CN104548923B - Filtration catalytic element and preparation method thereof - Google Patents
Filtration catalytic element and preparation method thereof Download PDFInfo
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- CN104548923B CN104548923B CN201410712568.6A CN201410712568A CN104548923B CN 104548923 B CN104548923 B CN 104548923B CN 201410712568 A CN201410712568 A CN 201410712568A CN 104548923 B CN104548923 B CN 104548923B
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Abstract
The invention discloses a kind of filtration catalytic element and preparation method thereof, thus realize treating the dual function of medium high-efficiency filtering and purifying and catalytic reaction.This filtration catalytic element is that a kind of medium for the treatment of has the function element filtered with catalytic reaction dual function, it has a porous complex, this porous complex includes porous matrix and catalytic active layer, described porous matrix is made up of porous material, described catalytic active layer is attached to porous matrix hole surface and is made up of catalytic active substance, described porous complex also includes 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.The hole surface of the surface ratio porous matrix in intermediate layer is coarse, improves the specific surface area of porous matrix, so that the content of catalytic active substance and the uniformity coefficient of setting are all remarkably improved in porous complex.
Description
Technical field
The present invention relates to the purified treatment of industrial furnace gas, particularly relate to dedusting and the denitration of industrial furnace gas.Wherein, term " industry
Furnace gas " refer to furnace gas produced by Industrial Stoves.Moreover, it relates to a kind of filtration catalytic element, i.e. treat filtrate
Matter has the function element filtered with catalytic reaction dual function.
Background technology
Often containing a large amount of dust and nitrogen oxides in industrial furnace gas, an i.e. coal-fired plant boiler furnace gas of typical example, contained by it
Nitrogen oxides be the main cause facilitating acid rain to be formed, and possibly together with the powder of tens of grams in general every liter of coal-fired plant boiler furnace gas
Dirt.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
It is: first furnace gas is introduced SCR reactor and (during furnace gas introduces SCR reactor, also needs to inject reduction in furnace gas
Agent, this reducing agent is usually ammonia) thus nitrogen oxides is reduced to harmless nitrogen gas, it is achieved furnace gas denitration purifies, then will be de-
Furnace gas introducing electric cleaner after nitre is to remove the dust in furnace gas, then the gas after dedusting is introduced desulfurizing tower desulfurizing and purifying heel row
Put.Described term " SCR " refers to Selective Catalytic Reduction, i.e. SCR.
Catalyst in above-mentioned SCR reactor is the key factor affecting SCR system entirety denitration effect.The SCR being originally developed
Catalyst is graininess, the cellular or tabular catalyst of main employing.On honeycombed catalyst and tabular catalyst
All being placed with and numerous be available for the checkerwork cell that furnace gas passes through, the big I of these checkerwork cells is selected according to concentration and the size of dust in furnace gas
Selecting, during use, furnace gas flows to the opposite side of catalyst, furnace gas therebetween from the side of catalyst by the passage being made up of these checkerwork cells
Contact with the catalytic active substance on checkerwork cell inwall, thus the nitrogen oxides in furnace gas is reduced to harmless nitrogen gas.Above-mentioned honeycomb
Shape catalyst and tabular catalyst are typically made up of carrier and catalytic active layer, and wherein carrier is first made into cellular or tabular
(general employing is extruded), adheres to the catalytic active layer being made up of catalytic active substance the most again on carrier.
Although the big I of the checkerwork cell of honeycombed catalyst and tabular catalyst is selected according to concentration and the size of dust in furnace gas
Select, but the problem yet suffering from actual use being blocked by dust.Further, since SCR catalyst is direct and high dustiness
Furnace gas contact, be therefore easily caused catalytic active substance poisoning, service life shorten.Additionally, said method employs electricity
Cleaner unit removes the dust in furnace gas, but is had selectivity factors such as feature of gathering dust by electric precipitation and affected and the most often occur that electricity removes
The problem that dirt device exit gas dustiness exceeds standard.Therefore, for the such as contour dust of coal-fired plant boiler furnace gas and nitrogen oxidation at present
The purification techniques of the industrial furnace gas of thing content need further to improve.
On the other hand, the applicant of the present patent application provides a kind of catalytic reforming in the Chinese patent literature of CN102925206A
Technique and the corresponding film filtering element for catalytic reforming.The document proposes by a kind of film filtering element retain and
Catalytic action realizes the filtration to oil gas and catalytic reforming simultaneously thus solves that reforming catalyst number of dropouts is big and reforming catalyst holds
The easily technology design of coking.But, the targeted technical field of the document belongs to cracking hydrocarbon oil field, residing for the present patent application
Industrial furnace gas dedusting denitration field relatively far apart；Further, cracking hydrocarbon oil and industrial furnace gas dedusting denitration face the most respectively many not
Same technical problem, such as industrial furnace gas dustiness are big, require hot conditions (SCR catalytic reaction temperature one in denitrification process
As require at 320～420 DEG C), denitration rate require the most high, the most again with denitration rate require a height of industrial furnace gas SCR urge
Change the technical difficult points of denitration.Therefore, general technical staff is not easy to recognize the technology design that will propose in above-mentioned document
Use for reference in industrial furnace gas dedusting denitration.
Summary of the invention
First the technical problem to be solved is to provide a kind of industrial furnace that industrial furnace gas can carry out dedusting and denitration simultaneously
Gas dedusting denitrification integral processing method and special equipment；Secondly the present invention also provides that one includes but not limited to can be in above-mentioned work
Filtration catalytic element of application and preparation method thereof in industry furnace gas dedusting denitrification integral processing method, thus realize treating filtrate
Matter high-efficiency filtering and purifying and the dual function of catalytic reaction.
To this end, the present invention proposes following industrial furnace gas dedusting denitrification integral processing method, the step of the method includes: (1)
With the pipeline closed, industrial furnace gas is passed through the air inlet of de-dusting de-nitration integrated, and is not taken off by dedusting to transmitting
Nitre integrated apparatus carries out injecting in the furnace gas of dedusting denitration process reducing agent；(2) furnace gas being mixed with reducing agent is made to pass through dedusting
Filtration catalytic element in denitrification integrated device, thus the gas-solid simultaneously carrying out furnace gas under the effect of filtration catalytic element is filtered
Separate and SCR denitration；(3) gas-solid is carried out from the air vent discharge of described de-dusting de-nitration integrated by filtration catalytic element
Gas after filter separation and SCR denitration, then leads to follow-up link by this gas；Wherein, described filtration catalytic element is one
Planting and have filtration and the function element of SCR denitration catalysis dual function to industrial furnace gas, it has average pore size is 1～200 μm
Porous complex, this porous complex includes: porous matrix, described porous matrix by sintering diamond bit or sintering pottery
Porcelain porous material is constituted, and has the network hole of 3 D stereo connection in this porous matrix；And catalytic active layer, described catalysis
Active layer is attached to porous matrix hole surface and is made up of catalytic active substance." average pore size " is that this area characterizes porous material hole
The generic term of structure, general employing bubble method measures.The average pore size of porous complex can basis in 1～200 μ m
Concrete industrial furnace gas gas solid separation filters needs and is set.In said method, due to attached on the hole surface of porous complex
The catalytic active layer being made up of catalytic active substance, furnace gas is being filtered the process separated by filtration catalytic element by gas-solid
In can contact with catalytic active substance again, it is achieved in furnace gas nitrogen oxides SCR denitration catalysis.Owing to porous matrix is by burning
Knot metal polyporous material or sintering ceramic porous material are constituted, and therefore have excellent resistance to elevated temperatures, it is possible to anti-in SCR catalysis
Work stable in answering temperature range；And porous matrix has the network hole of 3 D stereo connection, thus can ensure that stove
Gas is the most sufficient when by via matrix to be contacted with catalytic active substance.
On the basis of said method, inventor is it has furthermore been found that be made up of sintering diamond bit or sintering ceramic porous material
The hole surface generally speaking smoother of porous matrix, have impact on the specific surface area of porous matrix, if directly by catalytic active layer
Being attached to the hole surface of porous matrix, in porous complex, the content of catalytic active substance is the highest, thus can affect industrial furnace gas
Denitration rate.In order to solve the problems referred to above, above-mentioned industrial furnace gas dedusting denitrification integral processing method is improved to further: institute
Stating porous complex and also include the intermediate layer between porous matrix and catalytic active layer, described intermediate layer is by porous matrix table
The nano-particle that face is piled up is constituted, and catalytic active layer is attached to porous matrix hole surface by this intermediate layer.Owing to intermediate layer is
Being 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 coarse very
Many, thus substantially increase the specific surface area of porous matrix, so that the content of catalytic active substance and setting in porous complex
Uniformity coefficient is all remarkably improved, and the denitration rate of industrial furnace gas has been effectively ensured.
And as the another improvement to said method, described filtration catalytic element also include being positioned on porous complex windward side and with
Sintering diamond bit or the film layer that sintering ceramic porous material is matrix, the average pore size of this film layer is 1～100 μm and is less than
The average pore size of porous complex.Term " windward side " refers to the side surface first contacted on porous complex with furnace gas.When
After arranging film layer on the windward side of porous complex, due to the existence of film layer, furnace gas must first contact with film layer, thus by film layer
At least some of dust in furnace gas is intercepted, the touch opportunity of dust and porous complex is decreased or even eliminated, the most anti-
Only catalytic active substance poisoning.In the case of being provided with film layer, the average pore size of this film layer is preferably with as far as possible by furnace gas
Dust sets for the purpose of removing totally, and the average pore size of porous complex is preferably with the filtration flux at guarantee certain level
Set for the purpose of making SCR catalytic reaction as far as possible fully under premise.
The Special industrial furnace gas de-dusting de-nitration integrated of said method, including the gas being provided with air inlet, air vent and slag-drip opening
Body defecator, is provided with filtration catalytic element in this gas-filtering device, described filtration catalytic element is a kind of to industrial furnace gas
Having and filter and the function element of SCR denitration catalysis dual function, it has the porous complex that average pore size is 1～200 μm,
This porous complex includes: porous matrix, and described porous matrix is made up of sintering diamond bit or sintering ceramic porous material,
This porous matrix has the network hole of 3 D stereo connection；And catalytic active layer, described catalytic active layer is attached to porous
The hole surface of matrix is also made up of catalytic active substance.As a kind of improvement of said apparatus, described porous complex also includes
Intermediate layer between porous matrix and catalytic active layer, described intermediate layer is by the nano-particle institute structure piled up on porous matrix
Becoming, described catalytic active layer is attached to porous matrix hole surface by this intermediate layer.As the another improvement of said apparatus, described
Filtration catalytic element also includes being positioned on porous complex windward side and with sintering diamond bit or sintering ceramic porous material is
The film layer of matrix, the average pore size of this film layer is 1～100 μm and the average pore size less than porous complex.
Include but not limited to the filtration catalytic element can applied in above-mentioned industrial furnace gas dedusting denitrification integral processing method, be one
Kind is treated medium and is had the function element filtered with catalytic reaction dual function, and it has a porous complex, and this porous is multiple
Zoarium includes that porous matrix and catalytic active layer, described porous matrix are made up of porous material, and described catalytic active layer is attached to many
Matrix hole surface, hole is also made up of catalytic active substance, and described porous complex also includes intermediate layer, and described intermediate layer is by porous
The nano-particle that matrix surface is piled up is constituted, and described catalytic active layer is attached to porous matrix hole surface by intermediate layer.Due to
Intermediate layer is to be made up of the nano-particle at porous matrix surface sediment, therefore the hole table of the surface ratio porous matrix in intermediate layer
Face is coarse a lot, thus substantially increases the specific surface area of porous matrix, so that the content of catalytic active substance in porous complex
All it is remarkably improved with the uniformity coefficient arranged, improves catalytic reaction rate.
This filtration catalytic element can be specifically a kind of Functional Unit to industrial furnace gas with filtration and SCR denitration catalysis dual function
Part, the average pore size of described porous complex is 1～200 μm, and described porous matrix is by sintering diamond bit or sintering pottery
Porcelain porous material is constituted, and has the network hole of 3 D stereo connection in this porous matrix.Wherein, described intermediate layer can be by TiO2
Nano-particle, AlO2Nano-particle, ZrO2Nano-particle or SiO2Nano-particle is constituted.Described catalytic active layer can be by V2O5
Constitute or with V2O5For main component, with WO3And MoO3In the mixture that at least one is auxiliary element constitute.Additionally, this mistake
Filter catalysis element may also include further and is positioned on porous complex windward side and with sintering diamond bit or sinter ceramic porous
Material is the film layer of matrix, and the average pore size of this film layer is 1～100 μm and the average pore size less than porous complex.
The preparation method of above-mentioned filtration catalytic element, including following link: 1) prepare porous matrix；2) configuration is as intermediate layer
The colloidal sol of material source, then by described sol impregnation to porous matrix, then make the collosol and gel in porous matrix, more right
The porous matrix adhering to described gel carries out heat treatment, and making gel conversion is nano-particle, and then forms intermediate layer；3) configuration is urged
Change active substance precursor solution, more described precursor solution is impregnated in the porous matrix in attachment intermediate layer, then to attachment
The porous matrix having precursor solution carries out heat treatment, forms catalytic active layer on described intermediate layer.
When described filtration catalytic element is a kind of function element to industrial furnace gas with filtration and SCR denitration catalysis dual function,
The average pore size of described porous complex is 1～200 μm, and described porous matrix is many by sintering diamond bit or sintering pottery
Porous materials is constituted, when having the network hole of 3 D stereo connection in this porous matrix, in described link 1) and link 2) between
Following additional link be may further be provided, i.e. in the windward side overlying preparation liquid of porous matrix, the then porous to coherent film liquid
Matrix is sintered making film liquid be changed into sintering diamond bit or the sintering ceramic porous material film layer as matrix, this film layer
Average pore size be 1～100 μm and less than the average pore size of porous complex.
Accompanying drawing explanation
Fig. 1 is industrial furnace gas dedusting denitrification integral processing method process chart when coal-fired plant boiler furnace gas processes.
Fig. 2 is the schematic diagram of industrial furnace gas de-dusting de-nitration integrated in Fig. 1.
Fig. 3 is the structural representation of filtration catalytic element of the present invention.
Fig. 4 be in Fig. 3 A-A to sectional view.
The structural representation of the immersion system that the filtration catalytic element that Fig. 5 is the embodiment of the present invention is used when preparing.
Fig. 6 is the SEM photograph (before arranging intermediate layer, 100 times of amplifications) of the filtration catalytic element porous matrix of the embodiment of the present invention.
Fig. 7 is the SEM photograph (after arranging intermediate layer, 100 times of amplifications) of the filtration catalytic element porous matrix of the embodiment of the present invention.
Fig. 8 is the SEM photograph (before arranging intermediate layer, 500 times of amplifications) of the filtration catalytic element porous matrix of the embodiment of the present invention.
Fig. 9 is the SEM photograph (after arranging intermediate layer, 500 times of amplifications) of the filtration catalytic element porous matrix of the embodiment of the present invention.
Detailed description of the invention
Fig. 1 shows at the coal-fired plant boiler furnace gas of a kind of industrial furnace gas dedusting denitrification integral processing method applying the present invention
Science and engineering process flow.As it is shown in figure 1, this coal-fired plant boiler furnace gas processing technological flow is particularly as follows: first, with the pipeline closed
The high-temperature furnace gas that coal-fired plant boiler 200 economizer is got rid of is passed through the air inlet of de-dusting de-nitration integrated 100, simultaneously to
Furnace gas in pipeline injects reducing agent, such as ammonia；Then, make the furnace gas being mixed with reducing agent by dedusting denitrification integral
Filtration catalytic element in device 100, thus carry out under the effect of filtration catalytic element simultaneously furnace gas gas-solid filter separate and
SCR denitration；Afterwards, gas-solid is carried out from the air vent discharge of described de-dusting de-nitration integrated 100 by filtration catalytic element
Gas after filter separation and SCR denitration, then leads to this gas air preheater 300 (i.e. air preheater) and carries out waste heat recovery,
Air preheater 300 expellant gas is entered after blower fan 400 and is discharged by chimney 600 after desulfurizer 500 carries out desulfurization process.
The rear end being positioned at de-dusting de-nitration integrated 100 in this coal-fired plant boiler furnace gas processing technological flow does not has other dedusting to set
Standby, the dedusting of coal-fired plant boiler 200 furnace gas and denitration are only carried out by de-dusting de-nitration integrated 100, simplify current
Coal-fired plant boiler furnace gas processing technological flow.
As in figure 2 it is shown, the industrial furnace gas dedusting denitrification integral dress used in above-mentioned coal-fired plant boiler furnace gas processing technological flow
Putting 100 and can regard a gas-filtering device as, this gas-filtering device is provided with air inlet T1, air vent T2, slag-drip opening T3,
And be respectively equipped with at blowback medium entrance T4, described air inlet T1, air vent T2, slag-drip opening T3, blowback medium entrance T4
Control valve K1, K2, K3, K4, be provided with filtration catalytic element 110 in the shell of gas-filtering device, this filtration catalytic element
The existence of 110 makes to define two spaces kept apart through this filtration catalytic element 110 each other in gas-filtering device.
A kind of function that coal-fired plant boiler furnace gas is had filtration and SCR denitration catalysis dual function of filtration catalytic element 110
Element, as shown in Figure 3,4, it has the porous complex 111 that average pore size is 1～200 μm, this porous complex 111
Including: porous matrix 111a, described porous matrix 111a are made up of sintering diamond bit or sintering ceramic porous material,
This porous matrix has the network hole of 3 D stereo connection；Catalytic active layer 111c, described catalytic active layer 111c adhere to
In the hole surface of porous matrix 111a and it is made up of catalytic active substance；And it is positioned at porous matrix 111a and catalytic active layer
Intermediate layer 111b between 111c, described intermediate layer 111b are made up of the nano-particle at porous matrix 111a surface sediment,
Catalytic active layer 111c is attached to porous matrix 111a hole surface by this intermediate layer 111b.
Above-mentioned intermediate layer is preferably by TiO2Nano-particle, AlO2Nano-particle, ZrO2Nano-particle or SiO2Nano-particle is constituted.
TiO2、AlO2、ZrO2And SiO2It is proved to have good as the carrier material in existing honeycombed catalyst and tabular catalyst
Using effect.It is theoretically, all that in existing SCR catalyst, used catalytic active substance all can be as in the application
Constituting the catalytic active substance of catalytic active layer 111c, such as catalytic active layer 111c can be by V2O5Constitute or with V2O5For mainly
Composition, with WO3And MoO3In the mixture that at least one is auxiliary element constitute.
Above-mentioned filtration catalytic element 110 can be only made up of porous complex 111, now the average hole of porous complex 111
Footpath is typically based on the content of dust, dust granules thing size, design in actual targeted industrial furnace gas in 1～200 μ m
Efficiency of dust collection and filtration flux carry out concrete setting, usually 15～50 μm.Certainly, filtration catalytic element 110 can also
As shown in Figure 3 by porous complex 111 be positioned on porous complex 111 windward side and with sintering diamond bit or sintering
Ceramic porous material is that the film layer 112 of matrix is constituted, and the average pore size of this film layer 112 is 1～100 μm and is less than porous complex
The average pore size of 111.After arranging film layer 112 on the windward side at porous complex 111, due to the existence of film layer 112,
Furnace gas must first contact with film layer 112, thus is intercepted at least some of dust in furnace gas by film layer 112, reduces very
To elimination dust and the touch opportunity of porous complex 111, catalytic active substance is effectively prevented to be poisoned.It is being provided with film layer 112
In the case of, the average pore size of this film layer 112 preferably sets (one for the purpose of being removed totally by the dust in furnace gas as far as possible
As be 10～20 μm), and the average pore size of porous complex 111 preferably with ensure certain level filtration flux on the premise of
(generally 40～70 μm) is set for the purpose of making SCR catalytic reaction as far as possible fully.
Making of above-mentioned industrial furnace gas de-dusting de-nitration integrated 100 (filtration catalytic element 110 uses the structure shown in Fig. 3)
It is: opening controlling valve K1, K2, closing control valve K3, K4 that the furnace gas being mixed with reducing agent enters from air inlet T1 by method
Industrial furnace gas de-dusting de-nitration integrated 100, the most again the filtration catalytic element 110 in this device, at this moment, furnace gas is first
By film layer 112, the filtering accuracy of film layer 112 is higher, substantially completely can intercept also by the dust in furnace gas, filters
After gas again by porous complex 111, this process and the catalytic active layer on the 111d inwall of porous complex 111 duct
111c is fully contacted and makes the nitrogen oxides in gas be reduced to nitrogen, and reacted gas is from industrial furnace gas dedusting denitrification integral
The air vent T2 output of device 100.After continuing for some time, closing control valve K1, K2, opening controlling valve K4, thus sharp
With blowback medium, filtration catalytic element 110 is regenerated.When needing deslagging, opening control valve K3, dust is from this industrial furnace gas
The slag-drip opening T3 output of de-dusting de-nitration integrated 100.
The preparation method of above-mentioned filtration catalytic element 110 includes following link: 1) prepare porous matrix 111a；2) configuration conduct
The colloidal sol of intermediate layer 111c material source, then by described sol impregnation to porous matrix 111a, then make porous matrix 111a
In collosol and gel, then to adhere to described gel porous matrix 111a carry out heat treatment, making gel conversion is nano-particle,
And then form intermediate layer 111b；3) configuration catalytic active substance precursor solution, more described precursor solution is impregnated into attachment
In the porous matrix 111a of intermediate layer 111b, then the porous matrix 111a being attached with precursor solution is carried out heat treatment,
Catalytic active layer 111c is formed on described intermediate layer 111b.And when being provided with film layer 112 on the windward side of porous complex 111
Time, above-mentioned link 1) and link 2) between be additionally provided with following additional link, i.e. in the windward side overlying system of porous matrix 111a
Film liquid, then the porous matrix 111a to coherent film liquid is sintered making film liquid be changed into sintering diamond bit or sintering pottery
Porcelain porous material is the film layer 112 of matrix.
The above-mentioned filtration catalytic element 110 with film layer 112 is first to sinter shape film forming layer 112 on porous matrix 111a, then
Intermediate layer 111b and catalytic active layer 111c is formed again by subsequent technique.Owing to film layer 112 is formed at intermediate layer 111b and urges
Change before active layer 111c, it is thus possible to intermediate layer 111b and catalytic active layer 111c when avoiding high temperature sintering shape film forming layer 112
Damage.But, just because of film layer 112 is formed formerly, follow-up colloidal sol (intermediate layer 111c material source) is impregnated into many
Can be impregnated into the most equally on film layer 112 time in the matrix 111a of hole, on film layer 112, finally also can form shaggy intermediate layer,
The most both can change the pore structure of film layer 112, also increase the roughness on film layer 112 surface simultaneously, due to 112 master of film layer
Wanting filtration, in the case of film layer 112 pore structure changes and roughness increases, dust granules tiny in furnace gas more holds
Easily it is attached on film layer 112 and not easily passs through reverse gas cleaning remove from film layer 112.Therefore, by molten in above-mentioned preparation method
Glue and/or catalytic active substance precursor solution are avoided being impregnated into film layer 112 when being impregnated into porous matrix 111a the most as far as possible.
In order to avoid as far as possible being impregnated into when colloidal sol and/or catalytic active substance precursor solution are impregnated into porous matrix 111a
Film layer 112, a kind of way is the link 2 in above-mentioned preparation method) and/or link 3) in use by be used for the liquid of dipping from
The leeward impregnation technology carrying out towards direction, windward side permeating of porous matrix 111a, thus reduce the pickup on film layer 112.
It addition, on the basis of above-mentioned way, also can when dipping further windward side at film layer 112 maintain one and be used in dipping
Liquid can penetrate porous matrix from porous matrix 111a leeward towards direction, windward side but can not be through the reverse gas of film layer
Pressure.Below as a example by the porous matrix 111a of tubulose, illustrate how to use the immersion system shown in Fig. 5 to prevent colloidal sol, catalysis
Film layer 112 will not be impregnated into when active substance precursor solution is impregnated into porous matrix 111a.
As it is shown in figure 5, the both ends open of the tubular porous matrix 111a of coherent film layer 112 is (when catalytic active layer 111c is formed
After, then by a plug, filtration catalytic element 110 is made in one end closure of tubular porous matrix 111a, will filter during use
The opening of catalysis element 110 is arranged on the orifice plate of industrial furnace gas de-dusting de-nitration integrated 100, filtration catalytic element 110
Outer tube surface be windward side, during work furnace gas from outer tube towards tube chamber move, i.e. identical with current smoke filtration chimney filter working method),
The upper port of tubular porous matrix 111a and lower port are separately mounted on upper cover 710 and the low head 720 of immersion system, on
It is respectively equipped with inlet 711 and leakage fluid dram 721 on end socket 710 and low head 720, upper cover 710 and low head will be installed
The tubular porous matrix 111a of 720 loads in the shell 730 of immersion system, and by upper location-plate 740 and lower location-plate 750
Upper cover 710 and low head 720 are positioned, so that tubular porous matrix 111a is fixed on the shell 730 of immersion system
Internal.Inlet 711 and leakage fluid dram 721 are respectively connected to the pipe-line system for steeping liq flowing, this pipe-line system sets
There is regulator；Air inlet 731 on immersion system shell 730 is connected feeder, this feeder is again provided with adjust
Pressure device, air inlet 731 and immersion system are internally located at the cavity conducting on tubular porous matrix 111a outside film layer 112.Leaching
During stain, the liquid for dipping enters in the tube chamber of tubular porous matrix 111a from inlet 711 and flows from leakage fluid dram 721
Go out, make the tubular porous intraluminal liquid of matrix 111a maintain on pressure P1, simultaneously by the regulator in pipe-line system
It is passed through air from air inlet 731 to immersion system by feeder, utilizes the regulator in feeder to make tubular porous base
Body 111a extraneous air maintains on pressure P2, and wherein, P1-P2=P3, P3 are the liquid that ought be used for dipping tested out in advance
Penetrate pressure drop produced by the sample of tubular porous matrix 111a.So, it becomes possible to be used in the liquid of dipping from porous matrix
111a leeward penetrates porous matrix 111a towards direction, windward side but can not pass through film layer 112.
Embodiment
The filtration catalytic element 110 that preparation processes for coal-fired plant boiler furnace gas dedusting denitrification integral, and it is de-to test its dedusting
Nitre effect.The preparation of filtration catalytic element 110, first, uses-100 mesh aluminium powders 30% (weight) ,-200 mesh iron powders 70%
The formula of (weight), makes intermetallic Fe-Al compound porous matrix 111a by powder metallurgic method sintering, tests its air and leads to
Amount is 368m3/m2.h.kpa, average pore size is 65 μm, and room temperature tension is 90MPa, porosity 42%.Fig. 6 and Fig. 8 is respectively
Amplify 100 times and the photo of 500 times under an electron microscope for porous matrix 111a, porous matrix 111a wherein be can be observed
Hole surface relatively smooth.Then configuration film liquid, specific practice is with binder solution, powder to be mixed high speed dispersion, wherein
Powder is mixed with the aluminium powder 30% (weight) that particle diameter is 3～10 μm by the iron powder 70% (weight) that particle diameter is 5～15 μm,
Binder solution be with PVB as solute, ethanol configure by the mass concentration of 2% for solvent and form, the weight of powder after the configuration of film liquid
For film liquid weight 40%.At the film liquid that the windward side overlying system of porous matrix 111a configures, the then porous to coherent film liquid
Matrix 111a is sintered making film liquid be changed into sintering diamond bit or the sintering ceramic porous material film layer 112 as matrix,
The average pore size of film layer 112 is 25 μm.Hereafter prepare as intermediate layer material source colloidal sol, will butyl titanate, go from
Sub-water, ethanol and nitric acid acid 2:1:20 in mass ratio mixing, adjust acid content controlling pH value is 4, makes colloidal sol meet requirement,
Then by described sol impregnation to porous matrix 111a, at 105 DEG C, it is incubated 2 hours after dipping, puts after stable gel occurs
Enter and resistance furnace is fired at 450 DEG C 1h, form intermediate layer 111b.Fig. 7 and Fig. 9 is respectively after forming intermediate layer 111b
Porous matrix 111a amplifies 100 times and the photo of 500 times under an electron microscope, wherein can be observed porous matrix 111a's
Hole surface is attached to the rough surface formed by nano-particle.Finally use ammonium paratungstate and ammonium metavanadate preparation catalytic active substance
Precursor solution, more described precursor solution is impregnated in the porous matrix 111a of attachment intermediate layer 111b, then to attachment
The porous matrix having precursor solution burns into row heat treatment in resistance furnace, is incubated 2h, in described intermediate layer at 300～450 DEG C
111b upper formation catalytic active layer 111c.
Above-mentioned filtration catalytic element 110 is loaded in integrated apparatus, and with the pipeline closed by coal-fired plant boiler 200 province coal
The high-temperature furnace gas that device is got rid of is passed through the air inlet of integrated apparatus, makes the furnace gas being mixed with reducing agent pass through filtration catalytic element, from
And the gas-solid carrying out furnace gas under the effect of filtration catalytic element 110 is filtered and separated and SCR denitration simultaneously, integrated apparatus is discharged
Gas in dust content≤10mg/Nm3, denitration rate >=85%.
Claims (6)
1. filtration catalytic element, is that a kind of medium for the treatment of has the function element filtered with catalytic reaction dual function, its tool
Having a porous complex, this porous complex includes that porous matrix and catalytic active layer, described porous matrix are made up of porous material,
Described catalytic active layer is attached to porous matrix hole surface and is made up of catalytic active substance, it is characterised in that: described porous is combined
Body also includes that intermediate layer, described intermediate layer are made up of the nano-particle at porous matrix surface sediment, and described catalytic active layer leads to
Cross intermediate layer and be attached to porous matrix hole surface；Filtration catalytic element also includes being positioned on porous complex windward side and with sintered gold
Genus polyporus material or the film layer that sintering ceramic porous material is matrix, the average pore size of this film layer is 1～100 μm and is less than porous again
Fit average pore size, the unattached nano-particle in order to constitute intermediate layer in surface of described film layer；The system of this filtration catalytic element
Preparation Method includes following link: 1) prepare porous matrix；2) configuration is as the colloidal sol in intermediate layer material source, then by described molten
Glue is impregnated in porous matrix, then makes the collosol and gel in porous matrix, then carries out the porous matrix adhering to described gel
Heat treatment, making gel conversion is nano-particle, and then forms intermediate layer；3) configuration catalytic active substance precursor solution, then will
Described precursor solution is impregnated in the porous matrix in attachment intermediate layer, then carries out the porous matrix being attached with precursor solution
Heat treatment, forms catalytic active layer on described intermediate layer；In described link 1) and link 2) between be additionally provided with following additional ring
Joint, i.e. at the windward side overlying preparation liquid of porous matrix, then the porous matrix to coherent film liquid is sintered making film liquid be changed into
With sintering diamond bit or the sintering ceramic porous material film layer as matrix, the average pore size of this film layer is 1～100 μm and little
Average pore size in porous complex；Described link 2) in use and will be used for leeward towards meeting from porous matrix of liquid of dipping
Direction, wind face carries out the impregnation technology permeated, and during dipping, windward side one liquid being used in dipping of maintenance at film layer can be from many
Hole matrix leeward penetrates porous matrix towards direction, windward side but can not be through the reverse air pressure of film layer.
2. filtration catalytic element as claimed in claim 1, it is characterised in that: it is that one has filtration and SCR to industrial furnace gas
The function element of denitration catalyst dual function, the average pore size of described porous complex is 1～200 μm, and described porous matrix by
Sintering diamond bit or sintering ceramic porous material are constituted, and have the network hole of 3 D stereo connection in this porous matrix.
3. filtration catalytic element as claimed in claim 2, it is characterised in that: described intermediate layer is by TiO2Nano-particle, AlO2
Nano-particle, ZrO2Nano-particle or SiO2Nano-particle is constituted.
4. filtration catalytic element as claimed in claim 2 or claim 3, it is characterised in that: described catalytic active layer is by V2O5Constitute
Or with V2O5For main component, with WO3And MoO3In the mixture that at least one is auxiliary element constitute.
5. the preparation method of filtration catalytic element, including following link: 1) prepare porous matrix；2) configuration is as intermediate layer material
The colloidal sol in material source, then by described sol impregnation to porous matrix, then make the collosol and gel in porous matrix, then to attached
The porous matrix described gel carries out heat treatment, and making gel conversion is nano-particle, and then forms intermediate layer；3) configuration catalysis
Active substance precursor solution, more described precursor solution is impregnated in the porous matrix in attachment intermediate layer, then to being attached with
The porous matrix of precursor solution carries out heat treatment, forms catalytic active layer on described intermediate layer；In described link 1) and ring
Joint 2) between be additionally provided with following additional link, i.e. at the windward side overlying preparation liquid of porous matrix, then many to coherent film liquid
Hole matrix is sintered making film liquid be changed into sintering diamond bit or the sintering ceramic porous material film layer as matrix, this film
The average pore size of layer is 1～100 μm and the average pore size less than porous complex；Described link 2) and/or link 3) middle employing
By be used for dipping liquid from the leeward impregnation technology carrying out towards direction, windward side permeating of porous matrix, at film layer during dipping
Windward side maintain the liquid being used in dipping can penetrate porous matrix from porous matrix leeward towards direction, windward side but not
Can be through the reverse air pressure of film layer.
6. the preparation method of filtration catalytic element as claimed in claim 5, it is characterised in that: described filtration catalytic element is one
Planting and have filtration and the function element of SCR denitration catalysis dual function to industrial furnace gas, the average pore size of described porous complex is
1～200 μm, and described porous matrix by sintering diamond bit or sintering ceramic porous material constitute, in this porous matrix have
There is the network hole that 3 D stereo connects.
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| FR3036626B1 (en) * | 2015-05-29 | 2019-12-20 | Technologies Avancees Et Membranes Industrielles | SEPARATION ELEMENT WITH A THREE-DIMENSIONAL CIRCULATION NETWORK FOR THE FLUID MEDIUM TO BE TREATED |
| CN107876043B (en) * | 2017-11-24 | 2018-08-31 | 济南玉泉生物发电有限公司 | A kind of ceramic catalytic filter core and flue gas integration desulfurization denitration dust removal method for gas cleaning |
| CN113828149A (en) * | 2021-09-01 | 2021-12-24 | 浙江海亮环境材料有限公司 | Coating method for improving denitration efficiency of catalytic fiber filter tube and filter tube |
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