CN108249896A - A kind of low-temperature denitration accumulation of heat integration catalytic type Extruded Monolithic Celluar Ceramics - Google Patents
A kind of low-temperature denitration accumulation of heat integration catalytic type Extruded Monolithic Celluar Ceramics Download PDFInfo
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- CN108249896A CN108249896A CN201711492596.1A CN201711492596A CN108249896A CN 108249896 A CN108249896 A CN 108249896A CN 201711492596 A CN201711492596 A CN 201711492596A CN 108249896 A CN108249896 A CN 108249896A
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Abstract
The invention discloses a kind of low-temperature denitration accumulation of heat integration catalytic type Extruded Monolithic Celluar Ceramics, it is characterised in that the ceramic material mainly includes：70~80 parts of alumina in Nano level, 35~40 parts of nano magnesia, 30~35 parts of nano-titanium dioxide, 1~3 part of boron nitride, 50~60 parts of silicon dioxide powder, methyl methacrylate -4~10 parts of butadiene-styrene copolymer, 3~8 parts of glass fibre, 0.8~1 part of stearic acid, 0.8~1 part of high polymer fiber, 0.8~1 part of aminocellulose are mediated by catalyst pug, catalyst pug is aging, catalyst pug extrusion molding, shaping of catalyst, wet base are dry, calcination process is prepared.The present invention improves the catalytic efficiency of catalyst, reduces the use cost of catalyst；It is stearic to add in the shaping and demoulding for contributing to catalyst, improve the yield rate of catalyst making；Preparation process of the present invention is simple, and reaction condition is mild under medium temperature environment, of low cost.
Description
Technical field
The present invention relates to a kind of middle temperature catalyst, especially a kind of low-temperature denitration accumulation of heat integration catalytic type ceramic honey comb material
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 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 denitration accumulation of heat integration catalytic type Extruded Monolithic Celluar Ceramics, is asked with solving above-mentioned technology
Topic.
In order to solve the above technical problems, the present invention program the technical solution adopted is that：A kind of low-temperature denitration accumulation of heat integration
Catalytic type Extruded Monolithic Celluar Ceramics, it is characterised in that the ceramic material is mainly by following components：70~80 parts of alumina in Nano level is received
35~40 parts of magnesia of rice, 30~35 parts of nano-titanium dioxide, 1~3 part of boron nitride, 50~60 parts of silicon dioxide powder, methyl-prop
E pioic acid methyl ester -4~10 parts of butadiene-styrene copolymer, 3~8 parts of glass fibre, 0.8~1 part of stearic acid, high score
Sub- 0.8~1 part of polymer fiber, 0.8~1 part of aminocellulose are mediated by pug, aging, extrusion molding, drying and calcining,
Impregnation catalyst slurry, drying is prepared with calcination process again；
The catalysis slurry is mainly composed of the following components：Weigh 5~8 parts of alumina in Nano level, 5~10 parts of ferric nitrate, nitric acid
5~15 parts of manganese, 5~10 parts of mullite, 5~10 parts of ammonium dihydrogen phosphate, 0.5~2 part of dimethyl silicone polymer, aluminum stearate 6~
10 parts, 3~5 parts of Nanometer-sized Neodymium Oxide, 5~8 parts of ammonium metatungstate, 3~4 parts of nano zine oxide, 5~8 parts of cerous nitrate, lanthanum nitrate 5~6
Part, 4~5 parts of titanate coupling agent.
Preparation method includes the following steps：
（1）Pug is mediated：
i）Weigh alumina in Nano level, nano magnesia, nano-titanium dioxide, boron nitride, silicon dioxide powder mixing, addition go from
20min or so is mediated in sub- water and 20% ammonium hydroxide, stirring, and by mediating and adjusting the deionized water of addition, ammonium hydroxide adjusting pug refers to
Mark, pug are mediated（i）Pug moisture target value 38~45%, pH desired values 7.8~9.4；
ii）A small amount of 20% ammonium hydroxide is added, covers stirring machine cap, is heated to 95 DEG C or more while stirring, then opens 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 methyl methacrylate-butadiene-styrene copolymer, glass fibre, 20% successively while stirring
Ammonium hydroxide, stirring 15min or so, the pug moisture target value 29~34%, pH desired values 8.1~9.2；
iv）Stearic acid, high polymer fiber, aminocellulose are added successively, stir more than 10min, the pug moisture
Desired value 28~32%, pH desired values 8.1~9.2；
（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, 1200~1300 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, with nitric acid cleaning ceramic green body, is dried for standby；
（6）Starching：Weigh alumina in Nano level, ferric nitrate, manganese nitrate, mullite, ammonium dihydrogen phosphate, dimethyl silicone polymer,
Aluminum stearate, Nanometer-sized Neodymium Oxide, ammonium metatungstate, nano zine oxide, cerous nitrate, lanthanum nitrate, titanate coupling agent, at 70~95 DEG C
The aqueous solution containing 1.2~3.5 parts of oxalic acid is dissolved in, slurries are than 1:3, add and be warming up to 80 DEG C and keep the temperature, 1 is stirred with ultrasonic oscillation
~2 hours, slurry is made；Step 5 gained ceramic honey comb green body is put into slurry pool, drying oven is put into after wrapping slurry, is done
Dry temperature is 70 DEG C, after striking off the slurry on the outside of ceramic honey comb green body and cleaning out, is relay 20~30 minutes arid cycles
Enter 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 calcining furnace and is calcined, and 500 DEG C of calcination temperature is forged
During burning, control temperature is incremented by from 100 DEG C by 100 DEG C/h of gradients, and calcination time is 7~9h, obtains the present invention.
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, and denitration rate at low ambient temperatures is high, and reaction condition is mild, to environment without
Any pollution.The present invention first passes through high-temperature firing ceramic honey comb idiosome, then by ceramic honey comb green body starching, finally by low temperature
500 DEG C are fired.This technique can significantly improve the anti-caking power of catalyst, improve the uniformity of catalyst temperature, change
Kind catalytic performance is conducive to improve catalyst thermal stability, simultaneously as ceramic honey comb idiosome high-temperature firing, structural strength is big,
In use, can the heat accumulation function of honeycomb ceramic carrier be greatly enhanced with laminated multi-layer in this way.The design of cross positioning convex strip enables
Two heat storage installations are more convenient, the airflow hole inconsistent phenomenon between two honeycomb ceramics can be greatly decreased after installation, along gas
The channel for flowing direction is very unimpeded.
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
Low-temperature denitration accumulation of heat integration catalytic type Extruded Monolithic Celluar Ceramics are mainly by following components：Alumina in Nano level 70 part, nanometer
40 parts of magnesia, 35 parts of nano-titanium dioxide, 1 part of boron nitride, 50 parts of silicon dioxide powder, methyl methacrylate-butadiene-
10 parts of styrene copolymer, 8 parts of glass fibre, 0.8 part of stearic acid, 0.8 part of high polymer fiber, aminocellulose
1 part is mediated by pug, aging, and extrusion molding, drying and calcining, impregnation catalyst slurry, again prepared by dry and calcination process
It forms；
The catalysis slurry is mainly composed of the following components：Weigh 5 parts of alumina in Nano level, 5 parts of ferric nitrate, 15 parts of manganese nitrate,
10 parts of mullite, 5 parts of ammonium dihydrogen phosphate, 2 parts of dimethyl silicone polymer, 6 parts of aluminum stearate, 3 parts of Nanometer-sized Neodymium Oxide, ammonium metatungstate
8 parts, 3 parts of nano zine oxide, 5 parts of cerous nitrate, 6 parts of lanthanum nitrate, 4 parts of titanate coupling agent.
Preparation method includes the following steps：
（1）Pug is mediated：
i）Weigh alumina in Nano level, nano magnesia, nano-titanium dioxide, boron nitride, silicon dioxide powder mixing, addition go from
20min or so is mediated in sub- water and 20% ammonium hydroxide, stirring, and by mediating and adjusting the deionized water of addition, ammonium hydroxide adjusting pug refers to
Mark, pug are mediated（i）Pug moisture target value 38~45%, pH desired values 7.8~9.4；
ii）A small amount of 20% ammonium hydroxide is added, covers stirring machine cap, is heated to 95 DEG C or more while stirring, then opens 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 methyl methacrylate-butadiene-styrene copolymer, glass fibre, 20% successively while stirring
Ammonium hydroxide, stirring 15min or so, the pug moisture target value 29~34%, pH desired values 8.1~9.2；
iv）Stearic acid, high polymer fiber, aminocellulose are added successively, stir more than 10min, the pug moisture
Desired value 28~32%, pH desired values 8.1~9.2；
（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, strainer uses mesh specification as 1.0x4mm
Or the stainless steel filtering net of 0.8x3mm, extrusion force 1700~2200N of plasticity, filtering are 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, 1200~1300 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, with nitric acid cleaning ceramic green body, is dried for standby；
（6）Starching：Weigh alumina in Nano level, ferric nitrate, manganese nitrate, mullite, ammonium dihydrogen phosphate, dimethyl silicone polymer,
Aluminum stearate, Nanometer-sized Neodymium Oxide, ammonium metatungstate, nano zine oxide, cerous nitrate, lanthanum nitrate, titanate coupling agent, at 70~95 DEG C
The aqueous solution containing 1.2~3.5 parts of oxalic acid is dissolved in, slurries are than 1:3, add and be warming up to 80 DEG C and keep the temperature, 1 is stirred with ultrasonic oscillation
~2 hours, slurry is made；Step 5 gained ceramic honey comb green body is put into slurry pool, drying oven is put into after wrapping slurry, is done
Dry temperature is 70 DEG C, after striking off the slurry on the outside of ceramic honey comb green body and cleaning out, is relay 20~30 minutes arid cycles
Enter 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 calcining furnace and is calcined, and 500 DEG C of calcination temperature is forged
During burning, control temperature is incremented by from 100 DEG C by 100 DEG C/h of gradients, and calcination time is 7~9h, obtains the present invention.
Embodiment 2
Low-temperature denitration accumulation of heat integration catalytic type Extruded Monolithic Celluar Ceramics are mainly by following components：Alumina in Nano level 75 part, nanometer
38 parts of magnesia, 32 parts of nano-titanium dioxide, 2 parts of boron nitride, 55 parts of silicon dioxide powder, methyl methacrylate-butadiene-
8 parts of styrene copolymer, 5 parts of glass fibre, 0.9 part of stearic acid, 0.9 part of high polymer fiber, aminocellulose
0.9 part is mediated by pug, aging, extrusion molding, drying and calcining, again impregnation catalyst slurry, dry and calcination process system
It is standby to form；
The catalysis slurry is mainly composed of the following components：Weigh 6 parts of alumina in Nano level, 8 parts of ferric nitrate, 10 parts of manganese nitrate,
8 parts of mullite, 7 parts of ammonium dihydrogen phosphate, 1.2 parts of dimethyl silicone polymer, 8 parts of aluminum stearate, 4 parts of Nanometer-sized Neodymium Oxide, metatungstic acid
6 parts of ammonium, 3 parts of nano zine oxide, 7 parts of cerous nitrate, 5 parts of lanthanum nitrate, 4 parts of titanate coupling agent.
Preparation method includes the following steps：
（1）Pug is mediated：
i）Weigh alumina in Nano level, nano magnesia, nano-titanium dioxide, boron nitride, silicon dioxide powder mixing, addition go from
20min or so is mediated in sub- water and 20% ammonium hydroxide, stirring, and by mediating and adjusting the deionized water of addition, ammonium hydroxide adjusting pug refers to
Mark, pug are mediated（i）Pug moisture target value 38~45%, pH desired values 7.8~9.4；
ii）A small amount of 20% ammonium hydroxide is added, covers stirring machine cap, is heated to 95 DEG C or more while stirring, then opens 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 methyl methacrylate-butadiene-styrene copolymer, glass fibre, 20% successively while stirring
Ammonium hydroxide, stirring 15min or so, the pug moisture target value 29~34%, pH desired values 8.1~9.2；
iv）Stearic acid, high polymer fiber, aminocellulose are added successively, stir more than 10min, the pug moisture
Desired value 28~32%, pH desired values 8.1~9.2；
（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, strainer uses mesh specification as 1.0x4mm
Or the stainless steel filtering net of 0.8x3mm, extrusion force 1700~2200N of plasticity, filtering are 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, 1200~1300 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, with nitric acid cleaning ceramic green body, is dried for standby；
（6）Starching：Weigh alumina in Nano level, ferric nitrate, manganese nitrate, mullite, ammonium dihydrogen phosphate, dimethyl silicone polymer,
Aluminum stearate, Nanometer-sized Neodymium Oxide, ammonium metatungstate, nano zine oxide, cerous nitrate, lanthanum nitrate, titanate coupling agent, at 70~95 DEG C
The aqueous solution containing 1.2~3.5 parts of oxalic acid is dissolved in, slurries are than 1:3, add and be warming up to 80 DEG C and keep the temperature, 1 is stirred with ultrasonic oscillation
~2 hours, slurry is made；Step 5 gained ceramic honey comb green body is put into slurry pool, drying oven is put into after wrapping slurry, is done
Dry temperature is 70 DEG C, after striking off the slurry on the outside of ceramic honey comb green body and cleaning out, is relay 20~30 minutes arid cycles
Enter 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 calcining furnace and is calcined, and 500 DEG C of calcination temperature is forged
During burning, control temperature is incremented by from 100 DEG C by 100 DEG C/h of gradients, and calcination time is 7~9h, obtains the present invention.
Embodiment 3
Low-temperature denitration accumulation of heat integration catalytic type Extruded Monolithic Celluar Ceramics are mainly by following components：Alumina in Nano level 80 part, nanometer
35 parts of magnesia, 30 parts of nano-titanium dioxide, 3 parts of boron nitride, 60 parts of silicon dioxide powder, methyl methacrylate-butadiene-
4 parts of styrene copolymer, 3 parts of glass fibre, 1 part of stearic acid, 1 part of high polymer fiber, 0.8 part of aminocellulose
Mediated by pug, it is aging, extrusion molding, drying and calcining, impregnation catalyst slurry, again dry prepare with calcination process and
Into；
The catalysis slurry is mainly composed of the following components：Weigh 8 parts of alumina in Nano level, 10 parts of ferric nitrate, 5 parts of manganese nitrate,
5 parts of mullite, 10 parts of ammonium dihydrogen phosphate, 0.5 part of dimethyl silicone polymer, 10 parts of aluminum stearate, 5 parts of Nanometer-sized Neodymium Oxide, inclined tungsten
Sour 5 parts of ammonium, 4 parts of nano zine oxide, 8 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 alumina in Nano level, nano magnesia, nano-titanium dioxide, boron nitride, silicon dioxide powder mixing, addition go from
20min or so is mediated in sub- water and 20% ammonium hydroxide, stirring, and by mediating and adjusting the deionized water of addition, ammonium hydroxide adjusting pug refers to
Mark, pug are mediated（i）Pug moisture target value 38~45%, pH desired values 7.8~9.4；
ii）A small amount of 20% ammonium hydroxide is added, covers stirring machine cap, is heated to 95 DEG C or more while stirring, then opens 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 methyl methacrylate-butadiene-styrene copolymer, glass fibre, 20% successively while stirring
Ammonium hydroxide, stirring 15min or so, the pug moisture target value 29~34%, pH desired values 8.1~9.2；
iv）Stearic acid, high polymer fiber, aminocellulose are added successively, stir more than 10min, the pug moisture
Desired value 28~32%, pH desired values 8.1~9.2；
（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, strainer uses mesh specification as 1.0x4mm
Or the stainless steel filtering net of 0.8x3mm, extrusion force 1700~2200N of plasticity, filtering are 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, 1200~1300 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, with nitric acid cleaning ceramic green body, is dried for standby；
（6）Starching：Weigh alumina in Nano level, ferric nitrate, manganese nitrate, mullite, ammonium dihydrogen phosphate, dimethyl silicone polymer,
Aluminum stearate, Nanometer-sized Neodymium Oxide, ammonium metatungstate, nano zine oxide, cerous nitrate, lanthanum nitrate, titanate coupling agent, at 70~95 DEG C
The aqueous solution containing 1.2~3.5 parts of oxalic acid is dissolved in, slurries are than 1:3, add and be warming up to 80 DEG C and keep the temperature, 1 is stirred with ultrasonic oscillation
~2 hours, slurry is made；Step 5 gained ceramic honey comb green body is put into slurry pool, drying oven is put into after wrapping slurry, is done
Dry temperature is 70 DEG C, after striking off the slurry on the outside of ceramic honey comb green body and cleaning out, is relay 20~30 minutes arid cycles
Enter 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 calcining furnace and is calcined, and 500 DEG C of calcination temperature is forged
During burning, control temperature is incremented by from 100 DEG C by 100 DEG C/h of gradients, and calcination time is 7~9h, obtains the present invention.
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 up to axially 79MPa, wear-resistant 5.6~5.9cm3, 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 low-temperature denitration accumulation of heat integration catalytic type Extruded Monolithic Celluar Ceramics, it is characterised in that the ceramic material is mainly by following
Component：70~80 parts of alumina in Nano level, 35~40 parts of nano magnesia, 30~35 parts of nano-titanium dioxide, boron nitride 1~3
Part, 50~60 parts of silicon dioxide powder, methyl methacrylate -4~10 parts of butadiene-styrene copolymer, glass fibers
3~8 parts of dimension, 0.8~1 part of stearic acid, 0.8~1 part of high polymer fiber, 0.8~1 part of aminocellulose are pinched by pug
It closes, aging, extrusion molding, drying and calcining, impregnation catalyst slurry, drying is prepared with calcination process again；
The catalysis slurry is mainly composed of the following components：Weigh 5~8 parts of alumina in Nano level, 5~10 parts of ferric nitrate, nitric acid
5~15 parts of manganese, 5~10 parts of mullite, 5~10 parts of ammonium dihydrogen phosphate, 0.5~2 part of dimethyl silicone polymer, aluminum stearate 6~
10 parts, 3~5 parts of Nanometer-sized Neodymium Oxide, 5~8 parts of ammonium metatungstate, 3~4 parts of nano zine 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 denitration accumulation of heat integration catalytic type Extruded Monolithic Celluar Ceramics according to claim 1, it is characterised in that
Preparation method includes the following steps：
（1）Pug is mediated：
i）Weigh alumina in Nano level, nano magnesia, nano-titanium dioxide, boron nitride, silicon dioxide powder mixing, addition go from
20min or so is mediated in sub- water and 20% ammonium hydroxide, stirring, and by mediating and adjusting the deionized water of addition, ammonium hydroxide adjusting pug refers to
Mark, pug are mediated（i）Pug moisture target value 38~45%, pH desired values 7.8~9.4；
ii）A small amount of 20% ammonium hydroxide is added, covers stirring machine cap, is heated to 95 DEG C or more while stirring, then opens 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 methyl methacrylate-butadiene-styrene copolymer, glass fibre, 20% successively while stirring
Ammonium hydroxide, stirring 15min or so, the pug moisture target value 29~34%, pH desired values 8.1~9.2；
iv）Stearic acid, high polymer fiber, aminocellulose are added successively, stir more than 10min, the pug moisture
Desired value 28~32%, pH desired values 8.1~9.2；
（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, 1200~1300 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, with nitric acid cleaning ceramic green body, is dried for standby；
（6）Starching：Weigh alumina in Nano level, ferric nitrate, manganese nitrate, mullite, ammonium dihydrogen phosphate, dimethyl silicone polymer,
Aluminum stearate, Nanometer-sized Neodymium Oxide, ammonium metatungstate, nano zine oxide, cerous nitrate, lanthanum nitrate, titanate coupling agent, at 70~95 DEG C
The aqueous solution containing 1.2~3.5 parts of oxalic acid is dissolved in, slurries are than 1:3, add and be warming up to 80 DEG C and keep the temperature, 1 is stirred with ultrasonic oscillation
~2 hours, slurry is made；Step 5 gained ceramic honey comb green body is put into slurry pool, drying oven is put into after wrapping slurry, is done
Dry temperature is 70 DEG C, after striking off the slurry on the outside of ceramic honey comb green body and cleaning out, is relay 20~30 minutes arid cycles
Enter 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 calcining furnace and is calcined, and 500 DEG C of calcination temperature is forged
During burning, control temperature is incremented by from 100 DEG C by 100 DEG C/h of gradients, and calcination time is 7~9h, obtains the present invention.
3. a kind of low-temperature denitration accumulation of heat integration catalytic type Extruded Monolithic Celluar Ceramics according to claim 2, feature exist
In：Step（3）Pre-filtering squeezes out, and strainer uses stainless steel filtering net of the mesh specification for 1.0x4mm or 0.8x3mm.
4. low-temperature denitration accumulation of heat integration catalytic type Extruded Monolithic Celluar Ceramics according to claim 2, 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.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109675400A (en) * | 2018-12-28 | 2019-04-26 | 武汉理工大学 | Organic exhaust gas high temperature pyrolysis device |
| CN112354358A (en) * | 2020-09-17 | 2021-02-12 | 山东骏飞环保科技有限公司 | Catalytic cracking oxygen-poor regeneration denitration agent and preparation method thereof |
| CN113600179A (en) * | 2021-09-16 | 2021-11-05 | 山东博霖环保科技发展有限公司 | Denitration catalyst and preparation method thereof |
| CN114308013A (en) * | 2022-01-06 | 2022-04-12 | 浙江德创环保科技股份有限公司 | Production process of low-cost high-temperature denitration catalyst |
| CN115611616A (en) * | 2022-10-18 | 2023-01-17 | 国家电投集团远达环保催化剂有限公司 | Honeycomb wear-resistant unit body and preparation method thereof |
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2017
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109675400A (en) * | 2018-12-28 | 2019-04-26 | 武汉理工大学 | Organic exhaust gas high temperature pyrolysis device |
| CN109675400B (en) * | 2018-12-28 | 2021-01-26 | 武汉理工大学 | Organic waste gas high-temperature pyrolysis device |
| CN112354358A (en) * | 2020-09-17 | 2021-02-12 | 山东骏飞环保科技有限公司 | Catalytic cracking oxygen-poor regeneration denitration agent and preparation method thereof |
| CN113600179A (en) * | 2021-09-16 | 2021-11-05 | 山东博霖环保科技发展有限公司 | Denitration catalyst and preparation method thereof |
| CN114308013A (en) * | 2022-01-06 | 2022-04-12 | 浙江德创环保科技股份有限公司 | Production process of low-cost high-temperature denitration catalyst |
| CN115611616A (en) * | 2022-10-18 | 2023-01-17 | 国家电投集团远达环保催化剂有限公司 | Honeycomb wear-resistant unit body and preparation method thereof |
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