CN105435536A - Denitration catalysis membrane filtering material and preparation method thereof - Google Patents
Denitration catalysis membrane filtering material and preparation method thereof Download PDFInfo
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- CN105435536A CN105435536A CN201510873188.5A CN201510873188A CN105435536A CN 105435536 A CN105435536 A CN 105435536A CN 201510873188 A CN201510873188 A CN 201510873188A CN 105435536 A CN105435536 A CN 105435536A
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Abstract
The invention discloses a denitration catalysis membrane filtering material and a preparation method thereof. The denitration catalysis membrane filtering material comprises a membrane filtering material body and a catalytic active layer which is attached to the hole surfaces of the membrane filtering material body and composed of SCR denitration catalysis active substances to achieve SCR denitration catalysis on nitrogen oxides in furnace gas. A porous membrane with the thickness of 100-1000 micrometers and with the good flexibility serves as the membrane filtering material body, has the excellent high temperature resistance, can stably work within the SCR catalytic reaction temperature range, can be cut, folded and curled into various shapes and bonded or welded to an existing purification device to serve as a filtering element and has the good practicability. The mass of the catalytic active layer accounts for 5%-20% of the total mass of the denitration catalysis membrane filtering material, and the thickness of the catalytic active layer is 0.5-2.5 micrometers.
Description
Technical field
The present invention relates to membrane filtration material and preparation method thereof, particularly relate to membrane filtration material flue gas to filtration and SCR denitration catalysis double action and preparation method thereof.
Background technology
Normal containing a large amount of dust and nitrogen oxide in industrial furnace gas, a typical example and coal-fired plant boiler furnace gas, the nitrogen oxide contained by it is the main cause of facilitating acid rain to be formed, and also containing the dust of tens of grams in general often liter of coal-fired plant boiler furnace gas.The usual method taked for the purification of the such as industrial furnace gas of the contour dust of coal-fired plant boiler furnace gas and amount of nitrogen oxides is: first furnace gas is introduced SCR reactor (also needs to inject reducing agent in furnace gas in process furnace gas being introduced SCR reactor, this reducing agent is generally ammoniacal liquor) thus nitrogen oxides reduction is harmless nitrogen gas, realize furnace gas denitration purification, then the furnace gas after denitration is introduced electric cleaner to remove the dust in furnace gas, then discharge after the gas after dedusting is introduced desulfurizing tower desulfurizing and purifying.Said term " SCR " refers to SelectiveCatalyticReduction, i.e. SCR.
Catalyst in above-mentioned SCR reactor is the key factor affecting the overall denitration effect of SCR system.The SCR catalyst of initial exploitation is graininess, then mainly adopts cellular or tabular catalyst at present.Honeycombed catalyst and tabular catalyst are all placed with numerous checkerwork cell passed through for furnace gas, the large I of these checkerwork cells is selected according to the concentration of dust in furnace gas and size, during use, furnace gas flows to the opposite side of catalyst by the passage be made up of these checkerwork cells from the side of catalyst, furnace gas contacts with the catalytic active substance on checkerwork cell inwall therebetween, thus is harmless nitrogen gas by the reduction of nitrogen oxide in furnace gas.Above-mentioned honeycombed catalyst and tabular catalyst are generally made up of carrier and catalytic active layer, wherein carrier is first made into cellular or tabular (general employing is extruded), and then on carrier, adhere to the catalytic active layer be made up of catalytic active substance.
Although the large I of the checkerwork cell of honeycombed catalyst and tabular catalyst is selected according to the concentration of dust in furnace gas and size, still exist in actual use the problem that blocks by dust.In addition, because SCR catalyst directly contacts with the furnace gas of high dustiness, therefore easily cause catalytic active substance poisoning, service life shortens.In addition, employ electric cleaner in said method to remove the dust in furnace gas, but by electric precipitation, there is the selective factors such as feature of gathering dust and affect the problem also often occurring that electric cleaner exit gas dustiness exceeds standard.Therefore, the purification techniques for the current such as industrial furnace gas of the contour dust of coal-fired plant boiler furnace gas and amount of nitrogen oxides need further improvement.
Present invention applicant is called Chinese patent application file (the publication number CN104492189A of " industrial furnace gas dedusting denitrification integral processing method and special equipment " in name, call reference paper in the following text) in provide and can carry out the industrial furnace gas dedusting denitrification integral processing method of dedusting and denitration and special equipment to industrial furnace gas simultaneously and include but not limited to the filtration catalytic element that can apply in this industrial furnace gas dedusting denitrification integral processing method and preparation method thereof, to realize the double action treating medium high-efficiency filtering and purifying and catalytic reaction.The filtration catalytic element provided in this patent document has a porous complex, this porous complex comprises porous matrix and catalytic active layer, described porous matrix is made up of sintering diamond bit or sintered ceramic porous material, described catalytic active layer is attached to porous matrix hole surface and is made up of catalytic active substance, in addition porous complex also comprises intermediate layer, described intermediate layer is made up of the nano particle at porous matrix surface sediment, and described catalytic active layer is attached to porous matrix hole surface by intermediate layer.For this filtration catalytic element, because intermediate layer is made up of the nano particle at porous matrix surface sediment, therefore the hole surface of the surface ratio porous matrix in intermediate layer is much coarse, substantially increase the specific area of porous matrix thus, all can significantly improve with the uniformity coefficient of the content and setting that make catalytic active substance in porous complex, improve catalytic reaction rate.In addition, additionally provide filtration catalytic element in above-mentioned patent document and form as concrete structure when industrial furnace gas being had to filtration and a function element of SCR denitration catalysis double action and material, and the preparation method of this filtration catalytic element.
The present inventor's follow-up study finds, in the preparation process of the filtration catalytic element of reference paper, the preparation of porous matrix adopts cold isostatic compaction mode powder stock to be pressed into the shape of filter element, the flexibility of the porous matrix formed is poor, therefore can only be pressed into corresponding shape according to specific installation site.Because the size of the flue gas cleaning system of different Industrial Stoves often there are differences, therefore certain obstruction is caused to the application of the filtration catalytic element in reference paper.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of bending distortion easy for installation, easy and can filters industrial furnace gas and the membrane filtration material of SCR denitration catalysis double action simultaneously.The present invention also will provide the preparation method of this membrane filtration material.
The present invention solves the problems of the technologies described above used technological means for a kind of catalytic membrane filtering material including but not limited to can to apply in industrial furnace gas dedusting denitration, that a kind of medium for the treatment of has filtration and the functional material of catalytic reaction double action, comprise filtering material body and catalytic active layer, described filtering material body is made up of porous membrane, described catalytic active layer is attached to the hole surface of porous membrane and is made up of catalytic active substance, described catalytic membrane filtering material also comprises intermediate layer, the nano particle that described intermediate layer is piled up by the hole surface at porous membrane formed, described catalytic active layer is attached to the hole surface of porous membrane by intermediate layer.Because intermediate layer is that the nano particle piled up by the hole surface at porous membrane is formed, therefore the hole surface of the surface ratio porous membrane in intermediate layer is much coarse, substantially increase the specific area of porous membrane thus, all can significantly improve with the uniformity coefficient of the content and setting that make catalytic active substance in catalytic membrane filtering material, improve catalytic reaction rate.
This catalytic membrane filtering material can be specifically a kind of denitration catalyst membrane filtration material industrial furnace gas to filtration and SCR denitration catalysis double action, comprise membrane filtration material body and be attached to the hole surface of membrane filtration material body and the catalytic active layer be made up of SCR denitration catalytic active substance, membrane filtration material body is the porous membrane with good flexibility, not only there is excellent resistance to elevated temperatures, work that can be stable in SCR catalytic reaction temperature range, and can cutting, folding, be curled into various shape and bonding or be welded in existing purifier as filter element, there is good practicality.The average pore size of described porous membrane is 1-30 μm, thickness is 100-1000 μm, porosity is 25-75%.Preferably, the thickness of porous membrane is 200-500 μm.Owing to the hole surface of porous membrane attached to the catalytic active layer be made up of SCR denitration catalytic active substance, furnace gas can contact with catalytic active substance again in by the process of gas-solid isolated by filtration, realizes the SCR denitration catalysis to nitrogen oxide in furnace gas.The quality of catalytic active layer accounts for the 5-20% of denitration catalyst membrane filtration material gross mass; The thickness of catalytic active layer is 0.5-2.5 μm.Described SCR denitration catalytic active layer can by V
2o
5form or with V
2o
5for main component, with WO
3and MoO
3in at least one be auxiliary element mixture form.
In use, when the average pore size of porous membrane be 1-30 μm, porosity be 25-75% time, the side that denitration catalyst membrane filtration material first contacts with furnace gas can form filter cake, this filter cake can promote filter efficiency on the one hand, the touch opportunity of particle and SCR denitration catalytic active substance in furnace gas can be reduced on the other hand, extend the service life of SCR denitration catalytic active substance.In addition, the porous membrane that one is not adhered to SCR denitration catalytic active substance can be placed on the surface of above-mentioned denitration catalyst membrane filtration material, when furnace gas enters denitration catalyst membrane filtration material, wherein most of particle is trapped, the touch opportunity even eliminating dust and SCR denitration catalytic active substance can be reduced further, effectively prevent SCR denitration catalytic active substance poisoning.In order to be more convenient for installing, denitration catalyst membrane filtration material can be passed through to weld or bonding connection with the porous membrane not adhering to SCR denitration catalytic active substance.
As a further improvement on the present invention, described denitration catalyst membrane filtration material also comprises the intermediate layer between the hole surface and SCR denitration catalytic active layer of porous membrane, the nano particle that described intermediate layer is piled up by the hole surface at porous membrane formed, and SCR denitration catalytic active layer is attached to the hole surface of porous membrane by this intermediate layer.Because intermediate layer is that the nano particle piled up by the hole surface at porous membrane is formed, therefore the hole surface of the surface ratio porous membrane in intermediate layer is much coarse, substantially increase the specific area of porous membrane thus, to make the content of SCR denitration catalytic active substance and the uniformity coefficient of setting in denitration catalyst membrane filtration material all can significantly improve, effectively ensure that the denitration rate of industrial furnace gas.Described intermediate layer can by TiO
2nano particle, AlO
2nano particle, ZrO
2nano particle or SiO
2nano particle is formed.A kind of better mode makes intermediate layer be by TiO
2, AlO
2, ZrO
2, SiO
2in the compound of two or more formation, such intermediate layer has better architectural characteristic, mechanical strength, specific area, can improve catalytic active layer surface texture and mechanical performance, is conducive to improving catalytic reaction effect.
As a further improvement on the present invention, described porous membrane comprises supporter and sintered alloy porous material, and described sintering diamond bit is matrix phase by Ag-Au solid solution, Fe-Cr solid solution, Ti-Zr solid solution, Cu-Zn solid solution, Ni-Cr solid solution, Ni-Cu solid solution or Fe-C-Cr solid solution.Described sintering diamond bit is preferably matrix phase by Ni-Cr solid solution, and the pore size distribution in this porous material is even, has good permeance property, and has good flexibility (multi-folded) and physicochemical stability.Because in the preparation process of porous membrane, base substrate is supported by supporter, avoid the situations such as the cracking of material during sintering and distortion well, effectively can reduce without the shaping difficulty supporting porous membrane and improve Forming Quality.The thickness of supporter is 0.05-100 μm, mesh size is 35-100 μm, if mesh increases further on this number range basis, coating slurry, after easily causing slurry to cover imperfect, sintering, porous membrane exists the defects such as trachoma; If mesh reduces further on this number range basis, some adverse effects will be caused because the coated weight of slurry is less to porous membrane.Described supporter is Cu net, Ni net or screen cloth.
The step of the preparation method of above-mentioned denitration catalyst membrane filtration material comprises: 1) the raw meal dispersant and binding agent that form its metal polyporous material are configured to thick slurry, the supporter described slurry being coated in certain thickness and aperture is dried, is pressed into base substrate and sintering, after sintering, namely obtains porous membrane; 2) configuration is as the colloidal sol in intermediate layer material source, again by described sol impregnation in porous membrane, dip time is 5-15min, then the collosol and gel in porous membrane is made, again the porous membrane of the described gel of attachment is heat-treated, make gel conversion be nano particle, and then form intermediate layer, intermediate layer is by TiO
2nano particle, Al
2o
3nano particle, ZrO
2nano particle, SiO
2at least one in nano particle is formed; 3) SCR denitration catalytic active substance precursor solution is configured, again described precursor solution is impregnated in the porous membrane in attachment intermediate layer, dip time is 5-25min, then the porous membrane being attached with precursor solution is heat-treated, described intermediate layer is formed SCR denitration catalytic active layer, and described SCR denitration catalytic active layer can by V
2o
5form or with V
2o
5for main component, with WO
3and MoO
3in at least one be auxiliary element mixture form.
When described sintering diamond bit is matrix phase by Ni-Cr solid solution, the preparation method of denitration catalyst membrane filtration material, comprising the following steps: 1) prepare porous membrane: be the proportioning of 15-35% according to the percentage by weight of Cr, is that the Ni powder of 3-15 μm is configured to mixed powder with-400 order Cr powder by particle diameter; Then be dispersant with ethanol, PVB is for bonding agent is according to the proportional arrangement slurry adding 2-5gPVB, 50-70g mixed powder in every 100 milliliters of ethanol; Described slurry is coated in thickness is 0.05-100 μm, mesh size is on the supporter of 35-100 μm and dries, be pressed into base substrate and sintering, sintering temperature control 900-1250 DEG C is also incubated 2-8h, namely obtains porous membrane after sintering; 2) configuration is as the colloidal sol in intermediate layer material source, again by described sol impregnation in porous membrane, dip time is 5-15min, then the collosol and gel in porous membrane is made, again the porous membrane of the described gel of attachment is heat-treated, make gel conversion be nano particle, and then form intermediate layer, intermediate layer is by TiO
2nano particle, Al
2o
3nano particle, ZrO
2nano particle, SiO
2at least one in nano particle is formed; 3) SCR denitration catalytic active substance precursor solution is configured, again described precursor solution is impregnated in the porous membrane in attachment intermediate layer, dip time is 5-25min, then the porous membrane being attached with precursor solution is heat-treated, described intermediate layer is formed SCR denitration catalytic active layer, and described SCR denitration catalytic active layer can by V
2o
5form or with V
2o
5for main component, with WO
3and MoO
3in at least one be auxiliary element mixture form.
Detailed description of the invention
Embodiment 1
1) preparing porous membrane: first, is the proportioning of 15% according to the percentage by weight of Cr, is that Ni powder and the particle diameter of 3-15 μm is configured to mixed powder for-400 order Cr powder by particle diameter; Then be dispersant with ethanol, PVB is bonding agent, according to the proportional arrangement slurry adding 4gPVB, 60g mixed powder in every 100 milliliters of ethanol; Then, adopt Cu net to be supporter, its thickness is 70 μm, mesh greatly 35 μm, and described pulp spraying is coated in Cu online and make base substrate dry 4h at 60 DEG C after, the quantity for spray of slurry is every square metre of supporter spraying 600g slurry; Base substrate is positioned in sintering furnace, 8h is sintered at 900 DEG C, heating rate is 1-5 DEG C/min, cooling i.e. obtained porous membrane after sintering, in this porous membrane, sintering diamond bit is with Ni-Cr solid solution for matrix, and the thickness of this porous membrane is 1000 μm, average pore size 2 μm, porosity is 25%, and air permeability is 780m
3/ m
2hkpa.
2) configuration is as the colloidal sol in intermediate layer material source: by the 2:10:1 mixing by volume of butyl titanate, alcohol and aqueous solution of nitric acid, it is 4 that adjustment acid content controls pH value, colloidal sol is met the demands, then by described sol impregnation in porous membrane, dip time is 10min, at 80 DEG C, be incubated 4h after dipping, put into resistance furnace after there is stable gel and fire 4h at 450 DEG C, formed by TiO
2the intermediate layer that nano particle is formed.
3) ammonium paratungstate and ammonium metavanadate preparation SCR denitration catalytic active substance precursor solution is adopted, again described precursor solution is impregnated in the porous membrane in attachment intermediate layer, dip time is 5min, then the porous membrane being attached with precursor solution is heat-treated in resistance furnace, 2h is incubated at 300-450 DEG C, namely form SCR denitration catalytic active layer on the intermediate layer, namely obtain denitration catalyst membrane filtration material.In gained denitration catalyst membrane filtration material, the quality of SCR denitration catalytic active substance accounts for 5% of denitration catalyst membrane filtration material gross mass, and the thickness of SCR denitration catalytic active layer is 0.5 μm.
4) the result of use test of denitration catalyst membrane filtration material: above-mentioned denitration catalyst membrane filtration material is cut into suitable shape and loads in the SCR denitration oxidation catalyst filter element of integrated apparatus (see reference paper), and with the pipeline closed, the high-temperature furnace gas that coal-fired plant boiler economizer is got rid of is passed into the air inlet of integrated apparatus, make the furnace gas being mixed with reducing agent by SCR denitration oxidation catalyst filter element, thus under the effect of denitration catalyst membrane filtration material, carry out gas-solid isolated by filtration and the SCR denitration catalysis of furnace gas simultaneously, in the gas that integrated apparatus is discharged, dust content is at 4mg/Nm
3below, denitration rate is about 85%, and still can keep comparatively stable denitration rate after repeatedly pulse cleaning being carried out to denitration catalyst membrane filtration material, use denitration catalyst membrane filtration material to be pulled down after a period of time observe find SCR denitration catalytic active substance and porous membrane adhesion condition good.
Embodiment 2
1) preparing porous membrane: first, is the proportioning of 20% according to the percentage by weight of Cr, is that Ni powder and the particle diameter of 3-15 μm is configured to mixed powder for-400 order Cr powder by particle diameter; Then be dispersant with ethanol, PVB is bonding agent, according to the proportional arrangement slurry adding 4gPVB, 60g mixed powder in every 100 milliliters of ethanol; Then, adopt 304 stainless steel mesh to be supporter, its thickness is 70 μm, mesh greatly 50 μm, and described pulp spraying is coated in 304 stainless steel sifts online and make base substrate dry 4h at 60 DEG C after, the quantity for spray of slurry is every square metre of supporter spraying 550g slurry; Base substrate is positioned in sintering furnace, 6h is sintered at 1000 DEG C, heating rate is 1-5 DEG C/min, cooling i.e. obtained porous membrane after sintering, in this porous membrane, sintering diamond bit is with Ni-Cr solid solution for matrix, and the thickness of this porous membrane is 720 μm, average pore size 12 μm, porosity is 35%, and air permeability is 1120m
3/ m
2hkpa.
2) configuration is as the colloidal sol in intermediate layer material source: by Al (NO
3)
3, the 2:10:1 mixing by volume of alcohol and aqueous solution of nitric acid, it is 4 that adjustment acid content controls pH value, colloidal sol is met the demands, then by described sol impregnation in porous membrane, dip time is 10min, at 80 DEG C, be incubated 4h after dipping, put into resistance furnace after there is stable gel and fire 1h at 450 DEG C, formed by Al
2o
3the intermediate layer that nano particle is formed.
3) ammonium paratungstate and ammonium metavanadate preparation SCR denitration catalytic active substance precursor solution is adopted, again described precursor solution is impregnated in the porous membrane in attachment intermediate layer, dip time is 10min, then the porous membrane being attached with precursor solution is heat-treated in resistance furnace, 2h is incubated at 300-450 DEG C, namely form SCR denitration catalytic active layer on the intermediate layer, namely obtain denitration catalyst membrane filtration material.In gained denitration catalyst membrane filtration material, the quality of SCR denitration catalytic active substance accounts for 8% of denitration catalyst membrane filtration material gross mass, and the thickness of SCR denitration catalytic active layer is 0.9 μm.
4) the result of use test of denitration catalyst membrane filtration material: above-mentioned denitration catalyst membrane filtration material is cut into suitable shape and loads in the SCR denitration oxidation catalyst filter element of integrated apparatus (see reference paper), and with the pipeline closed, the high-temperature furnace gas that coal-fired plant boiler economizer is got rid of is passed into the air inlet of integrated apparatus, make the furnace gas being mixed with reducing agent by SCR denitration oxidation catalyst filter element, thus under the effect of denitration catalyst membrane filtration material, carry out gas-solid isolated by filtration and the SCR denitration catalysis of furnace gas simultaneously, in the gas that integrated apparatus is discharged, dust content is at 6mg/Nm
3below, denitration rate is about 90%, and still can keep comparatively stable denitration rate after repeatedly pulse cleaning being carried out to denitration catalyst membrane filtration material, use denitration catalyst membrane filtration material to be pulled down after a period of time observe find SCR denitration catalytic active substance and porous membrane adhesion condition good.
Embodiment 3
1) preparing porous membrane: first, is the proportioning of 25% according to the percentage by weight of Cr, is that Ni powder and the particle diameter of 3-15 μm is configured to mixed powder for-400 order Cr powder by particle diameter; Then be dispersant with ethanol, PVB is bonding agent, according to the proportional arrangement slurry adding 4gPVB, 60g mixed powder in every 100 milliliters of ethanol; Then, adopt 316 stainless steel mesh to be supporter, its thickness is 70 μm, mesh greatly 75 μm, and described pulp spraying is coated in 316 stainless steel sifts online and make base substrate dry 4h at 60 DEG C after, the quantity for spray of slurry is every square metre of supporter spraying 350g slurry; Base substrate is positioned in sintering furnace, 5h is sintered at 1050 DEG C, heating rate is 1-5 DEG C/min, cooling i.e. obtained porous membrane after sintering, in this porous membrane, sintering diamond bit is with Ni-Cr solid solution for matrix, and the thickness of this porous membrane is 500 μm, average pore size 18 μm, porosity is 52%, and air permeability is 1560m
3/ m
2hkpa.
2) configuration is as the colloidal sol in intermediate layer material source: by Al (NO
3)
3, butyl titanate, the 1:8:40:5 mixing by volume of alcohol and aqueous solution of nitric acid, it is 3 that adjustment acid content controls pH value, colloidal sol is met the demands, then by described sol impregnation in porous membrane, dip time is 10min, at 80 DEG C, be incubated 4h after dipping, put into resistance furnace after there is stable gel and fire 2h at 450 DEG C, formed by TiO
2nano particle and Al
2o
3the composite interlayer that nano particle is formed.
3) ammonium paratungstate and ammonium metavanadate preparation SCR denitration catalytic active substance precursor solution is adopted, again described precursor solution is impregnated in the porous membrane in attachment intermediate layer, dip time is 15min, then the porous membrane being attached with precursor solution is heat-treated in resistance furnace, 2h is incubated at 300-450 DEG C, namely form SCR denitration catalytic active layer on the intermediate layer, namely obtain denitration catalyst membrane filtration material.In gained denitration catalyst membrane filtration material, the quality of SCR denitration catalytic active substance accounts for 12% of denitration catalyst membrane filtration material gross mass, and the thickness of SCR denitration catalytic active layer is 1.5 μm.
4) the result of use test of denitration catalyst membrane filtration material: above-mentioned denitration catalyst membrane filtration material is cut into suitable shape and loads in the SCR denitration oxidation catalyst filter element of integrated apparatus (see reference paper), and with the pipeline closed, the high-temperature furnace gas that coal-fired plant boiler economizer is got rid of is passed into the air inlet of integrated apparatus, make the furnace gas being mixed with reducing agent by SCR denitration oxidation catalyst filter element, thus under the effect of denitration catalyst membrane filtration material, carry out gas-solid isolated by filtration and the SCR denitration catalysis of furnace gas simultaneously, in the gas that integrated apparatus is discharged, dust content is at 7mg/Nm
3below, denitration rate is about 92%, and still can keep comparatively stable denitration rate after repeatedly pulse cleaning being carried out to denitration catalyst membrane filtration material, use denitration catalyst membrane filtration material to be pulled down after a period of time observe find SCR denitration catalytic active substance and porous membrane adhesion condition good.
Embodiment 4
1) preparing porous membrane: first, is the proportioning of 30% according to the percentage by weight of Cr, is that Ni powder and the particle diameter of 3-15 μm is configured to mixed powder for-400 order Cr powder by particle diameter; Then be dispersant with ethanol, PVB is bonding agent, according to the proportional arrangement slurry adding 4gPVB, 60g mixed powder in every 100 milliliters of ethanol; Then, adopt 316L stainless steel mesh to be supporter, its thickness is 70 μm, mesh greatly 90 μm, described pulp spraying is coated in 316L stainless steel sift online and make base substrate dry 4h at 60 DEG C after, the quantity for spray of slurry is every square metre of supporter spraying 250g slurry; Base substrate is positioned in sintering furnace, 4h is sintered at 1150 DEG C, heating rate is 1-5 DEG C/min, cooling i.e. obtained porous membrane after sintering, in this porous membrane, sintering diamond bit is with Ni-Cr solid solution for matrix, and the thickness of this porous membrane is 200 μm, average pore size 24 μm, porosity is 65%, and air permeability is 1890m
3/ m
2hkpa.
2) configuration is as the colloidal sol in intermediate layer material source: by the 1:40:5 mixing by volume of trimethyl silicane sodium alkoxide, alcohol and aqueous solution of nitric acid, it is 3 that adjustment acid content controls pH value, colloidal sol is met the demands, then by described sol impregnation in porous membrane, dip time is 10min, at 80 DEG C, be incubated 4h after dipping, put into resistance furnace after there is stable gel and fire 3h at 400 DEG C, formed by SiO
2the intermediate layer that nano particle is formed.
3) ammonium paratungstate and ammonium metavanadate preparation SCR denitration catalytic active substance precursor solution is adopted, again described precursor solution is impregnated in the porous membrane in attachment intermediate layer, dip time is 20min, then the porous membrane being attached with precursor solution is heat-treated in resistance furnace, 2h is incubated at 300-450 DEG C, namely form SCR denitration catalytic active layer on the intermediate layer, namely obtain denitration catalyst membrane filtration material.In gained denitration catalyst membrane filtration material, the quality of SCR denitration catalytic active substance accounts for 15% of denitration catalyst membrane filtration material gross mass, and the thickness of SCR denitration catalytic active layer is 2.1 μm.
4) the result of use test of denitration catalyst membrane filtration material: above-mentioned denitration catalyst membrane filtration material is cut into suitable shape and loads in the SCR denitration oxidation catalyst filter element of integrated apparatus (see reference paper), and with the pipeline closed, the high-temperature furnace gas that coal-fired plant boiler economizer is got rid of is passed into the air inlet of integrated apparatus, make the furnace gas being mixed with reducing agent by SCR denitration oxidation catalyst filter element, thus under the effect of denitration catalyst membrane filtration material, carry out gas-solid isolated by filtration and the SCR denitration catalysis of furnace gas simultaneously, in the gas that integrated apparatus is discharged, dust content is at 9mg/Nm
3below, denitration rate is about 90%, and still can keep comparatively stable denitration rate after repeatedly pulse cleaning being carried out to denitration catalyst membrane filtration material, use denitration catalyst membrane filtration material to be pulled down after a period of time observe find SCR denitration catalytic active substance and porous membrane adhesion condition good.
Embodiment 5
1) preparing porous membrane: first, is the proportioning of 35% according to the percentage by weight of Cr, is that Ni powder and the particle diameter of 3-15 μm is configured to mixed powder for-400 order Cr powder by particle diameter; Then be dispersant with ethanol, PVB is bonding agent, according to the proportional arrangement slurry adding 4gPVB, 60g mixed powder in every 100 milliliters of ethanol; Then, adopt Ni net to be supporter, its thickness is 70 μm, mesh greatly 100 μm, and described pulp spraying is coated in Ni online and make base substrate dry 4h at 60 DEG C after, the quantity for spray of slurry is every square metre of supporter spraying 250g slurry; Base substrate is positioned in sintering furnace, 2h is sintered at 1250 DEG C, heating rate is 1-5 DEG C/min, cooling i.e. obtained porous membrane after sintering, in this porous membrane, sintering diamond bit is with Ni-Cr solid solution for matrix, and the thickness of this porous membrane is 100 μm, average pore size 30 μm, porosity is 75%, and air permeability is 2210m
3/ m
2hkpa.
2) configuration is as the colloidal sol in intermediate layer material source: by the 8:1:40:5 mixing by volume of butyl titanate, trimethyl silicane sodium alkoxide, alcohol and aqueous solution of nitric acid, it is 3 that adjustment acid content controls pH value, colloidal sol is met the demands, then by described sol impregnation in porous membrane, dip time is 10min, at 80 DEG C, be incubated 4h after dipping, put into resistance furnace after there is stable gel and fire 2h at 450 DEG C, formed by TiO
2nano particle and SiO
2the intermediate layer that nano particle is formed.
3) ammonium paratungstate and ammonium metavanadate preparation SCR denitration catalytic active substance precursor solution is adopted, again described precursor solution is impregnated in the porous membrane in attachment intermediate layer, dip time is 25min, then the porous membrane being attached with precursor solution is heat-treated in resistance furnace, 2h is incubated at 300-450 DEG C, namely form SCR denitration catalytic active layer on the intermediate layer, namely obtain denitration catalyst membrane filtration material.In gained denitration catalyst membrane filtration material, the quality of SCR denitration catalytic active substance accounts for 20% of denitration catalyst membrane filtration material gross mass, and the thickness of SCR denitration catalytic active layer is 2.5 μm.
4) the result of use test of denitration catalyst membrane filtration material: above-mentioned denitration catalyst membrane filtration material is cut into suitable shape and loads in the SCR denitration oxidation catalyst filter element of integrated apparatus (see reference paper), and with the pipeline closed, the high-temperature furnace gas that coal-fired plant boiler economizer is got rid of is passed into the air inlet of integrated apparatus, make the furnace gas being mixed with reducing agent by SCR denitration oxidation catalyst filter element, thus under the effect of denitration catalyst membrane filtration material, carry out gas-solid isolated by filtration and the SCR denitration catalysis of furnace gas simultaneously, in the gas that integrated apparatus is discharged, dust content is at 10mg/Nm
3below, denitration rate is about 92%, and still can keep comparatively stable denitration rate after repeatedly pulse cleaning being carried out to denitration catalyst membrane filtration material, use denitration catalyst membrane filtration material to be pulled down after a period of time observe find SCR denitration catalytic active substance and porous membrane adhesion condition good.
Claims (10)
1. denitration catalyst membrane filtration material, it is a kind of functional material industrial furnace gas to filtration and SCR denitration catalysis double action, comprise membrane filtration material body and be attached to the hole surface of membrane filtration material body and the catalytic active layer be made up of catalytic active substance, it is characterized in that: described membrane filtration material body to be thickness the be porous membrane of 100-1000 μm; The quality of catalytic active layer accounts for the 5-20% of denitration catalyst membrane filtration material gross mass; The thickness of catalytic active layer is 0.5-2.5 μm.
2. denitration catalyst membrane filtration material as claimed in claim 1, is characterized in that: the thickness of described porous membrane is 200-500 μm.
3. denitration catalyst membrane filtration material as claimed in claim 1, it is characterized in that: described denitration catalyst membrane filtration material also comprises the intermediate layer between the hole surface and catalytic active layer of porous membrane, the nano particle that described intermediate layer is piled up by the hole surface at porous membrane formed, and catalytic active layer is attached to the hole surface of porous membrane by this intermediate layer.
4. the denitration catalyst membrane filtration material as described in any one of claim 1-3, is characterized in that: catalytic active layer is by V
2o
5form or with V
2o
5for main component, with WO
3and MoO
3in at least one be auxiliary element mixture form.
5. the denitration catalyst membrane filtration material as described in any one of claim 1-3, is characterized in that: described porous membrane comprises supporter and sintering diamond bit.
6. denitration catalyst membrane filtration material as claimed in claim 5, it is characterized in that: the thickness of described supporter is 0.05-100 μm, the size of mesh is 35-100 μm.
7. denitration catalyst membrane filtration material as claimed in claim 3, is characterized in that: described intermediate layer is by TiO
2nano particle, Al
2o
3nano particle, ZrO
2nano particle, SiO
2at least one in nano particle is formed.
8. the preparation method of denitration catalyst membrane filtration material, comprises the following steps:
1) preparing porous membrane: be the proportioning of 15-35% according to the percentage by weight of Cr, is that Ni powder and the particle diameter of 3-15 μm is configured to mixed powder for-400 order Cr powder by particle diameter; Then be dispersant with ethanol, PVB is bonding agent, according to the proportional arrangement slurry adding 2-5gPVB, 50-70g mixed powder in every 100 milliliters of ethanol; Described slurry is coated in thickness is 0.05-100 μm, the size of mesh is on the supporter of 35-100 μm and dries, be pressed into base substrate and sintering, sintering temperature controls at 900-1250 DEG C and is incubated 2-8h;
2) configuration is as the colloidal sol in intermediate layer material source, again by described sol impregnation in porous membrane, then make the collosol and gel in porous membrane, then to attachment described gel porous membrane heat-treat, make gel conversion be nano particle, and then form intermediate layer;
3) configure catalytic active substance precursor solution, more described precursor solution is impregnated in the porous membrane in attachment intermediate layer, then the porous membrane being attached with precursor solution is heat-treated, namely on described intermediate layer, form catalytic active layer.
9. the preparation method of denitration catalyst membrane filtration material as claimed in claim 8, is characterized in that: described catalytic active layer is by V
2o
5form or with V
2o
5for main component, with WO
3and MoO
3in at least one be auxiliary element mixture form.
10. the preparation method of denitration catalyst membrane filtration material as claimed in claim 8, is characterized in that: described intermediate layer is by TiO
2nano particle, Al
2o
3nano particle, ZrO
2nano particle, SiO
2at least one in nano particle is formed.
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