CN104548923A - Filtrating and catalyzing component and preparation method thereof - Google Patents
Filtrating and catalyzing component and preparation method thereof Download PDFInfo
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- CN104548923A CN104548923A CN201410712568.6A CN201410712568A CN104548923A CN 104548923 A CN104548923 A CN 104548923A CN 201410712568 A CN201410712568 A CN 201410712568A CN 104548923 A CN104548923 A CN 104548923A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000003197 catalytic effect Effects 0.000 claims abstract description 124
- 238000001914 filtration Methods 0.000 claims abstract description 91
- 239000011148 porous material Substances 0.000 claims abstract description 55
- 239000013543 active substance Substances 0.000 claims abstract description 28
- 239000002105 nanoparticle Substances 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 239000011159 matrix material Substances 0.000 claims description 122
- 239000007788 liquid Substances 0.000 claims description 22
- 238000005245 sintering Methods 0.000 claims description 21
- 239000000919 ceramic Substances 0.000 claims description 18
- 229910003460 diamond Inorganic materials 0.000 claims description 18
- 239000010432 diamond Substances 0.000 claims description 18
- 238000006555 catalytic reaction Methods 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 15
- 230000009471 action Effects 0.000 claims description 11
- 238000007598 dipping method Methods 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- 229910017090 AlO 2 Inorganic materials 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 230000001427 coherent effect Effects 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000000746 purification Methods 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract 7
- 230000004913 activation Effects 0.000 abstract 3
- 230000009977 dual effect Effects 0.000 abstract 2
- 239000007789 gas Substances 0.000 description 103
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 24
- 239000000428 dust Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 22
- 239000003054 catalyst Substances 0.000 description 17
- 238000010410 dusting Methods 0.000 description 17
- 238000006396 nitration reaction Methods 0.000 description 17
- 230000008569 process Effects 0.000 description 10
- 239000003638 chemical reducing agent Substances 0.000 description 8
- 238000007654 immersion Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 238000003672 processing method Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000003321 amplification Effects 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 238000003199 nucleic acid amplification method Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000001833 catalytic reforming Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000006424 Flood reaction Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Catalysts (AREA)
- Filtering Materials (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a filtrating and catalyzing component and a preparation method thereof. The component can be used for achieving the dual effects of efficient filtration and purification and reaction catalyzing on to-be-filtered materials. The filtrating and catalyzing component is a component with the dual effects of filtration and reaction catalyzing on the to-be-filtered materials, and comprises a porous complex, wherein the porous complex comprises a porous substrate and a catalytic activation layer, the porous substrate is made of porous materials, the catalytic activation layer is attached to the hole surface of the porous substrate and made of catalytic active substances, the porous complex also comprises a middle layer, the middle layer is made of nanoparticles accumulated on the surface of the porous substrate, and the catalytic activation layer is attached to the hole surface of the porous substrate by the middle layer. The surface of the middle layer is rougher than the hole surface of the porous substrate, so that the specific surface area of the porous substrate is increased, the content of the catalytic active substances in the porous complex can be significantly increased, and the uniformity of the catalytic active substances in the porous complex can be significantly improved.
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 " industrial furnace gas " refers to the furnace gas that Industrial Stoves produce.In addition, the invention still further relates to a kind of filtration catalytic element, namely treat the function element that medium has filtration and catalytic reaction double action.
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 be harmless nitrogen gas by reduction of nitrogen oxide, 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 Selective Catalytic Reduction, 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.
On the other hand, the applicant of the present patent application provides a kind of catalytic reforming process and the corresponding film filtering element for catalytic reforming in the Chinese patent literature of CN102925206A.Propose in the document and to realize with catalytic action the filtration of oil gas and catalytic reforming simultaneously by retaining of a kind of film filtering element thus solve the technical conceive of the large and easy coking of reforming catalyst of reforming catalyst number of dropouts.But, the document for technical field belong to cracking hydrocarbon oil field, with the industrial furnace gas dedusting denitration field residing for the present patent application relatively far apart; And, cracking hydrocarbon oil faces again many different technical problems respectively from industrial furnace gas dedusting denitration, such as industrial furnace gas dustiness is large, in denitrification process, require that hot conditions (SCR catalytic reaction temperature General Requirements is at 320 ~ 420 DEG C), denitration rate require very high, wherein requires the high technical difficult points for industrial furnace gas SCR catalytic denitration with denitration rate especially again.Therefore, general technical staff is not easy to recognize and is used for reference in industrial furnace gas dedusting denitration by the technical conceive proposed in above-mentioned document.
Summary of the invention
First technical problem to be solved by this invention is to provide a kind of industrial furnace gas dedusting denitrification integral processing method and the special equipment that can carry out dedusting and denitration to industrial furnace gas simultaneously; Secondly also will provide a kind of includes but not limited to filtration catalytic element can applied in above-mentioned industrial furnace gas dedusting denitrification integral processing method and preparation method thereof in the present invention, thus realizes the double action treating medium high-efficiency filtering and purifying and catalytic reaction.
For this reason, the present invention proposes following industrial furnace gas dedusting denitrification integral processing method, the step of the method comprises: industrial furnace gas is passed into the air inlet of de-dusting de-nitration integrated with the pipeline closed by (1), and to being transmitted but also not undertaken injecting reducing agent in the furnace gas of dedusting denitration process by de-dusting de-nitration integrated; (2) make the furnace gas being mixed with reducing agent by the filtration catalytic element in de-dusting de-nitration integrated, thus under the effect of filtration catalytic element, carry out gas-solid isolated by filtration and the SCR denitration of furnace gas simultaneously; (3) carry out the gas after gas-solid isolated by filtration and SCR denitration from the exhaust outlet discharge of described de-dusting de-nitration integrated by filtration catalytic element, then this gas is led to follow-up link; Wherein, described filtration catalytic element is a kind of function element industrial furnace gas to filtration and SCR denitration catalysis double action, it has the porous complex that average pore size is 1 ~ 200 μm, this porous complex comprises: porous matrix, described porous matrix is made up of sintering diamond bit or sintered ceramic porous material, has the network hole that 3 D stereo is communicated with in this porous matrix; And catalytic active layer, described catalytic active layer is attached to porous matrix hole surface and is made up of catalytic active substance." average pore size " is the generic term of this area characterizing porous materials pore structure, and the general bubble method that adopts measures.The average pore size of porous complex can be filtered needs according to concrete industrial furnace gas gas solid separation and be set within the scope of 1 ~ 200 μm.In said method, hole surface due to porous complex attached to the catalytic active layer be made up of catalytic active substance, furnace gas by filtration catalytic element by the process of gas-solid isolated by filtration in can contact with catalytic active substance, realize the SCR denitration catalysis to nitrogen oxide in furnace gas.Because porous matrix is made up of sintering diamond bit or sintered ceramic porous material, therefore there is excellent resistance to elevated temperatures, work that can be stable in SCR catalytic reaction temperature range; And there is in porous matrix the network hole that 3 D stereo is communicated with, so just can guarantee that furnace gas is contacting with catalytic active substance by more sufficient during via hole matrix.
On said method basis, inventor finds further, the hole surface generally speaking smoother of the porous matrix be made up of sintering diamond bit or sintered ceramic porous material, have impact on the specific area of porous matrix, if directly catalytic active layer to be attached to the hole surface of porous matrix, in porous complex, the content of catalytic active substance is not high, thus can affect the denitration rate to industrial furnace gas.In order to solve the problem, above-mentioned industrial furnace gas dedusting denitrification integral processing method is improved to further: described porous complex also comprises the intermediate layer between porous matrix and catalytic active layer, described intermediate layer is made up of the nano particle at porous matrix surface sediment, and catalytic active layer is attached to porous matrix hole surface by this intermediate layer.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, effectively ensure that the denitration rate of industrial furnace gas.
And as the another improvement to said method, described filtration catalytic element also comprises and being positioned on porous complex windward side and the rete being matrix with sintering diamond bit or sintered ceramic porous material, and the average pore size of this rete is 1 ~ 100 μm and is less than the average pore size of porous complex.Term " windward side " refers to the side surface that porous complex first contacts with furnace gas.After the windward side at porous complex arranges rete, due to the existence of rete, furnace gas must first contact with rete, thus is tackled the dust at least partially in furnace gas by rete, reduce the touch opportunity even eliminating dust and porous complex, effectively prevent catalytic active substance poisoning.When being provided with rete, the average pore size of this rete preferably by as far as possible the dust in furnace gas is removed clean for the purpose of set, and the average pore size of porous complex preferably by make under the prerequisite of filtration flux ensureing certain level SCR catalytic reaction as far as possible fully for the purpose of set.
The Special industrial furnace gas de-dusting de-nitration integrated of said method, comprise and be provided with air inlet, the gas-filtering device of exhaust outlet and slag-drip opening, filtration catalytic element is installed in this gas-filtering device, described filtration catalytic element is a kind of function element industrial furnace gas to filtration and SCR denitration catalysis double action, it has the porous complex that average pore size is 1 ~ 200 μm, this porous complex comprises: porous matrix, described porous matrix is made up of sintering diamond bit or sintered ceramic porous material, there is in this porous matrix the network hole that 3 D stereo is communicated with, and catalytic active layer, described catalytic active layer is attached to the hole surface of porous matrix and is made up of catalytic active substance.One as said apparatus is improved, described porous complex also comprises the intermediate layer between porous matrix and catalytic active layer, described intermediate layer is made up of the nano particle piled up on porous matrix, and 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 comprises and being positioned on porous complex windward side and the rete being matrix with sintering diamond bit or sintered ceramic porous material, and the average pore size of this rete is 1 ~ 100 μm and is less than the average pore size of porous complex.
Include but not limited to the filtration catalytic element can applied in above-mentioned industrial furnace gas dedusting denitrification integral processing method, that a kind of medium for the treatment of has filtration and the function element of catalytic reaction double action, it has a porous complex, this porous complex comprises 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 comprises intermediate layer, described intermediate layer is made up of the nano particle at porous matrix surface sediment, described catalytic active layer is attached to porous matrix hole surface by intermediate layer.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.
This filtration catalytic element can be specifically a kind of function element industrial furnace gas to filtration and SCR denitration catalysis double action, the average pore size of described porous complex is 1 ~ 200 μm, and described porous matrix is made up of sintering diamond bit or sintered ceramic porous material, there is in this porous matrix the network hole that 3 D stereo is communicated with.Wherein, described intermediate layer can by TiO
2nano particle, AlO
2nano particle, ZrO
2nano particle or SiO
2nano particle is formed.Described 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 addition, this filtration catalytic element also can comprise further and being positioned on porous complex windward side and the rete being matrix with sintering diamond bit or sintered ceramic porous material, and the average pore size of this rete is 1 ~ 100 μm and is less than the average pore size of porous complex.
The preparation method of above-mentioned filtration catalytic element, comprises following link: 1) prepare porous matrix; 2) configuration is as the colloidal sol in intermediate layer material source, again by described sol impregnation in porous matrix, then make the collosol and gel in porous matrix, then to attachment described gel porous matrix 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 matrix in attachment intermediate layer, then the porous matrix being attached with precursor solution is heat-treated, described intermediate layer forms catalytic active layer.
When described filtration catalytic element is a kind of function element industrial furnace gas to filtration and SCR denitration catalysis double action, the average pore size of described porous complex is 1 ~ 200 μm, and described porous matrix is made up of sintering diamond bit or sintered ceramic porous material, when there is in this porous matrix the network hole of 3 D stereo connection, in described link 1) and link 2) between also following additional link can be set further, namely on the windward side of porous matrix, preparation liquid is covered, then the rete that to make film liquid change into sintering diamond bit or sintered ceramic porous material be matrix is sintered to the porous matrix of coherent film liquid, the average pore size of this rete is 1 ~ 100 μm and is less than the average pore size of porous complex.
Accompanying drawing explanation
Fig. 1 is that industrial furnace gas dedusting denitrification integral processing method is for the process chart during process of coal-fired plant boiler furnace gas.
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 uses when preparing.
Fig. 6 is the SEM photo (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 photo (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 photo (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 photo (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 a kind of coal-fired plant boiler furnace gas processing technological flow applying industrial furnace gas dedusting denitrification integral processing method of the present invention.As shown in Figure 1, this coal-fired plant boiler furnace gas processing technological flow is specially: first, with the pipeline closed, the high-temperature furnace gas that coal-fired plant boiler 200 economizer is got rid of is passed into the air inlet of de-dusting de-nitration integrated 100, in ducted furnace gas, inject reducing agent, such as ammoniacal liquor simultaneously; Then, make the furnace gas being mixed with reducing agent by the filtration catalytic element in de-dusting de-nitration integrated 100, thus under the effect of filtration catalytic element, carry out gas-solid isolated by filtration and the SCR denitration of furnace gas simultaneously; Afterwards, discharge from the exhaust outlet of described de-dusting de-nitration integrated 100 and carry out the gas after gas-solid isolated by filtration and SCR denitration by filtration catalytic element, then this gas is led to air preheater 300 (i.e. air preheater) and carry out waste heat recovery, the gas that air preheater 300 is discharged is entered after desulfurizer 500 carries out desulfurization process and is discharged by chimney 600 after blower fan 400.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 have other cleaner, the dedusting of coal-fired plant boiler 200 furnace gas and denitration are only undertaken by de-dusting de-nitration integrated 100, simplify current coal-fired plant boiler furnace gas processing technological flow.
As shown in Figure 2, the industrial furnace gas de-dusting de-nitration integrated 100 used in above-mentioned coal-fired plant boiler furnace gas processing technological flow can regard a gas-filtering device as, this gas-filtering device is provided with air inlet T1, exhaust outlet T2, slag-drip opening T3, and blowback medium entrance T4, described air inlet T1, exhaust outlet T2, slag-drip opening T3, blowback medium entrance T4 place is respectively equipped with control valve K1, K2, K3, K4, filtration catalytic element 110 is installed in the shell of gas-filtering device, the existence of this filtration catalytic element 110 makes to define in gas-filtering device two each other through space that this filtration catalytic element 110 is kept apart.Filtration catalytic element 110 is a kind of function element coal-fired plant boiler furnace gas to filtration and SCR denitration catalysis double action specifically, as shown in Figure 3,4, it has the porous complex 111 that average pore size is 1 ~ 200 μm, this porous complex 111 comprises: porous matrix 111a, described porous matrix 111a is made up of sintering diamond bit or sintered ceramic porous material, has the network hole that 3 D stereo is communicated with in this porous matrix; Catalytic active layer 111c, described catalytic active layer 111c is attached to the hole surface of porous matrix 111a and is made up of catalytic active substance; And the intermediate layer 111b between porous matrix 111a and catalytic active layer 111c, described intermediate layer 111b is made up of the nano particle at porous matrix 111a surface sediment, and catalytic active layer 111c is attached to porous matrix 111a hole surface by this intermediate layer 111b.
Above-mentioned intermediate layer is preferably by TiO
2nano particle, AlO
2nano particle, ZrO
2nano particle or SiO
2nano particle is formed.TiO
2, AlO
2, ZrO
2and SiO
2prove that there is good result of use as the carrier material in existing honeycombed catalyst and tabular catalyst.Theoretically, all in existing SCR catalyst used catalytic active substance all can be used as in the application the catalytic active substance forming catalytic active layer 111c, such as catalytic active layer 111c 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.
Above-mentioned filtration catalytic element 110 can be only made up of porous complex 111, now the average pore size of porous complex 111 within the scope of 1 ~ 200 μm generally according to actual for industrial furnace gas in the content of dust, dust granules thing size, the efficiency of dust collection of design and filtration flux carry out concrete setting, be generally 15 ~ 50 μm.Certainly, filtration catalytic element 110 also can as shown in Figure 3 by porous complex 111 with to be positioned on porous complex 111 windward side and to be formed with the rete 112 that sintering diamond bit or sintered ceramic porous material are matrix, and the average pore size of this rete 112 is 1 ~ 100 μm and is less than the average pore size of porous complex 111.After the windward side at porous complex 111 arranges rete 112, due to the existence of rete 112, furnace gas must first contact with rete 112, thus tackled by the dust at least partially in rete 112 pairs of furnace gases, reduce the touch opportunity even eliminating dust and porous complex 111, effectively prevent catalytic active substance poisoning.When being provided with rete 112, the average pore size of this rete 112 preferably by as far as possible the dust in furnace gas is removed clean for the purpose of set (being generally 10 ~ 20 μm), and the average pore size of porous complex 111 preferably by make under the prerequisite of filtration flux ensureing certain level SCR catalytic reaction as far as possible fully for the purpose of set (being generally 40 ~ 70 μm).
The using method of above-mentioned industrial furnace gas de-dusting de-nitration integrated 100 (filtration catalytic element 110 adopts the structure shown in Fig. 3) is: opening controlling valve K1, K2, closed control valve K3, K4, the furnace gas being mixed with reducing agent enters industrial furnace gas de-dusting de-nitration integrated 100 from air inlet T1, and then the filtration catalytic element 110 in this device, at this moment, furnace gas is first by rete 112, the filtering accuracy of rete 112 is higher, dust in furnace gas can be tackled also substantially completely, gas after filtration is again by porous complex 111, this process fully contacts with the catalytic active layer 111c on the 111d inwall of porous complex 111 duct and makes the reduction of nitrogen oxide in gas be nitrogen, reacted gas exports from the exhaust outlet T2 of industrial furnace gas de-dusting de-nitration integrated 100.After continuing for some time, closed control valve K1, K2, opening controlling valve K4, thus utilize blowback medium to regenerate filtration catalytic element 110.When needing deslagging, open control valve K3, dust exports from the slag-drip opening T3 of this industrial furnace gas de-dusting de-nitration integrated 100.
The preparation method of above-mentioned filtration catalytic element 110 comprises following link: 1) prepare porous matrix 111a; 2) configuration is as the colloidal sol of intermediate layer 111c material source, again by described sol impregnation in porous matrix 111a, then the collosol and gel in porous matrix 111a is made, again the porous matrix 111a of the described gel of attachment is heat-treated, make gel conversion be nano particle, and then form intermediate layer 111b; 3) catalytic active substance precursor solution is configured, again described precursor solution is impregnated in the porous matrix 111a of attachment intermediate layer 111b, then the porous matrix 111a being attached with precursor solution is heat-treated, described intermediate layer 111b forms catalytic active layer 111c.And when being provided with rete 112 on the windward side of porous complex 111, above-mentioned link 1) and link 2) between be also provided with following additional link, namely on the windward side of porous matrix 111a, cover preparation liquid, then the rete 112 that to make film liquid change into sintering diamond bit or sintered ceramic porous material be matrix is sintered to the porous matrix 111a of coherent film liquid.
The above-mentioned filtration catalytic element 110 with rete 112 is that first on porous matrix 111a, sintering forms rete 112, and then forms intermediate layer 111b and catalytic active layer 111c by subsequent technique.Before rete 112 is formed at intermediate layer 111b and catalytic active layer 111c, when high temperature sintering thus can be avoided to form rete 112, intermediate layer 111b and catalytic active layer 111c is damaged.But, just because of rete 112 is formed formerly, follow-uply then to be impregnated into equally on rete 112 when colloidal sol (intermediate layer 111c material source) is impregnated in porous matrix 111a, finally on rete 112, also can form shaggy intermediate layer, so both can change the pore structure of rete 112, also increase the roughness on rete 112 surface simultaneously, because rete 112 plays main filtration effect, when rete 112 pore structure changes and roughness increases, dust granules tiny in furnace gas to be more easily attached on rete 112 and to not easily pass through reverse gas cleaning and removes from rete 112.Therefore, preferably avoid as far as possible being impregnated into rete 112 when colloidal sol and/or catalytic active substance precursor solution being impregnated into porous matrix 111a in above-mentioned preparation method.
In order to avoid as far as possible being impregnated into rete 112 when colloidal sol and/or catalytic active substance precursor solution are impregnated into porous matrix 111a, way is the link 2 in above-mentioned preparation method) and/or link 3) in adopt and the liquid being used for flooding carried out an impregnation technology of permeating from the lee face of porous matrix 111a to direction, windward side, thus reduce the pickup on rete 112.In addition, on the basis of above-mentioned way, also can maintain the liquid being used in dipping at the windward side of rete 112 further when flooding and can penetrate porous matrix from the lee face of porous matrix 111a to direction, windward side but can not through the reverse air pressure of rete.Below for the porous matrix 111a of tubulose, illustrate how to use the immersion system shown in Fig. 5 to prevent colloidal sol, catalytic active substance precursor solution can not be impregnated into rete 112 when being impregnated into porous matrix 111a.
As shown in Figure 5, the both ends open of the tubular porous matrix 111a of attachment rete 112 is (after catalytic active layer 111c is formed, by a plug, filtration catalytic element 110 is made in one end shutoff of tubular porous matrix 111a again, during use, the openend of filtration catalytic element 110 is arranged on the orifice plate of industrial furnace gas de-dusting de-nitration integrated 100, the outer tube surface of filtration catalytic element 110 is windward side, during work, furnace gas moves from outer tube surface to tube chamber, namely identical with current smoke filtration chimney filter working method), on the upper cover 710 that the upper port of tubular porous matrix 111a and lower port are arranged on immersion system respectively and low head 720, upper cover 710 and low head 720 are respectively equipped with inlet 711 and leakage fluid dram 721, the tubular porous matrix 111a installing upper cover 710 and low head 720 is loaded in the shell 730 of immersion system, and positioned by upper location-plate 740 and lower location-plate 750 pairs of upper covers 710 and low head 720, thus make tubular porous matrix 111a be fixed on shell 730 inside of immersion system.Inlet 711 and leakage fluid dram 721 are accessed respectively the pipe-line system being used for steeping liq flowing, in this pipe-line system, be provided with regulator; Air inlet 731 on immersion system shell 730 is connected feeder, is provided with regulator equally in this feeder, air inlet 731 is positioned at the cavity conducting on tubular porous matrix 111a outside rete 112 with immersion system inside.During dipping, flow out in the tube chamber entering tubular porous matrix 111a for the liquid that floods from inlet 711 and then from leakage fluid dram 721, make the intraluminal liquid-retentive of tubular porous matrix 111a in pressure P 1 by the regulator in pipe-line system, pass into air from air inlet 731 to immersion system by feeder simultaneously, the regulator in feeder is utilized to make tubular porous matrix 111a extraneous air maintain in pressure P 2, wherein, P1-P2=P3, the pressure drop that the sample that P3 crosses tubular porous matrix 111a for the Liquid Penetrant that ought be used for flooding tested out in advance produces.Like this, the liquid that just can be used in dipping penetrates porous matrix 111a from the lee face of porous matrix 111a to direction, windward side but can not through rete 112.
Embodiment
For the preparation of the filtration catalytic element 110 of coal-fired plant boiler furnace gas dedusting denitrification integral process, and test its dedusting denitration effect.The preparation of filtration catalytic element 110, first ,-100 order aluminium powders 30% (weight) are adopted, the formula of-200 order iron powders 70% (weight), make intermetallic Fe-Al compound porous matrix 111a by powder metallurgic method sintering, testing its air flux is 368m
3/ m
2.h.kpa, average pore size is 65 μm, and normal temperature tension is 90MPa, porosity 42%.Fig. 6 and Fig. 8 is respectively the photo that porous matrix 111a amplifies 100 times and 500 times under an electron microscope, and the hole surface that wherein can be observed porous matrix 111a is comparatively smooth.Then film liquid is configured, specific practice is that powder is mixed high speed dispersion with binder solution, iron powder 70% (weight) and particle diameter that wherein powder is 5 ~ 15 μm by particle diameter are that the aluminium powder 30% (weight) of 3 ~ 10 μm mixes, binder solution is take PVB as solute, alcohol for solvent by 2% mass concentration configuration form, after the configuration of film liquid, the weight of powder is 40% of film liquid weight.The windward side of porous matrix 111a is covered the film liquid made and configure, then sinter to the porous matrix 111a of coherent film liquid the rete 112 that to make film liquid change into sintering diamond bit or sintered ceramic porous material be matrix, the average pore size of rete 112 is 25 μm.After this colloidal sol as intermediate layer material source is prepared, be about to the 2:1:20 mixing in mass ratio of butyl titanate, deionized water, alcohol and nitric acid acid, it is 4 that adjustment acid content controls pH value, colloidal sol is met the demands, then by described sol impregnation in porous matrix 111a, at 105 DEG C, be incubated 2 hours after dipping, put into resistance furnace after there is stable gel and fire 1h at 450 DEG C, form intermediate layer 111b.Fig. 7 and Fig. 9 is respectively the photo that the porous matrix 111a after forming intermediate layer 111b amplifies 100 times and 500 times under an electron microscope, and the hole surface that wherein can be observed porous matrix 111a attached to the rough surface formed by nano particle.Finally adopt ammonium paratungstate and ammonium metavanadate preparation catalytic active substance precursor solution, again described precursor solution is impregnated in the porous matrix 111a of attachment intermediate layer 111b, then the porous matrix being attached with precursor solution is burnt in resistance furnace and heat-treat, at 300 ~ 450 DEG C, be incubated 2h, described intermediate layer 111b forms catalytic active layer 111c.
Above-mentioned filtration catalytic element 110 is loaded in integrated apparatus, and with the pipeline closed, the high-temperature furnace gas that coal-fired plant boiler 200 economizer is got rid of is passed into the air inlet of integrated apparatus, make the furnace gas being mixed with reducing agent by filtration catalytic element, thus under the effect of filtration catalytic element 110, carry out gas-solid isolated by filtration and the SCR denitration of furnace gas, dust content≤10mg/Nm in the gas that integrated apparatus is discharged simultaneously
3, denitration rate>=85%.
Claims (10)
1. filtration catalytic element, that a kind of medium for the treatment of has filtration and the function element of catalytic reaction double action, it has a porous complex, this porous complex comprises 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, it is characterized in that: described 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.
2. filtration catalytic element as claimed in claim 1, it is characterized in that: be a kind of function element industrial furnace gas to filtration and SCR denitration catalysis double action, the average pore size of described porous complex is 1 ~ 200 μm, and described porous matrix is made up of sintering diamond bit or sintered ceramic porous material, there is in this porous matrix the network hole that 3 D stereo is communicated with.
3. filtration catalytic element as claimed in claim 2, is characterized in that: described intermediate layer is by TiO
2nano particle, AlO
2nano particle, ZrO
2nano particle or SiO
2nano particle is formed.
4. filtration catalytic element as claimed in claim 2 or claim 3, 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.
5. filtration catalytic element as claimed in claim 2, it is characterized in that: comprise and being positioned on porous complex windward side and the rete being matrix with sintering diamond bit or sintered ceramic porous material, the average pore size of this rete is 1 ~ 100 μm and is less than the average pore size of porous complex.
6. the preparation method of filtration catalytic element, comprises following link: 1) prepare porous matrix; 2) configuration is as the colloidal sol in intermediate layer material source, again by described sol impregnation in porous matrix, then make the collosol and gel in porous matrix, then to attachment described gel porous matrix 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 matrix in attachment intermediate layer, then the porous matrix being attached with precursor solution is heat-treated, described intermediate layer forms catalytic active layer.
7. the preparation method of filtration catalytic element as claimed in claim 6, it is characterized in that: described filtration catalytic element is a kind of function element industrial furnace gas to filtration and SCR denitration catalysis double action, the average pore size of described porous complex is 1 ~ 200 μm, and described porous matrix is made up of sintering diamond bit or sintered ceramic porous material, there is in this porous matrix the network hole that 3 D stereo is communicated with.
8. the preparation method of filtration catalytic element as claimed in claim 7, it is characterized in that: in described link 1) and link 2) between be also provided with following additional link, namely on the windward side of porous matrix, preparation liquid is covered, then sinter to the porous matrix of coherent film liquid the rete that to make film liquid change into sintering diamond bit or sintered ceramic porous material be matrix, the average pore size of this rete is 1 ~ 100 μm and is less than the average pore size of porous complex.
9. the preparation method of filtration catalytic element as claimed in claim 8, is characterized in that: described link 2) and/or link 3) in adopt the impregnation technology of being carried out from the lee face of porous matrix to direction, windward side by the liquid being used for flooding permeating.
10. the preparation method of filtration catalytic element as claimed in claim 9, is characterized in that: maintain the liquid being used in dipping at the windward side of rete during dipping and can penetrate porous matrix from the lee face of porous matrix to direction, windward side but can not through the reverse air pressure of rete.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107708844A (en) * | 2015-05-29 | 2018-02-16 | 高技术与膜工业公司 | Separator element with the three-dimensional circular matrix for pending fluid media (medium) |
| CN107876043A (en) * | 2017-11-24 | 2018-04-06 | 李建州 | 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102008857A (en) * | 2010-09-21 | 2011-04-13 | 广州格瑞特材料科技有限公司 | Filter element for filtering high-temperature dust and purifying gas as well as preparation method and application thereof |
-
2014
- 2014-11-30 CN CN201410712568.6A patent/CN104548923B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102008857A (en) * | 2010-09-21 | 2011-04-13 | 广州格瑞特材料科技有限公司 | Filter element for filtering high-temperature dust and purifying gas as well as preparation method and application thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107708844A (en) * | 2015-05-29 | 2018-02-16 | 高技术与膜工业公司 | Separator element with the three-dimensional circular matrix for pending fluid media (medium) |
| CN107708844B (en) * | 2015-05-29 | 2022-04-19 | 高技术与膜工业公司 | Separator element with three-dimensional circulating matrix for fluid medium to be treated |
| CN107876043A (en) * | 2017-11-24 | 2018-04-06 | 李建州 | A kind of ceramic catalytic filter core and flue gas integration desulfurization denitration dust removal method for gas cleaning |
| 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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|---|---|
| CN104548923B (en) | 2016-12-07 |
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Denomination of invention: Filter catalytic element and its preparation method Granted publication date: 20161207 Pledgee: Shanghai Pudong Development Bank Co.,Ltd. Chengdu Branch Pledgor: INTERMET TECHNOLOGIES CHENGDU Co.,Ltd. Registration number: Y2024980039664 |