CN103769236A - Catalyst module element for selective catalytic reduction, catalyst module using the element, and method for manufacturing the same - Google Patents
Catalyst module element for selective catalytic reduction, catalyst module using the element, and method for manufacturing the same Download PDFInfo
- Publication number
- CN103769236A CN103769236A CN201310489054.4A CN201310489054A CN103769236A CN 103769236 A CN103769236 A CN 103769236A CN 201310489054 A CN201310489054 A CN 201310489054A CN 103769236 A CN103769236 A CN 103769236A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- scr
- catalyst module
- thin slice
- wire netting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
Abstract
In a method of using a catalyst for selective catalytic reduction to remove nitrogen oxide included in flue gas, a catalyst module element and a catalyst module are provided which have excellent wear resistance, durability, thermal shock resistance and impact resistance, stable and continuous operation is provided by prevention of damage of a catalyst, and the fracture of the catalyst is caused by the flow velocity of the flue gas. A method for manufacturing the catalyst module element and the catalyst module are also provided. The catalyst module has excellent wear resistance, durability, thermal shock resistance and impact resistance, and damage of the catalyst is minimized, even if impact is applied to the flow velocity of the flue gas containing coal dust when the flue gas passes through a catalyst reactor, and thus shortening of life is suppressed, stable operation can be realized. The removal efficiency of the nitrogen oxide is excellent, and the manufacturing method is simple.
Description
Technical field
The present invention relates to for the catalyst module element of SCR and comprise its catalyst module, they provide good wearability, persistence and heat resistance and impact resistance, and provide stable and continuous operation by preventing that catalyst from breaking, it is to cause by use the flowing velocity of waste gas during the process that removes the nitrogen oxide that waste gas comprises for the catalyst of SCR in operation that described catalyst breaks, and also relates to the method for manufacturing described catalyst module element and the method for manufacturing described catalyst module.
Background technology
Comprise harmful polluter, for example nitrogen oxide (NO at such as, for example, waste gas from combustion plant (incinerator or the boiler) discharge of the industrial plants (power plant, chemical plant etc.) that use fossil fuel
x: NO, NO
2, N
2o, N
2o
5deng), oxysulfide (SO
x), dust, bioxin, heavy metal, VOC (VOC) etc.These polluters needed to carry out processing to a certain degree with lower than management and control concentration before discharge.
In this type of polluter, think that nitrogen oxide is the immediate cause material that atmosphere pollution occurs, it brings out acid rain and smog.Therefore, whole world All Countries (comprising Korea S) is strictly forbidden the nitrogen oxide higher than certain level from discharges such as industrial plants by various laws.
Nitrogen oxide is produced by the reaction of nitrogen and oxygen conventionally in the combustion plant of high temperature under excess air exists.For the generation of restriction nitrogen oxide, research and develop the technology producing by improving burning condition restriction nitrogen oxide, be included in burning, cycle gas etc. under low oxygen concentration.But, be different from other air pollutant, at high temperature between main combustion period, inevitably produce nitrogen oxide.In addition, nitrogen oxide is highly stable compound.Nitrogen oxide can not remove completely by improving burning condition.Therefore, research and develop for the treatment of the post-processing approach of waste gas.
In post-processing approach, attractive method comprises the method that uses SCR (SCR) and SNCR (SNCR).SCR method is to inject reducing agent (for example urea or ammonia) by nitrogen oxide (NO under existing at catalyst
x) be reduced into nitrogen (N
2) method, and SNCR method is the method that uses SCR method under catalyst not existing.
In the known method using reduction reaction, use the method for catalyst effectively to reduce the amount of air pollutant with low cost.Therefore, in view of economy and the state of the art, be, the main flow of post processing by ammonia is fed to waste gas to carry out with nitrogen oxide the method for utilizing SCR that selective reaction produces nitrogen and water under suitable catalyst.
SCR mainly comprises carrier with catalyst, such as titanium dioxide, aluminium oxide, silica, zirconia etc.; And catalyst component, such as metal oxide, zeolite, alkaline-earth metal, rare earth metal etc., and specifically, the oxide of vanadium, molybdenum, nickel, tungsten, iron, copper etc. is widely used.More particularly, vanadium oxide (V
2o
5) and titanium dioxide (TiO
2) be widely used in most in commercialization exhaust gas denitration process.
As the catalyst module element for SCR, conventionally use honeycomb type pottery, and as the method for manufacturing catalyst module element, conventionally use washing to apply (wash coating) method and extrusion method.
Washing painting method is the technology for the manufacture of the catalyst converter of the purifier apparatus as automobile exhaust gas, and is the surperficial technology by catalyst-coated with the cordierite carrier of honeycomb shape.
According to said method, need manually to implement the process of dense coating SCR catalyst, and comparatively difficulty of large-scale production.In price, owing to using expensive cordierite as carrier, so compared with directly extruding cheap catalyst, price competitiveness is lower.
In addition, according to extrusion method, obtain and be in a liquid state and there is full-bodied SCR catalyst fines, and can be by extruding generation honeycomb shape.
But the honeycomb shape producing by extrusion method is heavier, and there is exothermic reaction in the time of dry catalyst.Therefore, organic bond can volatilize suddenly, and dry and cure extrusion die during can produce crack.
In addition, according to extrusion method, need to cure considerable time, therefore, described method is uneconomic.And physical strength may reduce, the efficiency that removes of nitrogen oxide may be lower, and manufacture there is the catalyst module element of various shapes may be more difficult.
Main reaction in SCR is the reduction of nitrogen oxide.But, when reaction temperature is higher, be 400 ℃ or during higher than 400 ℃, oxidation reaction can occur ammonia, and the performance of catalyst may worsen, or can regenerate nitrogen oxide from ammonia.When reaction temperature is lower and during lower than 300 ℃, ammonia can with waste gas in reaction of moisture and can produce ammonium nitrate or ammonium sulfate, ammonium nitrate or ammonium sulfate can hinder operation.
When shut-down operation and while again operating in the moisture in the carrier absorption waste gas by catalyst layer subsequently, can in carrier, produce crack due to heating, and the function possible loss of catalyst.
In No. 0473080th, Korean registered patent, dipping by tungsten, copper, vanadium, zirconium, silver or cerium metal oxide simultaneously with natural manganese ores as carrier and at 300 ℃ to 400 ℃ heat treatment manufacture catalyst, and disclose the SCR method that uses this type of catalyst to remove nitrogen oxide by waste gas and reacting of ammonia.
According to described method, can obtain at low temperatures good denitration effect, and can reduce the use amount of reducing agent (being ammonia) and the discharge capacity of carbon dioxide simultaneously.But, hard but frangible as the natural manganese ores of carrier, easily react with many kinds of substance and produce compound, and be easily oxidized in air, and this type of catalyst easily breaks during operation.
For addressing the aforementioned drawbacks, inventor of the present invention proposes in No. 0589513rd, Korean registered patent, the method of the coating composition of catalyst for preparation SCR, such composition comprises silicone-based polymer, silicon based ceramic powder or glass fibre powder and SCR catalyst fines, by composition being coated in to the catalyst module element obtaining in fiberglass carrier and the catalyst module obtaining by modularization catalyst module element.
Above-mentioned manufacture method is simple, economy and tool productivity.For the nitrogen oxide in waste gas, the decomposition efficiency of catalyst is fabulous, and can obtain good persistence, business efficiency and heat resistance and impact resistance.But the cinder that waste gas comprises can, because flowing velocity applies impact to the catalyst in reactor when by catalytic reactor, break thereby bring out catalyst.Therefore, the efficiency of catalyst and life-span may reduce.In addition, the obstruction that often generation is caused by cinder, need cleaned at regular intervals, and continued operation is more difficult.
Inventor of the present invention proposes to manufacture by manufacturing in the following manner catalyst module sub-assembly the method for catalyst module element in No. 0868958th, Korean registered patent: in catalyst module mould, replace stacking corrugated glass sheets of fibres and plate shape glass fibre thin slice, use inorganic bond to apply as coating material deposition, be dried and cure to adhere to thin slice, with the catalyst-coated of the SCR for removing nitrogen oxide catalyst module sub-assembly, be dried and cure.
Said method is simple, and can shorten manufacturing time compared with conventional method.In addition, ceramic inorganic bond permeates between glass fibre mat, and glass fibre can keep the intensity same with ceramic phase and can form an entirety.Therefore,, compared with general catalyst module, intensity can increase.But, the prevention deficiency that the catalyst being caused by backblast is broken.
Even while using the method for above-mentioned use SCR nitrogen oxide to remove efficiency good, for applying in industry, also still exist and need improved defect.
Summary of the invention
The invention provides for the catalyst module element of SCR and by the catalyst module that comprises that this type of catalyst module element is manufactured, this type of catalyst module has good decomposition efficiency to the nitrogen oxide in waste gas, good wearability, persistence and heat resistance and impact resistance is provided, and prevent that the catalyst being caused by waste gas from breaking, and the method for manufacturing it is provided.
Embodiment of the present invention are provided for the catalyst module element of SCR (SCR), it comprises that thickness or sanded treatment by using silicone-based polymer bottoming to be coated to 0.1 μ m to 100.0 μ m carry out surface-treated metal mesh carrier, and by SCR is coated in to the coating of the thickness formation that reaches 10 μ m to 200 μ m in metal mesh carrier with the coating composition of catalyst, the polymer based on silicone that this type of coating composition comprises 4 to 10 weight portions, the SCR catalyst fines of the silicon based ceramic powder of 1 to 5 weight portion or glass fibre powder and 40 to 80 weight portions.Silicone-based polymer is prepared by the alkoxy silane that represented by Chemical formula 1 and hydrolysis and the condensation reaction of water-dispersible silica, and water-dispersible silica has 3 to 11 pH, the particle diameter of 15 μ m to 40 μ m and the solids content of 20wt% to 80wt%.
Embodiment of the present invention are provided for the catalyst module of SCR, and it comprises the catalyst module element for SCR and the top of seal case and the lid of base section that are arranged in the casing with hollow cube shape and top and bottom opening part.
Embodiment of the present invention provide the method for manufacturing for the catalyst module element of SCR (SCR).Described method comprises by using silicone-based polymer bottoming apply or by sand milling, wire netting carried out to surface treatment, apply surface treated wire netting with the coating composition of SCR catalyst, the silicone-based polymer that this type of coating composition comprises 4 to 10 weight portions, the silicon based ceramic powder of 1 to 5 weight portion or glass fibre powder, the organic solvent of catalyst fines and 5 to 15 weight portions for the SCR of 40 to 80 weight portions, the wire netting applying with the coating composition of SCR catalyst is dried to 5 minutes to 5 hours to form coating at 50 ℃ to 500 ℃, make the wire netting that comprises coating form plate shape thin slice or waveform thin slice, and plate shape thin slice or waveform thin slice are cured 10 minutes to 50 minutes at 100 ℃ to 500 ℃.Silicone-based polymer is prepared by hydrolysis and the condensation reaction of the alkoxy silane by below Chemical formula 1 represents and water-dispersible silica, and water-dispersible silica has 3 to 11 pH, the particle diameter of 15 μ m to 40 μ m and the solids content of 20wt% to 80wt%.
Embodiment of the present invention provide the method for manufacturing catalyst module.Described method comprises the catalyst module arrangements of elements for SCR of manufacturing by said method in the inner space of casing with hollow cube shape and top and base apertures part, and with top and the base section of sealing of lid casing.
[Chemical formula 1]
Rm-Si-(O-R')n
Wherein R and R ' are independently selected from having the alkyl of 1 to 6 carbon atom and having the aryl of 6 to 20 carbon atoms, and m is 1 or 2, and n is 2 or 3.
The catalyst module for SCR of manufacturing by the inventive method has good wearability, persistence and heat resistance and impact resistance, even and the waste gas that comprises cinder when by catalytic reactor because flowing velocity applies impact to the catalyst in reactor, breaking of catalyst also can alleviate, thereby restriction catalytic efficiency and the reduction in life-span and maintenance are stable and continuous operation.
In addition, nitrogen oxide to remove efficiency good, and the manufacture method of catalyst module element is simple.Therefore, can be economical and produce on a large scale catalyst module element and catalyst module.
Accompanying drawing explanation
Comprise accompanying drawing to a further understanding of the present invention is provided, and accompanying drawing is incorporated in this description and forms the part of this description.These are graphic illustrates exemplary embodiment of the present invention, and with illustrate that one is used from and explains principle of the present invention herein.In graphic:
Fig. 1 is that exemplary according to the present invention is manufactured catalyst module element by precoating and used the flow chart of the catalyst module of described catalyst module element;
To be exemplary according to the present invention manufactured catalyst module element and used the flow chart of the catalyst module of described catalyst module element by sanded treatment method Fig. 2;
Fig. 3 is the schematic diagram illustrating according to the bottoming coating procedure of exemplary of the present invention;
Fig. 4 is the schematic diagram that illustrates exemplary according to the present invention and form the manufacture method of waveform thin slice after the SCR coating of catalyst in metal mesh carrier;
Fig. 5 is the perspective view of the wire netting 1 that applies with SCR catalyst 10;
Fig. 6 is the sectional view that illustrates the structure of the thin slice by obtaining with SCR catalyst 10 metallizing nets 1;
Fig. 7 to 11 illustrates according to the preferred embodiments of the invention according to the perspective view of the waveform thin slice of the kind of the catalyst module element for SCR;
Figure 12 to 15 illustrates pitch 11, thickness 12 and the height 12 of each waveform thin slice;
Figure 16 replaces by the vertical direction according to the preferred embodiments of the invention and stacking shape that the waveform thin slice of the orthogonal stacking catalyst module element for SCR obtains;
Figure 17 to 21 replaces the plate shape thin slice of the stacking catalyst module element for SCR and the stacking shape that waveform thin slice obtains according to the preferred embodiments of the invention by the vertical direction;
Figure 22 illustrates to be had hollow cube shape and comprises top and the casing of bottom opening part 14, and it is in order to hold the catalyst module element for SCR;
Figure 23 is the perspective view illustrating for the catalyst module of SCR, and its shows the confined state that is positioned at casing 14 for the stacking plate shape thin slice 19 of the catalyst module element of SCR and waveform thin slice 20; And
Figure 24 is the perspective view that illustrates the stacked structure 21 of multiple catalyst modules.
The specific embodiment
According to the present invention, be provided for removing the SCR catalyst module element of nitrogen oxide, it obtains by using XPM as carrier and forming coating through the coating composition of coated catalysts, and the catalyst module obtaining by modularization catalyst module element is also provided.
According to the present invention, the method of manufacturing catalyst module element is provided, described method comprises by bottoming silicone-coating based polyalcohol or sand milling carries out surface treatment so that SCR catalyst is securely attached to the carrier that comprises porous screen cloth, by the surface treated metal mesh carrier of SCR catalyst-coated dry, the metal mesh carrier that comprises coating is molded into plate shape or waveform thin slice, and cures plate shape or waveform thin slice.Also provide modularization catalyst module element to manufacture the method for catalyst module.
Catalyst module element for SCR constructed in accordance and the exemplary of catalyst module will be described in detail hereinafter.
According to embodiment of the present invention, use the screen cloth of metal material as the carrier of catalyst module element.Application temperature for the SCR catalyst that removes nitrogen oxide in power plant etc. is generally 250 ℃ to 400 ℃.In addition, often shut-down operation, and may there is the corrosion of wire netting.Therefore, catalyst can easily separate, and the life-span of catalyst can shorten.
Therefore, the selection of the material of wire netting is most important.In embodiments of the invention, use the material of stainless steel as wire netting.Preferably, can use aptly Koream Industrial Standard (Korean Industrial Standard) STS300 series, STS400 series and STS430 series (KS).More preferably, the thickness of the metal of screen cloth is 0.3mm to 2.0mm, and the catercorner length of the opening of screen cloth is 1mm to 4mm.
In the time that the thickness of the metal of screen cloth is less than 0.3mm, is difficult to keep the constant intensity of catalyst on carrier, and in the time that thickness exceedes 2.0mm, may be difficult to form waveform.The described magnitude range in the hole of screen cloth is that the OK range on wire netting is stably fixed and remain on to the coating composition for SCR.
Can implement the pretreatment of wire netting, for example at high temperature heat treatment is to remove remaining oil and pollutant, or use phosphorus compound (H
3pO
4) process to remove the rust of wire netting.
Then, apply by silicone-based polymer being dissolved in to the solution obtaining in organic solvent by bottoming, metal mesh carrier is carried out to surface treatment, to SCR catalyst is securely attached in metal mesh carrier.Silicone-based polymer has good heat resistance and wearability, and is preferably by implementing alkoxy silane and the hydrolysis of water-dispersible silica and the nanometer grade silica base oxide prepared by condensation reaction by below Chemical formula 1 represents.
[Chemical formula 1]
Rm-Si-(O-R')n
Wherein, R and R ' are independently selected from having the alkyl of 1 to 6 carbon atom and having the aryl of 6 to 20 carbon atoms, and m is 1 or 2, and n is 2 or 3.
The preferred embodiment of the alkoxy silane being represented by Chemical formula 1 can comprise MTMS, MTES, dimethyldiethoxysilane, dimethoxydiphenylsilane etc.
Water-dispersible silica preferably has 3 to 11 pH, the particle diameter of 15 μ m to 40 μ m and the solids content of 20wt% to 80wt%.
In the time that water-dispersible silica is neutral or alkaline, reaction may postpone and gelatification may occur.Therefore, neutral or alkaline water-dispersible silica uses after using the acidifying of pH conversion curing catalysts.PH transforms curing catalysts and comprises hydrochloric acid, sulfuric acid, nitric acid, dicyandiamide etc.
The hydrolysis of alkoxy silane and water-dispersible silica and condensation reaction are schematically illustrated in below in Chemical formula 2.
[Chemical formula 2]
Wherein Condensation reaction represents condensation reaction.
Preferably, implement bottoming and apply the thickness that reaches 0.1 μ m to 100.0 μ m, and at 50 ℃ to 300 ℃, implement dry 5 minutes to 3 hours after bottoming coating.
Replace bottoming to apply, can use aluminium oxide, silica etc. to carry out sanded treatment to wire netting, to SCR catalyst is securely attached on wire netting.
Then, preparation intend to be coated in that economy-combat primary coat is covered or the wire netting of sanded treatment on the coating composition for SCR.
Comprise silicone-based polymer, silicon based ceramic powder or glass fibre powder and SCR catalyst fines according to the coating composition for SCR of embodiment of the present invention.
Silicone-based polymer is can be described in bottoming coating step synthetic from alkoxy silane and water-dispersible silica, and can 4 to 10 weight portions and preferably 5 to 9 weight portions be contained in total coating composition.
In the time that the amount of silicone-based polymer is less than 4 weight portion, the size of the particle forming is thus too little, and SCR may worsen to the adherence in metal mesh carrier with catalyst, and in the time that described amount exceedes 10 weight portion, the particle forming thus may wrap up SCR catalyst, the specific area of catalyst may reduce, and the decomposition efficiency of nitrogen oxide may reduce.
Described silicon based ceramic powder or described glass fibre powder are blended in coating composition, to increase hardness and the wearability of SCR catalyst.
Silicon based ceramic powder is to comprise SiO
xmetal oxide powder, and glass fibre powder is by prepared by glass fibre fine cut powdered state.The particle diameter of powder preferably diameter is 0.1mm to 3.0mm.
In the time that particle diameter is less than 0.1mm, the specific area of catalyst may reduce, and SCR may reduce with the catalytic efficiency of catalyst.In the time that particle diameter exceedes 3mm, specific area and hardness may increase.In this case, surface roughness and hardness may be higher, even if catalytic efficiency may increase.Therefore, can be easily because external impact produces crack.
The amount of silicon based ceramic powder or glass fibre powder accounts for 1 to 5 weight portion of coating composition total amount, and 2 to 4 weight portions preferably.
In the time that the amount of silicon based ceramic powder or glass fibre powder is less than 1 weight portion, the hardness of coating may reduce, and in the time that described amount exceedes 5 weight portion, SCR may be deteriorated with the reaction efficiency of catalyst.
Can use the conventional in the art SCR catalyst fines of all kinds, its amount accounts for 40 to 80 weight portions of coating composition total amount.
In the time that SCR is less than 40 weight portion by the amount of catalyst fines, the hardness of coating may be a little less than, and catalyst fines can easily separate from carrier, and in the time that described amount exceedes 80 weight portion, the hardness of coating may be too high, and may produce crack due to slight impact, and nitrogen transformation efficiency may reduce.
Preparation SCR comprises silicone-based polymer is dissolved in organic solvent by the method for the coating composition of catalyst, in thus obtained solution, add silicon based ceramic powder or glass fibre powder and mix, and add SCR catalyst fines and mix in thus obtained mixture.
With an organic solvent to increase the dispersion effect of the storage stability of silicone-based polymer and SCR catalyst, and can be preferably at least one and be selected from the solvent of methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, ethylene glycol, diethylene glycol, propane diols etc.
The amount of organic solvent preferably accounts for 5 to 15 weight portions of coating composition total amount.In the time that described amount is less than 5 weight portion, the viscosity of coating composition may increase, and may produce crack in the time being coated in metal mesh carrier, and due to weak adherence, coat can easily separate, thereby reduces persistence.In the time that described amount exceedes 15 weight portion, the viscosity of coating composition may reduce, and SCR can reduce by the relative quantity of catalyst, thereby reduces the decomposition efficiency of nitrogen oxide.
Then, the wire netting covering with the cutting of the coating composition for SCR coating (cut coat) economy-combat primary coat of preparation above, and use roll-in to apply, and dry.
In this case, the suitable thickness that is coated in the dry rear coating of the catalyst coat composition on wire netting is to fill hole surface 10 μ m to the 200 μ m of distance wire netting afterwards of wire netting completely with coating composition.
Implement pressure dressing and dry to easily form waveform and improve the adherence in the process of below recording in waveform press roller.Dry preferably enforcement at 50 ℃ to 500 ℃.When temperature is during lower than 50 ℃, the solvent of catalyst coat composition is not emptying, and may not obtain the performance of catalyst, and in the time that temperature exceedes 500 ℃, coating may break or damage.
In addition, dry enforcement is dried to realize fully for 5 minutes to 5 hours, removes efficiency to improve the nitrogen oxide of the fixing character of the adhesion of catalyst and raising catalyst element.
The metal mesh carrier that forms coating is above processed into plate shape thin slice or waveform thin slice and cures.
Plate shape thin slice can be manufactured by the metal mesh carrier that comprises coating is cut into a certain size, and waveform thin slice can be manufactured in the following manner: use the mould of various shapes exert pressure and be molded as roll forming to plate shape thin slice, or it is also molded to obtain waveform and then to cut into a certain size to exert pressure to the metal mesh carrier that comprises coating.
Waveform wafer warpage can be become to definite shape, for example, bending many times with obtain sinusoidal waveform cross section shape, bending many times with obtain copped wave tee section shape, have the cross section that alternately comprises crest and butt crest shape, there is the shape in the cross section that alternately comprises crest-horizontal component-trough-horizontal component or there is the shape in the cross section that alternately comprises trough-crest-horizontal component.
Can and measure according to the kind of fuel used and the nitrogen oxide that discharges the height H and the large fine pith L that design different waveform thin slices.But the proper height of waveform is 3mm to 120mm, and suitable pitch L is 10mm to 150mm.
The process of curing is preferably implemented 10 minutes to 50 minutes at 100 ℃ to 500 ℃.When stoving temperature is during lower than 100 ℃, the processing time can extend, and in the time that stoving temperature exceedes 500 ℃, coating may break or damage.The time of curing is the optimization scope in view of the raising of the productivity that removes efficiency and catalyst module element of nitrogen oxide.
As described above, when the metal mesh carrier of covering with SCR catalyst-coated economy-combat primary coat, dry, manufacture plate shape thin slice or waveform thin slice, and while curing, can complete according to the catalyst module element for SCR of embodiment of the present invention.Catalyst module element can have the alternately stacked structure of the catalyst module element of plate shape thin slice or waveform thin slice.
Preferably, stacked structure can by the mode of upper and lower lamellae cross repeatedly stacking waveform thin slice obtain.
Or stacked structure can by the vertical direction, alternately stacking plate shape thin slice and waveform thin slice obtain one by one.
The chemical reaction carrying out in catalyst coat in the catalyst module element of manufacturing by said method is schematically illustrated in below in chemical formula 3.
[chemical formula 3]
4NO+4NO
3+O
2→4N
2+6H
2O
6NO
2+8NO
3→7N
2+12H
2O
With reference to chemical formula 3, SCR implements by following principle: by the ammonia and the catalyst that are used as reducing agent, nitric oxide and nitrogen dioxide are changed into harmless nitrogen and moisture.Specifically, when ammonia is with the nitric oxide production mol ratio of reacting while being 1.0, condition of work can be the best.
In addition, the present invention includes the catalyst module for SCR.
Catalyst module for SCR according to the present invention comprise hollow cube shape casing (described casing comprises top and base apertures), be arranged in the catalyst module element for SCR and the top of seal case and the lid of base section of the inner space of casing.
Casing preferably, by using the material manufactures such as such as steel, stainless steel or galvanized steel thin slice, has the thickness of 0.2mm to 2.0mm, and width, length and the height of 15cm to 100cm respectively.
Explain with reference to accompanying drawing that in more detail exemplary is to help understanding the present invention hereinafter.
Fig. 1 and 2 manufactures catalyst module element and uses the flow chart of the catalyst module of described catalyst module element according to exemplary of the present invention;
Fig. 1 comprises treated wire netting is impregnated in silicone-based polymer solution to process and the dry run to form priming coat, and Fig. 2 comprises sanded treatment process and dry run.
Fig. 3 is schematic diagram, it illustrate according to exemplary of the present invention pass through use applicator roll 3 bottoming to be coated in the process of the silicone-based polymer coating composition 4 containing in the container 2 of silicone-based polymer coating composition, and by using the dry run of drying equipment 5, be securely attached in metal mesh carrier 1 for use in the catalyst coat of SCR.
Fig. 4 is the schematic diagram that illustrates the manufacture process of waveform, it completes in the following manner: the coating that forms SCR catalyst in metal mesh carrier, this is to cut coating machine 7 by use the coating composition 6 of SCR catalyst to be coated in the metal mesh carrier of covering according to the economy-combat primary coat in Fig. 3 of exemplary of the present invention, use pressure roller 8 pressure dressings, and be dried to realize with drying equipment 5.Then, when by waveform press roller 9, manufacture the effigurate waveform of tool.
Fig. 5 is the perspective view of the wire netting 1 that applies with SCR catalyst 10.
Fig. 6 is the sectional view that illustrates the flake structure by obtaining with SCR catalyst 10 metallizing nets 1.
Fig. 7 to 11 illustrates according to the preferred embodiments of the invention according to the perspective view of the waveform thin slice of the kind of the catalyst module element for SCR.
Fig. 7 has bending many times to obtain the shape in sinusoidal waveform cross section, Fig. 8 has bending many times to obtain the shape of copped wave tee section, Fig. 9 has the shape in the cross section alternately with crest and butt crest, Figure 10 has the shape in the cross section alternately with crest-horizontal component-trough-horizontal component, and Figure 11 has the shape in the cross section alternately with trough-crest-horizontal component.
Figure 12 to 15 illustrates pitch 11, thickness 12 and the height 13 of each waveform thin slice.
Figure 16 replaces by the vertical direction according to the preferred embodiments of the invention and stacking shape that the waveform thin slice of the orthogonal stacking catalyst module element for SCR obtains.
Figure 17 to 21 replaces the plate shape thin slice of the stacking catalyst module element for SCR and the stacking shape that waveform thin slice obtains according to the preferred embodiments of the invention by the vertical direction.
Figure 22 illustrates the casing 14 that has height 15, width 16, length 17 and thickness 18 and have opening on its top and base section, and it is in order to hold the catalyst module element for SCR.
Figure 23 is the perspective view that illustrates the catalyst module for SCR of the casing 14 that is arranged in Figure 22, and it shows for the stacking plate shape thin slice 19 of the catalyst module element of SCR and the confined state of waveform thin slice 20.
Figure 24 is the perspective view that illustrates the stacked structure 21 of the catalyst module of multiple Figure 23.
Explain in more detail the present invention with reference to embodiment and EXPERIMENTAL EXAMPLE hereinafter.
But the present invention can be presented as many multi-form and should not be understood as and be confined to described exemplary herein.On the contrary, provide these exemplary to make this explanation thorough and complete, and pass on all sidedly scope of the present invention to those skilled in the art.
< embodiment 1 is to 6>
First, the metallic sieve (3P, Hyugjae metal lath Co.) of preparation STS304 stainless steel material, iron net thickness is that the distance between 0.35mm, wiring is that 3mm and width are 450mm.
By metallic sieve heat treatment use phosphoric acid to process to remove oil and pollutant at 400 ℃, to make the coating composition for SCR of metal can be securely attached to metallic sieve.
Use aluminium oxide or silica to carry out sanded treatment to metallic sieve.Respectively, by making, MTMS and pH are 4, particle diameter is the water-dispersible silica (Ludox that 25 μ m and solids content are 50wt%
tM, DuPont) react and prepare silicone-based polymer solution.Metallic sieve is impregnated in silicone-based polymer solution to form priming coat, and at 300 ℃ dry 1 hour.In this case, the average thickness of dry coating is 10 μ m.
After this, by by silicone-based polymer, silicon based ceramic powder or glass fibre powder (Glassue
tM, KumKang Fiber Industries), for SCR, catalyst fines (Daeyoung C & E Co., Ltd) and organic solvent mix to come the coating composition for the preparation of SCR with ratio of component illustrated in table 1.
SCR is injected into the groove for cutting coating with the coating composition of catalyst, and by the groove being immersed in for cutting coating through the metallic sieve of sanded treatment or bottoming coating is cut to coating.Use roller to implement pressure dressing, and be dried 3 hours at 300 ℃.
After filling the hole of metallic sieve completely, the thickness that cutting is coated in the dry coating of the catalyst on metallic sieve is the surface 50 μ m apart from metallic sieve, and is dried 5 hours at 450 ℃.
Metallic sieve by SCR catalyst-coated is suppressed in plate shape or waveform press roller, and cured 50 minutes at 450 ℃, to manufacture plate shape or waveform catalyst module element.In this case, the pitch P of waveform is 70mm, and height H is 12mm.
In the vertical direction replaces stacking plate shape catalyst module element and waveform catalyst module element, and stacked structure is introduced and had in the casing (width × length × highly × thickness=150 × 150 × 500 × 1mm) of stainless steel material of top and bottom opening, to manufacture catalyst module.
Mixing ratio (the unit: g) of the coating composition of catalyst for table 1SCR
< EXPERIMENTAL EXAMPLE > is for the performance evaluation of the catalyst module of SCR
Make waste gas from power plant by the catalyst module for SCR of being manufactured by above-described embodiment, to measure decomposition efficiency, wearability and heat resistance and impact resistance.Result explanation in following table 2.
In this case, condition determination is: operating temperature is 180 ℃ to 450 ℃, and flowing velocity is 100Nm
3/ h to 250Nm
3/ h (Sv=2,500 to 30,000/hr), the NO of waste gas
xconcentration is 10ppm to 1,000ppm, NH
3concentration be 10ppm to 1,000ppm, SO
xconcentration be 100ppm to 1,500ppm, and O
2concentration be 1wt% to 21wt%.
Table 2 is for the performance evaluation of the catalyst module of SCR
As illustrated in table 2, along with SCR reduces with the amount increase of catalyst and the amount of silicone-based polymer, the decomposition efficiency of nitrogen oxide improves, but, for sand trail and heat resistance and the impact resistance reduction of wearability.
In addition, also find, along with operating temperature raises, the decomposition efficiency of nitrogen oxide improves.In the time not considering running cost, operation is preferably at high temperature implemented with environment protection.
As described above, the catalyst module element for SCR and the catalyst module manufactured by the inventive method have good wearability, persistence and heat resistance and impact resistance.Therefore, can be by reducing catalyst the deteriorated of the catalytic efficiency of limiting catalyst module and life-span of breaking, even if the flowing velocity due to the waste gas that comprises carbonizable substance during by catalytic reactor applies impact to the catalyst in reactor.Can stably operate.
In addition, nitrogen oxide to remove efficiency good, and production method is simple.Therefore, can be economical and produce on a large scale catalyst module element and catalyst module.
To the explanation of reference number
1: wire netting
2: the container of the silicone-based polymer coating composition applying for bottoming
3: wire netting applicator roll
4: the silicone-based polymer coating composition applying for bottoming
5: drying equipment
The coating composition of catalyst for 6:SCR
7: cutting coating equipment
8: pressure roller
9: waveform press roller
10: be coated in the SCR catalyst on wire netting
11: the length (pitch) between ripple
12: the thickness of wire netting
13: the height of waveform
14: catalyst casing
15: the height of casing
16: the width of casing
17: the length of casing
18: the thickness of casing
19: the catalyst element for SCR of plate shape
20: the catalyst element for SCR of waveform
21: for the catalyst module of SCR
Claims (16)
1. for a catalyst module element for SCR (SCR), it comprises:
Metal mesh carrier, it is by using silicone-based polymer bottoming be coated to 0.1 μ m to 100.0 μ m thickness or carry out surface treatment by sanded treatment; And
By SCR is coated in to the coating of the thickness formation that reaches 10 μ m to 200 μ m in described metal mesh carrier, the SCR catalyst fines of the described silicone-based polymer that described coating composition comprises 4 to 10 weight portions, the silicon based ceramic powder of 1 to 5 weight portion or glass fibre powder and 40 to 80 weight portions with the coating composition of catalyst;
Wherein, described silicone-based polymer is prepared by hydrolysis and the condensation reaction of the alkoxy silane by below Chemical formula 1 represents and water-dispersible silica, and described water-dispersible silica has 3 to 11 pH, the particle diameter of 15 μ m to 40 μ m and the solids content of 20wt% to 80wt%:
[Chemical formula 1]
Rm-Si-(O-R')n
Wherein, R and R ' are independently selected from having the alkyl of 1 to 6 carbon atom and having the aryl of 6 to 20 carbon atoms, and m is 1 or 2, and n is 2 or 3.
2. catalyst module element according to claim 1, wherein, described wire netting comprises stainless steel material, the wire thickness of described wire netting is 0.3mm to 2.0mm, and the catercorner length in the hole of described wire netting is 1mm to 4mm.
3. catalyst module according to claim 1, wherein, described catalyst module element be plate shape thin slice or bending repeatedly and there is the waveform thin slice of the pitch of height, the 10mm to 150mm of 3mm to 120mm.
4. catalyst module according to claim 3, wherein, described waveform thin slice has the cross section of following shape: sinusoidal waveform, copped wave shape, alternately comprise the shape of crest and butt crest, alternately comprise the shape of crest-horizontal component-trough-horizontal component or comprise the shape of trough-crest-horizontal component.
5. catalyst module according to claim 3, wherein, described catalyst module element in the vertical direction has the alternately stacked structure of described plate shape thin slice and described waveform thin slice.
6. the catalyst module for SCR, it comprises: be arranged in have hollow cube shape and top and bottom opening part casing according to the catalyst module element for SCR described in the arbitrary claim of claim 1 to 5, and seal the top of described casing and the lid of base section.
7. manufacture is for a method for the catalyst module element of SCR (SCR), and described method comprises:
By using silicone-based polymer bottoming apply or by sand milling, wire netting carried out to surface treatment;
Apply surface treated wire netting with the coating composition of SCR catalyst, the organic solvent of catalyst fines and 5 to 15 weight portions for the SCR of the silicone-based polymer that described coating composition comprises 4 to 10 weight portions, the silicon based ceramic powder of 1 to 5 weight portion or glass fibre powder, 40 to 80 weight portions;
The described wire netting applying with the coating composition of described SCR catalyst is dried to 5 minutes to 5 hours to form coating at 50 ℃ to 500 ℃;
Make the described wire netting that comprises described coating be formed as plate shape thin slice or waveform thin slice; And
Described plate shape thin slice or described waveform thin slice are cured 10 minutes to 50 minutes at 100 ℃ to 500 ℃,
Wherein, described silicone-based polymer is prepared by hydrolysis and the condensation reaction of the alkoxy silane by below Chemical formula 1 represents and water-dispersible silica, and described water-dispersible silica has 3 to 11 pH, the particle diameter of 15 μ m to 40 μ m and the solids content of 20wt% to 80wt%:
[Chemical formula 1]
Rm-Si-(O-R')n
Wherein, R and R ' are independently selected from having the alkyl of 1 to 6 carbon atom and having the aryl of 6 to 20 carbon atoms, and m is 1 or 2, and n is 2 or 3.
8. method according to claim 7, wherein, described wire netting comprises stainless steel material, the wire thickness of described wire netting is 0.3mm to 2.0mm, and the catercorner length in the hole of described wire netting is 1mm to 4mm.
9. method according to claim 7, it is acid that wherein said water-dispersible silica is.
10. method according to claim 7, the thickness of wherein said priming coat is 0.1 μ m to 100.0 μ m.
11. methods according to claim 7, the particle diameter of wherein said silicon based ceramic powder or described glass fibre powder is diameter 0.1mm to 3.0mm.
12. methods according to claim 7, wherein said organic solvent is at least one solvent that selects the group of free methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, ethylene glycol, diethylene glycol and propane diols composition.
13. methods according to claim 7, the thickness of wherein said coating is surface 10 μ m to the 200 μ m of the described wire netting of distance.
14. methods according to claim 7, wherein, the described catalyst module element for SCR is described plate shape thin slice, or bending repeatedly and there is the described waveform thin slice of the height of 3mm to 120mm and the pitch of 10mm to 150mm.
15. methods according to claim 7, wherein, described catalyst module element in the vertical direction has the alternately stacked structure of described plate shape thin slice and described waveform thin slice.
Manufacture the method for catalyst module for 16. 1 kinds, described method comprises:
By by according to the described catalyst module arrangements of elements for SCR of the method manufacture described in any one in claim 7 to 15 in the inner space of casing with hollow cube shape and top and bottom opening part; And
With top and the base section of casing described in sealing of lid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2012-0115415 | 2012-10-17 | ||
| KR1020120115415A KR101254068B1 (en) | 2012-10-17 | 2012-10-17 | Selective catalytic reduction element, module produced using the element, and method for manufacturing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103769236A true CN103769236A (en) | 2014-05-07 |
| CN103769236B CN103769236B (en) | 2016-01-20 |
Family
ID=48443023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310489054.4A Active CN103769236B (en) | 2012-10-17 | 2013-10-17 | SCR catalyst module element and the catalyst module and their manufacture methods that contain this element |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR101254068B1 (en) |
| CN (1) | CN103769236B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104624049A (en) * | 2014-12-12 | 2015-05-20 | 李可文 | Diesel engine tail gas reducing agent with lubrication action as well as application and preparation method of diesel engine tail gas reducing agent |
| CN113803732A (en) * | 2021-10-12 | 2021-12-17 | 上海市计量测试技术研究院 | Heat accumulating type catalytic combustion waste gas treatment device and treatment method thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101724233B1 (en) * | 2016-05-27 | 2017-04-11 | 주식회사 나노 | Sheet type cartridge having excellent formability and air pollution reducing apparatus using the same |
| KR101952314B1 (en) * | 2017-03-29 | 2019-02-27 | 주식회사 나노 | Method of stacked hexagonal type catalyst cartridge for selective catalytic reduction and catalyst carrier using the same |
| KR101909231B1 (en) | 2018-01-22 | 2018-10-18 | 주식회사 나노 | Apparatus for manufacturing catalyst cartridge for selective catalytic reduction and method of the same |
| CN114509111B (en) * | 2022-01-26 | 2023-06-27 | 华能威海发电有限责任公司 | Power station boiler abnormal condition detection method and system |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1978568A (en) * | 2005-11-29 | 2007-06-13 | 大荣C&E株式会社 | Composition, catalytic module element, and catalytic module for selective catalytic reduction of nitrogen oxides |
| KR100868958B1 (en) * | 2008-07-24 | 2008-11-17 | 대영케미칼(주) | A manufacturing process of advanced selective catalytic reduction element for denitrification and a module piled up by catalytic elements for selective catalytic reduction |
| CN101391214A (en) * | 2008-11-07 | 2009-03-25 | 哈尔滨工业大学 | Cellular metal screen catalyst for selective catalytic reduction of nitrogen oxide and preparation method thereof |
| CN101564646A (en) * | 2008-04-22 | 2009-10-28 | 赫多特普索化工设备公司 | Method for purification of an exhaust gas from a diesel engine |
-
2012
- 2012-10-17 KR KR1020120115415A patent/KR101254068B1/en active IP Right Grant
-
2013
- 2013-10-17 CN CN201310489054.4A patent/CN103769236B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1978568A (en) * | 2005-11-29 | 2007-06-13 | 大荣C&E株式会社 | Composition, catalytic module element, and catalytic module for selective catalytic reduction of nitrogen oxides |
| CN101564646A (en) * | 2008-04-22 | 2009-10-28 | 赫多特普索化工设备公司 | Method for purification of an exhaust gas from a diesel engine |
| KR100868958B1 (en) * | 2008-07-24 | 2008-11-17 | 대영케미칼(주) | A manufacturing process of advanced selective catalytic reduction element for denitrification and a module piled up by catalytic elements for selective catalytic reduction |
| CN101391214A (en) * | 2008-11-07 | 2009-03-25 | 哈尔滨工业大学 | Cellular metal screen catalyst for selective catalytic reduction of nitrogen oxide and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104624049A (en) * | 2014-12-12 | 2015-05-20 | 李可文 | Diesel engine tail gas reducing agent with lubrication action as well as application and preparation method of diesel engine tail gas reducing agent |
| CN113803732A (en) * | 2021-10-12 | 2021-12-17 | 上海市计量测试技术研究院 | Heat accumulating type catalytic combustion waste gas treatment device and treatment method thereof |
| CN113803732B (en) * | 2021-10-12 | 2023-09-26 | 上海市计量测试技术研究院 | Heat accumulating type catalytic combustion waste gas treatment device and treatment method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101254068B1 (en) | 2013-04-12 |
| CN103769236B (en) | 2016-01-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103769236B (en) | SCR catalyst module element and the catalyst module and their manufacture methods that contain this element | |
| CN1978568B (en) | Composition, catalytic module element, and catalytic module for selective catalytic reduction of nitrogen oxides | |
| US10322403B2 (en) | Coating for reducing nitrogen oxides | |
| CN100566823C (en) | A kind of SCR denitrating catalyst and preparation method thereof | |
| CN104591204A (en) | Aei zeolite synthesis | |
| WO2014141198A1 (en) | Cerium-modified manganese octahedral molecular sieves as catalysts for selective catalytic reduction | |
| CN111013566B (en) | Novel rare earth modified aerogel denitration flue gas catalyst and preparation method thereof | |
| KR102340327B1 (en) | Catalyst and method for purifying combustion exhaust gas | |
| GB2026336A (en) | Plate-shaped denitrating catalysts | |
| CN101584999A (en) | Honeycomb structure | |
| KR102090726B1 (en) | Metal Structure based NOx Removal Catalyst for Selective Catalyst Reduction using Coating Slurry and Method for Manufacturing Same | |
| CN102015098A (en) | Slurry for produciton of denitration catalyst, process for production of the slurry, process for production of denitration catalyst by using the slurry, and denitration catalyst produced thereby | |
| CN103846083A (en) | Tungsten titanium composite oxide supported cerium oxide catalyst, preparation method as well as application of catalyst | |
| CN105939775A (en) | Selective catalytic reduction processes using doped cerias | |
| WO2011073396A2 (en) | DEACTIVATION-RESISTANT CATALYST FOR SELECTIVE CATALYST REDUCTION OF NOx | |
| CN103619467A (en) | Catalysts possessing an improved resistance to poisoning | |
| CA2486158C (en) | Catalyst for removing nitrogen oxides, method for production the same, and method for removing nitrogen oxides | |
| KR101891233B1 (en) | Catalyst for removing nitrogen oxide comprising catalyst layer formed on the body surface, a preparation method and use thereof | |
| CA1122584A (en) | Process for producing plate-shaped denitrating catalysts | |
| CN101585001A (en) | Honeycomb structured body | |
| CN103442802B (en) | Preparation method for denitration catalyst | |
| CN109069994A (en) | For hot gas filtration catalytic activity filter, prepare the method for the filter and from air-flow while the method that removes solid particle and undesirable compound | |
| KR100868958B1 (en) | A manufacturing process of advanced selective catalytic reduction element for denitrification and a module piled up by catalytic elements for selective catalytic reduction | |
| CN1209196C (en) | Exhaust-gas purifying catalyst compound, catalyst comprising said compound and method for preparing the compound | |
| EP1431431B1 (en) | Zirconia-containing inorganic fiber and method for production thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |