5；
iii）Add methyl methacrylate-butadiene-styrene copolymer, cyanoethyl fiber successively while stirring Element adds 20% ammonium hydroxide, stirring 15min or so, the pug moisture target value 29~34%, pH desired values 8.1~9.2；
iv）Phthalic acid ester, monoethanolamine, stearic acid 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 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；By dried catalyst blank be sent into kiln into Row calcining, 1100~1200 DEG C of calcination temperature, in calcination process, control temperature is passed from 100 DEG C by 100 DEG C/h of gradients Increase, calcination time 21h obtains ceramic honey comb green body.
（6）Starching：Weigh aluminium oxide, ferric nitrate, manganese nitrate, anorthite, ammonium dihydrogen phosphate, dimethyl silicone polymer, carbon Fiber, yttrium nitrate, ammonium metatungstate, cerous nitrate, lanthanum nitrate, titanate coupling agent are dissolved in water-soluble containing 2.2 parts of oxalic acid at 85 DEG C Liquid, slurries are than 1:3, add and be warming up to 80 DEG C and keep the temperature, stirred 1.5 hours with ultrasonic oscillation, catalysis slurry is made；By step 5 Gained ceramic honey comb green body is put into catalysis slurry pool, is put into drying oven after wrapping catalysis slurry, drying temperature is 70 DEG C, dry 25 minutes periods after striking off the catalysis slurry on the outside of ceramic honey comb green body and cleaning out, were reentered into drying oven, drying temperature Be 90 DEG C, arid cycle 1h；
（7）Calcining：By step（6）Obtained ceramic honey comb green body is sent into kiln and is calcined, 550 DEG C of calcination temperature, calcining In the process, control temperature is incremented by, calcination time 8h obtains medium temperature ceramic honey comb from 100 DEG C by 100 DEG C/h of gradients. Products obtained therefrom geometric dimension is 150x150x（500~1250）Mm, aperture are 5~8mm, interior 0.7~1.2mm of wall thickness.
Embodiment 3
A kind of medium temperature denitration, accumulation of heat integration rare earth composite ceramic material are mainly by following components：30 parts of Zirconium oxide fibre, calcium are long 70 parts of stone, 10 parts of boron nitride, 5 parts of barium carbonate, 15 parts of montmorillonite, 3 parts of carbon fiber, 5 parts of titanium dioxide, 6 parts of haloflex, first Base methyl acrylate -3 parts of butadiene-styrene copolymer, 6 parts of cyanethyl cellulose, 2 parts of phthalic acid ester, list 2 parts of ethanol amine, 1 part of stearic acid are mediated by pug, and aging, extrusion molding, drying and calcining, are done impregnation catalyst slurry again It is dry to be prepared with calcination process.
The catalysis slurry is mainly composed of the following components：8 parts of aluminium oxide, 5 parts of ferric nitrate, 5 parts of manganese nitrate, anorthite 10 Part, 10 parts of ammonium dihydrogen phosphate, 0.5 part of dimethyl silicone polymer, 6 parts of carbon fiber, 3 parts of yttrium nitrate, 5 parts of ammonium metatungstate, cerous nitrate 8 Part, 2 parts of lanthanum nitrate, 3 parts of titanate coupling agent.
（1）Pug is mediated：
i）Zirconium oxide fibre, anorthite, boron nitride, barium carbonate, montmorillonite, titanium dioxide, carbon fiber, haloflex is weighed to mix It closes, adds in deionized water and 20% ammonium hydroxide, 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 20% ammonium hydroxide, cover stirring machine cap, be heated to 95 DEG C or more while stirring, then open head cover, steam Hair concentration pug moisture to pug is in granular form, the pug moisture target value 25~28%, pH desired values 7.8~8.5；
iii）Add methyl methacrylate-butadiene-styrene copolymer, cyanoethyl fiber successively while stirring Element adds 20% ammonium hydroxide, stirring 15min or so, the pug moisture target value 29~34%, pH desired values 8.1~9.2；
iv）Phthalic acid ester, monoethanolamine, stearic acid 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 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；By dried catalyst blank be sent into kiln into Row calcining, 1100~1200 DEG C of calcination temperature, in calcination process, control temperature is passed from 100 DEG C by 100 DEG C/h of gradients Increase, calcination time 22h obtains ceramic honey comb green body.
（6）Starching：Weigh aluminium oxide, ferric nitrate, manganese nitrate, anorthite, ammonium dihydrogen phosphate, dimethyl silicone polymer, carbon Fiber, yttrium nitrate, ammonium metatungstate, cerous nitrate, lanthanum nitrate, titanate coupling agent are dissolved at 95 DEG C containing 1.2~3.5 parts of oxalic acid Aqueous solution, slurries are than 1:3, add and be warming up to 80 DEG C and keep the temperature, stirred 2 hours with ultrasonic oscillation, catalysis slurry is made；It will step Rapid 5 gained ceramic honey comb green body is put into catalysis slurry pool, and drying oven is put into after wrapping catalysis slurry, and drying temperature is 70 DEG C, After striking off the catalysis slurry on the outside of ceramic honey comb green body and cleaning out, it is reentered into drying oven 30 minutes arid cycles, it is dry Temperature be 90 DEG C, arid cycle 1h；
（7）Calcining：By step（6）Obtained ceramic honey comb green body is sent into kiln and is calcined, 550 DEG C of calcination temperature, calcining In the process, control temperature is incremented by, calcination time 7h obtains medium temperature ceramic honey comb from 100 DEG C by 100 DEG C/h of gradients. Products obtained therefrom geometric dimension is 150x150x（500~1250）Mm, aperture are 5~8mm, interior 0.7~1.2mm of wall thickness.
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 45~48MPa, wear-resistant 2.7~3.0cm3, catalyst Service life had higher intensity and thermal conductivity factor, therefore with extensive society and economic value in 5 ~ 6 years.
Extruded Monolithic Celluar Ceramics produced by the invention are as follows：Appearance and size is 150mm × 150mm, length 500mm.
As shown in Figure 1, the cross sectional shape of the composite honeycomb ceramic heat storage body 1 of the precise positioning is square, rectangle etc. One kind of the shapes such as one kind or semicircle of polygon, circle, arch, sector.Heat storage sectional dimension >=150mm is long Diameter ratio >=3（That is cylinder length and section circumscribed circle diameter ratio >=3）, heat storage be internally provided with it is uniform in size and in it is parallel or hand over The duct 11 of mistake arrangement, the shape in 11 section of duct are selected according to actual demand：Can be rectangular, triangle, pentagon, six sides One kind or semicircle of the polygons such as shape, circle, arch, sector one or more of various shapes combination.
As shown in Figs. 1-2, heat storage upper surface, lower face are respectively equipped with positioning groove 2, and positioning groove is cross. Heat storage upper surface or lower face are equipped with the positioning convex strip 3 coordinated with positioning groove, and positioning convex strip is cross.
Positioning convex strip 3 coordinates with positioning groove 2, can allow up and down two pieces of heat storage accurate positionings, prevent two honeycomb ceramics Airflow hole inconsistent phenomenon occurs between upper and lower end face.
As shown in figure 3, in the duct 11 and upper surface of heat storage 1 and lower face are compounded with resistant to corrosion layer 12.It is resistance to invade Erosion layer may be used the raw material that existing anticorrosive, anti-flue gas corrodes and make.
During installation, the first layer heat storage of bottom is first installed, then cross raised line is placed on to the top of the heat storage, then Second layer heat storage is placed at the top of first layer heat storage；Enable the groove, cross raised line, second layer accumulation of heat of first layer heat storage Body groove is mutually aligned, and then can accurately be installed.Unimpeded along airflow direction channel after installation, resistance is small, and dust stratification is few.Actually make With showing：Because the honeycomb ceramic heat accumulator size is big, shape is regular, after installation, the duct 1 between upper and lower two honeycomb ceramics aligns Accurately, as long as along airflow direction usually 1-2 pieces of honeycomb ceramic heat accumulator series connection it is ensured that airway patency, allows entire accumulation of heat to fill Storage exothermicity, high-temperature behavior and the thermal shock resistance put are not fully exerted.
Finally it is pointed out that Yi Shang specific embodiment is only the more representational example of the present invention.Obviously, it is of the invention Above-mentioned specific embodiment is not limited to, acceptable there are many deform.Every technical spirit according to the present invention is to above specific real Any simple modification, equivalent change and modification that the mode of applying is made is considered as belonging to the scope of protection of the present invention.

Claims (6)

1. a kind of medium temperature denitration, accumulation of heat integration rare earth composite ceramic material, it is characterised in that the ceramic material is mainly by following Component：25~30 parts of Zirconium oxide fibre, 70~80 parts of anorthite, 5~10 parts of boron nitride, 5~8 parts of barium carbonate, montmorillonite 10~ 15 parts, 4~5 parts of titanium dioxide, 2~3 parts of carbon fiber, 3~6 parts of haloflex, methyl methacrylate-butadiene-benzene It is 3~5 parts of ethylene-dien terpolymer, 3~6 parts of cyanethyl cellulose, 2~3 parts of phthalic acid ester, 2~3 parts of monoethanolamine, hard 1~3 part of resin acid is mediated by pug, aging, extrusion molding, drying and calcining, again impregnation catalyst slurry, dry and calciner Sequence is prepared；
The catalysis slurry is mainly composed of the following components：5~8 parts of aluminium oxide, 5~10 parts of ferric nitrate, 5~15 parts of manganese nitrate, 5~10 parts of anorthite, 5~10 parts of ammonium dihydrogen phosphate, 0.5~2 part of dimethyl silicone polymer, 6~10 parts of carbon fiber；Yttrium nitrate 3 ~5 parts, 5~8 parts of ammonium metatungstate, 5~8 parts of cerous nitrate, 2~4 parts of lanthanum nitrate, 3 parts of titanate coupling agent.
2. a kind of medium temperature denitration according to claim 1, accumulation of heat integration rare earth composite ceramic material, it is characterised in that its Preparation method includes the following steps：
（1）Pug is mediated：
i）Zirconium oxide fibre, anorthite, boron nitride, barium carbonate, montmorillonite, titanium dioxide, carbon fiber, haloflex is weighed to mix It closes, adds in deionized water and 20% ammonium hydroxide, 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 20% ammonium hydroxide, cover stirring machine cap, be heated to 95 DEG C or more while stirring, then open head cover, steam Hair concentration pug moisture to pug is in granular form, the pug moisture target value 25~28%, pH desired values 7.8~8.5；
iii）Add methyl methacrylate-butadiene-styrene copolymer, cyanoethyl fiber successively while stirring Element adds 20% ammonium hydroxide, stirring 15min or so, the pug moisture target value 29~34%, pH desired values 8.1~9.2；
iv）Phthalic acid ester, monoethanolamine, stearic acid 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；By dried catalyst blank be sent into kiln into Row calcining, 1100~1200 DEG C of calcination temperature, in calcination process, control temperature is passed from 100 DEG C by 100 DEG C/h of gradients Increase, calcination time is 18~22h, obtains ceramic honey comb green body；
（6）Starching：Weigh aluminium oxide, ferric nitrate, manganese nitrate, anorthite, ammonium dihydrogen phosphate, dimethyl silicone polymer, carbon fiber, Yttrium nitrate, ammonium metatungstate, cerous nitrate, lanthanum nitrate, titanate coupling agent are dissolved at 70~95 DEG C containing 1.2~3.5 parts of oxalic acid Aqueous solution, slurries are than 1:3, add and be warming up to 80 DEG C and keep the temperature, stirred 1~2 hour with ultrasonic oscillation, catalysis slurry is made；It will Step 5 gained ceramic honey comb green body is put into catalysis slurry pool, and drying oven, drying temperature 70 are put into after wrapping catalysis slurry DEG C, after striking off the catalysis slurry on the outside of ceramic honey comb green body and cleaning out, it is reentered into drying 20~30 minutes arid cycles Stove, drying temperature be 90 DEG C, arid cycle 1h；
（7）Calcining：By step（6）Obtained ceramic honey comb green body is sent into kiln and is calcined, 550 DEG C of calcination temperature, calcining In the process, control temperature is incremented by from 100 DEG C by 100 DEG C/h of gradients, and calcination time is 7~9h, obtains medium temperature honeycomb pottery Porcelain.
3. a kind of medium temperature denitration according to claim 2, accumulation of heat integration rare earth composite ceramic material, it is characterised in that： Step（3）Pre-filtering squeezes out, and strainer uses stainless steel filtering net of the mesh specification for 1.0x4mm or 0.8x3mm.
4. medium temperature denitration according to claim 2, accumulation of heat integration rare earth composite ceramic material, it is characterised in that：Step （4）Molding squeezes out, and extruder control condition is extrusion pressure 7MPa, 35 DEG C of extrusion temperature ＜, vacuum degree -0.094MPa or so.
5. low-temperature denitration accumulation of heat integration catalytic type Extruded Monolithic Celluar Ceramics according to claim 2, it is characterised in that：It is described Extruded Monolithic Celluar Ceramics are column structure, and Extruded Monolithic Celluar Ceramics are internally provided with the duct of multiple perforation cylinders, the ceramic honey comb material The cross sectional shape of material is polygon, semicircle, circle, arch, one kind of sector, the cross sectional shape in the duct is polygon, One or more combinations of semicircle, circle, arch, sector, in the duct and upper surface and lower end of Extruded Monolithic Celluar Ceramics Face is compounded with resistant to corrosion layer, and the Extruded Monolithic Celluar Ceramics upper surface, lower face are respectively equipped with positioning groove, in Extruded Monolithic Celluar Ceramics Upper surface or lower face are equipped with the positioning convex strip coordinated with positioning groove.
6. low-temperature denitration accumulation of heat integration catalytic type Extruded Monolithic Celluar Ceramics according to claim 5, it is characterised in that：It is described Positioning groove is cross, and the positioning convex strip is cross.
CN201711492590.4A 2017-12-30 2017-12-30 A kind of medium temperature denitration, accumulation of heat integration rare earth composite ceramic material Withdrawn CN108191444A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109737444A (en) * 2019-03-19 2019-05-10 烟台龙源电力技术股份有限公司 Rotary regenerative air preheater
CN109999790A (en) * 2019-04-04 2019-07-12 山东东源新材料科技有限公司 A kind of low-temperature denitration is without vanadium rare-earth base catalyst and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109737444A (en) * 2019-03-19 2019-05-10 烟台龙源电力技术股份有限公司 Rotary regenerative air preheater
CN109999790A (en) * 2019-04-04 2019-07-12 山东东源新材料科技有限公司 A kind of low-temperature denitration is without vanadium rare-earth base catalyst and preparation method thereof

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