CN103464139A - Preparation method of structured flue gas denitrification catalyst - Google Patents
Preparation method of structured flue gas denitrification catalyst Download PDFInfo
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- CN103464139A CN103464139A CN2013104242170A CN201310424217A CN103464139A CN 103464139 A CN103464139 A CN 103464139A CN 2013104242170 A CN2013104242170 A CN 2013104242170A CN 201310424217 A CN201310424217 A CN 201310424217A CN 103464139 A CN103464139 A CN 103464139A
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Abstract
The invention relates to a preparation method of a structured flue gas denitrification catalyst, and particularly relates to a preparation method of a plate type structured vanadium-titanium based denitrification catalyst with high strength, high activity and low SO2 oxidation rate. The method comprises the following steps: mixing, stirring and grinding TiO2 powder, a binding agent, a plasticizer and glass fiber so as to obtain mixed powder; adding an oxalic acid solution containing ammonium metavanadate and a water solution containing ammonium metatungstate or ammonium paratungstate to the solid mixed powder in sequence, stirring uniformly, adding ammonia water and a lubricating auxiliary agent, mixing, kneading, and aging; performing pressure filtering and impurity removal on aged pug, uniformly coating the pug on a metal net, and rolling to prepare a raw catalyst; drying and roasting by using a specific technology under a specific atmosphere. The method is efficient and simple; through the improvement of a formula of the plate type structured catalyst and the control of drying and roasting technologies, the prepared plate type catalyst has the outstanding characteristics of high strength, low activity, low SO2 oxidation rate and the like.
Description
Technical field
The present invention relates to a kind of preparation method of structured flue gas denitration catalyst, be specifically related to a kind of high strength, high activity and low SO
2the preparation method of the plank frame vanadium titanium based denitration catalyst of oxygenation efficiency.
Background technology
NO
xacid rain phenomenon and photochemical fog that (nitre) discharge causes bring very large harm to ecological environment and human health, cause in the world already concern.There are stationary source (comprising fire coal/oil and gas boiler, nitric acid industry etc.) and moving source (being mainly vehicle exhaust), wherein stationary source NO in the source of nitre
xaccount for more than 70% of its total emission volumn.At present, ammine selectivity catalytic reduction (SCR) NO
xtechnology is widely used in the stationary source denitrating flue gas, its economical and effective, mature and reliable.One of core of this technology is catalyst, and its performance directly affects the whole denitration effect of SCR system.Abroad, through the industrial practice of more than 30 years, established with V
2o
5/ TiO
2for the core component, with WO
3or MoO
3sCR catalyst system and catalyzing for co-catalyst.
Because the coal-fired flue-gas amount is large, dust is many, allowable pressure drop is low, denitrating catalyst must adopt the structuring moulding, comprises the overall structures such as honeycomb fashion, flat and corrugated plate dst.Japan Patent JP1317545A has developed extrusion moulding large-scale production honeycomb V
2o
5/ TiO
2catalyst based technology.CN101396656A and CN101396657A disclose a kind of V
2o
5-WO
3/ TiO
2catalyst for denitrating flue gas and preparation method thereof, it first mixes the tungsten titanium valve with metatitanic acid and ammonium paratungstate calcining preparation, add again ammonium metavanadate and auxiliary agent (comprising clay, methylcellulose, PEO, Ludox, glass fibre, MEA), the final drying calcining makes catalyst, and this patent does not relate to the structuring moulding.
Honeycomb catalyst has solved the problem that exhaust gas volumn is large, allowable pressure drop is low really, but the antidusting ability still is apparent not enough.Therefore, some offshore companies have researched and developed the plank frame denitrating catalyst, and not only antidusting ability is strong, and have overcome the low problem of yield rate in the honeycomb ceramics extrusion.Because the manufacture craft of plank frame catalyst is different from the manufacture craft of honeycomb catalyst and column preformed catalyst fully, therefore, the formula of plank frame catalyst in making, pug character, drying and roasting condition etc. all have its particularity.Japan Patent JP2284630A discloses a kind of technology of preparing of board-like catalyst, is about to catalyst powder (V
2o
5: WO
3: TiO
2=4: 10: 86) with Ludox be mixed to form pug, then be coated on Cr-Ni online, after drying 200 ℃ of lower heat treatments.The preparation method of the disclosed board-like denitrating catalyst of CN1151705A1 is: to TiO
2in add water to make the material that can mediate, add again the water soluble compound of Mo and V to mediate, also add the inorganic material such as clay and glass fibre to improve intensity, add other fillers such as coalescents, dispersant, thickener in kneaded material, then roll-in is on metallic plate.In the disclosed board-like denitrating catalyst preparation method of CN101371970A, at first prepare the powder body material of titanium dioxide, ammonium metavanadate, ammonium paratungstate, methylcellulose, PEO and aluminum sulfate, and the liquid slurry of preparation liquid-state silicon colloidal sol, monoethanol ammonium and glass fiber, again both are mixed and made into to slurry, last roll-in is made to stainless (steel) wire.The disclosed board-like V of CN101428215A
2o
5/ TiO
2in the preparation method of base flue gas denitration catalyst agent, point out at first the solid materials such as titanium valve, binding agent (mixture of polyvinyl alcohol and hydroxypropyl methylcellulose), lubricating auxiliary agent (glycerine or monoethanolamine) to be mixed, then will with the solids mixing powder, mix containing the oxalic acid solution of vanadium and tungsten, obtain pug after stirring, finally by the pug blade coating to roll-in on stainless (steel) wire, dry, 340～480 ℃ of roastings obtain catalyst.As everyone knows, glycerine or monoethanolamine are also non-solid, polyvinyl alcohol and hydroxypropyl methylcellulose will decompose fully and stay space in 250 ℃ of left and right, if there is no inorganic binder or inorganic strengthening agent in formula, the intensity of catalyst is difficult to ensure, so the operability of this patent is worth the mechanical strength of discussion, catalyst low.
Due to exhaust gas dust, to the washing away of catalyst, catalyst strength is the factor that must consider in its preparation.Dry and roasting technique directly affects the bulk strength (comprise and come off and wear and tear) of catalyst.The above-mentioned patent overwhelming majority is improved from raw material and formula, rare patent or bibliographical information drying and roasting technique parameter (as heating rate, atmosphere, time etc.).Thicker a kind of board-like catalyst drying and the roasting condition of disclosing of CN101711978A is followed successively by 80 ℃ and keeps 2～3 hours, 105 ℃ to keep 2～3 hours, 450 ℃ lower roastings of 3～5 hours, 250 ℃ lower roastings 4～5 hours spaciously.CN102872919A has disclosed drying and the roasting technique in the preparation of a kind of honeycomb catalyst, and catalyst is dry at twice, in the primary drying process temperature from 22～68 ℃ by gradient increase progressively, humidity successively decreases by gradient from 95～10%; The redrying process temperature is 60～105 ℃, 12～24 hours arid cycles; Then temperature increases progressively by gradient from 68～600 ℃, and roasting time is 20～30 hours.Thereby above-mentioned board-like catalyst is from raw material, formula or later stage technique dry, roasting the space that all is significantly improved, to promote the properties of board-like catalyst.
Summary of the invention
The object of the invention is to solve " poor, active low, the SO of catalyst strength existed in existing plank frame vanadium titanium based denitration catalyst preparation
2high and production cycle of oxygenation efficiency is long " etc. problem; by improving the plank frame catalyst formulation; regulation and control drying and roasting technique, provide a kind of preparation method of efficient simple structured flue gas denitration catalyst, prepared board-like catalyst to there is high strength, high activity, low SO
2oxygenation efficiency and the outstanding feature such as with short production cycle.
For achieving the above object, concrete scheme provided by the invention is as follows:
A kind of preparation method of structured flue gas denitration catalyst, comprise the steps:
(1) be in mass ratio 100:(5-10): (4-8): (4-8) by TiO
2powder, binding agent, plasticizer and glass fibre mix, and high-speed stirred to be ground to particle diameter be 100 orders and following obtains the solids mixing powder;
(2), in the solids mixing powder that the aqueous solution that will contain the oxalic acid solution of ammonium metavanadate and contain ammonium metatungstate or ammonium paratungstate adds step (1) to make successively, wherein, the oxalic acid solution addition of ammonium metavanadate is according to being scaled V
2o
5rear and TiO
2the powder mass ratio is (0.8-3): 100 meterings; The addition of the aqueous solution that contains ammonium metatungstate or ammonium paratungstate is according to being scaled WO
3rear and TiO
2the powder mass ratio is (5-10): 100 meterings;
Add ammoniacal liquor and lubricating auxiliary agent after stirring, make pug show slightly alkalescence, mixing kneading afterwards, make pug and in 20-40 ℃ of constant humidity ageing 1-2 days; Preferably 30-35 ℃ of lower constant humidity ageing;
(3) pug after ageing in step (2) is carried out to the press filtration removal of impurities, enable and evenly be coated on wire netting, roll-in makes living catalyst; Wire netting is preferably stainless (steel) wire;
(4) living catalyst step (3) made rises to 100-130 ℃ with the heating rate of 0.1-3 ℃/min, freeze-day with constant temperature 0-300min, then rise to 450-550 ℃ with 1-5 ℃/min heating rate under oxygenous atmosphere, constant temperature calcining 10-300min, preferred 10-60min, then be cooled to room temperature with 3-8 ℃/min, obtain.
Heating rate in dry and roasting process and rate of temperature fall affects the rate of volatilization of moisture and plasticizer in pug, and moisture and the plasticizer volatilization is too fast can produce strong air flow causes catalyst to loosen or ftractures.The inventor, by great many of experiments and research, finds that heating rate is larger on the impact of intensity than sintering temperature, and the intensity of the catalyst that adopts above-mentioned drying and roasting technique to make is high.
Simultaneously, calcination atmosphere also can affect catalyst performance.For the agent of vanadium titanium-base flue gas denitration catalyst, the active component ammonium metavanadate mainly occurs in roasting and partially/ammonium paratungstate is decomposed into V
2o
5and WO
3reaction.Because this decomposition reaction discharges reducing agent NH simultaneously
3, so V probably occurs in roasting process
2o
5and WO
3be reduced to Low Valent Vanadium VO
x(x<2.5) and low price WO
xthe phenomenon of (x<3.0).The oxidisability of calcination atmosphere directly affects the reducing degree of active component and then affects activity and the SO of catalyst
2oxidisability.Therefore, in described step (4), adopted and carry out roasting under oxygenous atmosphere, in oxygenous atmosphere, oxygen content is about 0.5-30%, has effectively suppressed V
2o
5and WO
3by NH
3reduction, not only improve effective V(V in catalyst
5+) ratio, and improve the surface acidity of catalyst, therefore, the denitration activity of catalyst is high, SO
2oxygenation efficiency is low, has obtained good effect.
Plasticizer in described step (1) can be wherein a kind of or its mixture of polyvinyl alcohol, polyethylene glycol, polyethylene glycol oxide, carboxymethyl cellulose, hydroxypropyl methylcellulose; Be preferably polyvinyl alcohol.Large quantity research discovery, take polyvinyl alcohol as the prepared pug of plasticizer, and its ductility and plasticity are good, are conducive to pug and evenly apply; And take various methylcellulose as the prepared pug of plasticizer, its poor ductility, be unfavorable for that pug applies, and only is suitable for extruding honeycomb catalyst.Simultaneously, above-mentioned plasticizer also has the effect of organic binder bond in the present invention.
Binding agent in described step (1) can be bentonite, diatomite, kaolinic wherein a kind of or its mixture.
Lubricating auxiliary agent in described step (2) can be wherein a kind of or its mixture of monoethanolamine, glycerine, tung oil, its objective is pug roll banding when preventing roll-in.
Pug in described step (2) is mediated pressure and is about 0.12-3.00MPa, and kneading time is about 1-10h, preferably 2-8h.With normal pressure is mixing, compare, the mixing kneading of pressurizeing is significantly shortened material and is reached the mixed uniformly time.
Pug moisture content in described step (2) is 30-45%.The present invention adopts the roll-forming method to make board-like catalyst, and due to the extrusion pressure of roll-in pressure higher than honeycomb moulding, so the pug moisture content need be lower than the moisture content of the pug for preparing honeycomb catalyst.The pug moisture content is low has also shortened the drying and roasting equal time, makes the whole production cycle shorten.
After the middle press filtration of described step (3), the particle diameter of pug is less than or equal to 60 orders.Adopt the particulate material mixed in the following filter screen pressure filtration pug of 60 orders, not only be conducive to the pug even roller and be depressed into stainless (steel) wire, and improve the bulk strength of catalyst.Bulky grain material in pug can destroy combining closely of pug and steel mesh, not only can cause catalyst to come off, and reduces catalyst abrasion intensity.
The present invention has following advantage:
(1) existing patent majority adopts solid the mixing or employing titanium tungsten powder, and the ammonium metavanadate in the present invention and ammonium tungstate all add solid powder with the solution form, be conducive to active component and diffuse in the titanium valve micropore, improve the dispersiveness of active component, and then improve active.
(2) with existing patent, compare, the present invention adopts the method for the mixing kneading pug of pressurization, and the pug mixing time is short and even; By improving plank frame catalyst formulation and regulation and control drying and the conditions such as roasting technique, especially heating rate, significantly improved the intensity of board-like catalyst.
(3) the present invention has considered the transition of active component in vanadium Ti-base catalyst roasting process, adopts containing O
2atmosphere improves the ratio of effective V, and catalyst activity is high.
The specific embodiment
Below in conjunction with the specific embodiment, the present invention is further detailed explanation.
Embodiment 1
Take 100g TiO
2powder, 7g bentonite, 4g polyvinyl alcohol and 6g glass fibre, mix it rear high-speed stirred and be ground to below 100 orders, obtains the solids mixing powder.Add the oxalic acid solution of 20ml ammonium metavanadate (with V
2o
5convert metering for 1g) and the aqueous solution of 80ml ammonium metatungstate (with WO
3metering is 8g), add ammoniacal liquor and monoethanolamine after stirring, regulating its pH value is 9, supplementary deionized water makes the pug moisture content reach 35%; Pug is mediated 1 hour under 0.20MPa pressure, then pug is placed in to 30 ℃ of constant humidity ageings 2 days; Afterwards, by the press filtration removal of impurities in 60 mesh filter screens of this pug, then evenly be coated on stainless (steel) wire, roll-in makes living catalyst.To give birth to catalyst and rise to 110 ℃ of dryings 4 hours with the heating rate of 0.5 ℃/min, then containing 20%O
2rise to 450 ℃ with 1 ℃/min heating rate under atmosphere, roasting 1 hour, then be cooled to room temperature with 3 ℃/min and make catalyst.
The tear strength evaluation of this catalyst is carried out in self-control normal temperature and pressure fluid bed intensity meter, and the board-like catalyst of 7.3 * 7.3cm size is fixed in to the fluid bed middle part, in fluid bed, adds 350mg quartz sand (20-80 order), then passes into 4.0m
3the air of/h makes the quartz sand fluidisation, washes away catalyst, measures the weight of catalyst after 2 hours, and wear rate is 2.2%.This catalyst is 400 ℃ in reaction temperature, and air speed is 4800h
-1, flue gas composition is 1500ppm SO
2, 590ppm NO, 500ppm NH
3, 5%O
2and 5%H
2o, stable state NO removal efficiency is 91%, SO
2oxygenation efficiency is 0.9%.
Embodiment 2
Take 100g TiO
2powder, 7g bentonite, 4g polyvinyl alcohol and 6g glass fibre, mix it rear high-speed stirred and be ground to below 100 orders, obtains the solids mixing powder.Add the oxalic acid solution of 20ml ammonium metavanadate (with V
2o
5metering is for 1g) and the aqueous solution of 80ml ammonium metatungstate (with WO
3metering is 8g), add ammoniacal liquor and monoethanolamine after stirring, regulating its pH value is 9, supplementary deionized water makes the pug moisture content reach 30%; Pug is mediated 1 hour under 1.00MPa pressure, then pug is placed in to 30 ℃ of constant humidity ageings 2 days; Afterwards, by the press filtration removal of impurities in 60 mesh filter screens of this pug, then evenly be coated on stainless (steel) wire, roll-in makes living catalyst.To give birth to catalyst and rise to 110 ℃ of dryings 4 hours with the heating rate of 0.1 ℃/min, then containing 30%O
2rise to 450 ℃ with 1 ℃/min heating rate under atmosphere, roasting 1 hour, then be cooled to room temperature with 3 ℃/min and make catalyst.
This catalyst is through evaluation means test in the same manner as in Example 1, and wear rate is 1.3%; Stable state NO removal efficiency is 95%, SO
2oxygenation efficiency is 0.8%.
Embodiment 3
Take 100g TiO
2powder, 10g diatomite, 8g polyethylene glycol and 8g glass fibre, mix it rear high-speed stirred and be ground to below 120 orders, obtains the solids mixing powder.Add the oxalic acid solution of 20ml ammonium metavanadate (with V
2o
5metering is for 0.3g) and the aqueous solution of 80ml ammonium metatungstate (with WO
3metering is 5g), add ammoniacal liquor and glycerine after stirring, regulating its pH value is 9, supplementary deionized water makes the pug moisture content reach 45%; Pug is mediated 8 hours under 3.00MPa pressure, then pug is placed in to 40 ℃ of constant humidity ageings 1 day; Afterwards, by the press filtration removal of impurities in 80 mesh filter screens of this pug, then evenly be coated on copper mesh, roll-in makes living catalyst.To give birth to catalyst and rise to 100 ℃ of dryings 5 hours with the heating rate of 3 ℃/min, then containing 0.5%O
2rise to 550 ℃ with 5 ℃/min heating rate under atmosphere, roasting 10min, then be cooled to room temperature with 8 ℃/min and make catalyst.
This catalyst is through evaluation means test in the same manner as in Example 1, and wear rate is 2.5%; Stable state NO removal efficiency is 89%, SO
2oxygenation efficiency is 1.3%.
Embodiment 4
Take 100g TiO
2powder, 5g kaolin, 4g polyethylene glycol oxide and 4g glass fibre, mix it rear high-speed stirred and be ground to below 100 orders, obtains the solids mixing powder.Add the oxalic acid solution of 20ml ammonium metavanadate (with V
2o
5metering is for 3g) and the aqueous solution of 80ml ammonium paratungstate (with WO
3metering is 10g), add ammoniacal liquor and tung oil after stirring, regulating its pH value is 9, supplementary deionized water makes the pug moisture content reach 40%; Pug is mediated 10 hours under 0.12MPa pressure, then pug is placed in to 20 ℃ of constant humidity ageings 2 days; Afterwards, by the press filtration removal of impurities in 60 mesh filter screens of this pug, then evenly be coated on stainless (steel) wire, roll-in makes living catalyst.Then containing 20%O
2rise to 450 ℃ with 1 ℃/min heating rate under atmosphere, roasting 5 hours, then be cooled to room temperature with 5 ℃/min and make catalyst.
This catalyst is through evaluation means test in the same manner as in Example 1, and wear rate is 1.2%; Stable state NO removal efficiency is 93%, SO
2oxygenation efficiency is 0.9%.
Embodiment 5
Take 100g TiO
2powder, 10g bentonite, 5g carboxymethyl cellulose and 5g glass fibre, mix it rear high-speed stirred and be ground to below 100 orders, obtains the solids mixing powder.Add the oxalic acid solution of 20ml ammonium metavanadate (with V
2o
5metering is for 1g) and the aqueous solution of 80ml ammonium metatungstate (with WO
3metering is 8g), add ammoniacal liquor and monoethanolamine after stirring, regulating its pH value is 9, supplementary deionized water makes the pug moisture content reach 45%; Pug is mediated 5 hours under 1.00MPa pressure, then pug is placed in to 30 ℃ of constant humidity ageings 2 days; Afterwards, by the press filtration removal of impurities in 60 mesh filter screens of this pug, then evenly be coated on stainless (steel) wire, roll-in makes living catalyst.To give birth to catalyst and rise to 130 ℃ of dryings 1 hour with the heating rate of 0.5 ℃/min, then containing 5%O
2rise to 500 ℃ with 2 ℃/min heating rate under atmosphere, roasting 30min, then be cooled to room temperature with 3 ℃/min and make catalyst.
This catalyst is through evaluation means test in the same manner as in Example 1, and wear rate is 2.2%; Stable state NO removal efficiency is 92%, SO
2oxygenation efficiency is 1.2%.
Embodiment 6
Take 100g TiO
2powder, 8g bentonite and diatomaceous mixture, 5g polyvinyl alcohol and hydroxypropyl methylcellulose mixtures and 6g glass fibre, mix it rear high-speed stirred and be ground to below 100 orders, obtains the solids mixing powder.Add the oxalic acid solution of 20ml ammonium metavanadate (with V
2o
5metering is for 1g) and the aqueous solution of 80ml ammonium paratungstate (with WO
3metering is for 8g), add the mixture of ammoniacal liquor and glycerine and tung oil after stirring, regulating its pH value is 8.5, supplementary deionized water makes the pug moisture content reach 45%; Pug is mediated 2 hours under 1.00MPa pressure, then pug is placed in to 30 ℃ of constant humidity ageings 2 days; Afterwards, by the press filtration removal of impurities in 60 mesh filter screens of this pug, then evenly be coated on stainless (steel) wire, roll-in makes living catalyst.To give birth to catalyst and rise to 130 ℃ of dryings 1 hour with the heating rate of 1 ℃/min, then containing 10%O
2rise to 500 ℃ with 2 ℃/min heating rate under atmosphere, roasting 30min, then be cooled to room temperature with 3 ℃/min and make catalyst.
This catalyst is through evaluation means test in the same manner as in Example 1, and wear rate is 1.5%; Stable state NO removal efficiency is 91%, SO
2oxygenation efficiency is 1.3%.
Comparative Examples 1
Basic preparation method is identical with embodiment 1, and remove following condition: the pug moisture content is 43%, and it is 0.1MPa that pug is mediated pressure, and dry heating rate is 14 ℃/min, and the roasting heating rate is 5 ℃/min, and the roasting oxygen atmosphere is 21%O
2under atmosphere.
This catalyst is through evaluation means test in the same manner as in Example 1, and test result is in Table 1.
Comparative Examples 2
Basic preparation method is identical with embodiment 1, and remove following condition: the pug moisture content is 43%, and it is 0.2MPa that pug is mediated pressure, and dry heating rate is 4 ℃/min, and the roasting heating rate is 5 ℃/min, and the roasting oxygen atmosphere is 57%O
2under atmosphere.
This catalyst is through evaluation means test in the same manner as in Example 1, and test result is in Table 1.
Comparative Examples 3
Basic preparation method is identical with embodiment 1, and remove following condition: the pug moisture content is 75%, and it is 0.1MPa that pug is mediated pressure, and dry heating rate is 10 ℃/min, and the roasting heating rate is 5 ℃/min, and the roasting oxygen atmosphere is 21%O
2under atmosphere.
This catalyst is through evaluation means test in the same manner as in Example 1, and test result is in Table 1.
The above, be only preferred embodiment of the present invention, the interest field that can not limit the present invention with this, and the equivalent variations of doing according to the claims in the present invention, still belong to the scope that the present invention is contained.
The Performance Ratio that table 1 Different Preparation makes catalyst
Claims (10)
1. the preparation method of a structured flue gas denitration catalyst comprises the following steps:
(1) be in mass ratio 100:(5-10): (4-8): (4-8) by TiO
2powder, binding agent, plasticizer and glass fibre mix, and high-speed stirred to be ground to particle diameter be 100 orders and following obtains the solids mixing powder;
(2) in the solids mixing powder that the aqueous solution that will contain the oxalic acid solution of ammonium metavanadate and contain ammonium metatungstate or ammonium paratungstate adds step (1) to make successively, add ammoniacal liquor and lubricating auxiliary agent after stirring, mixing kneading, make pug and in 20-40 ℃ of constant humidity ageing;
(3) pug after ageing in step (2) is carried out to the press filtration removal of impurities, then evenly be coated on wire netting, roll-in makes living catalyst;
(4) living catalyst step (3) made rises to 100-130 ℃ with the heating rate of 0.1-3 ℃/min, after freeze-day with constant temperature, rise to 450-550 ℃ with 1-5 ℃/min heating rate under oxygenous atmosphere, constant temperature calcining 10-300min, then be cooled to room temperature with 3-8 ℃/min, obtain.
2. the preparation method of structured flue gas denitration catalyst according to claim 1, is characterized in that the binding agent in described step (1) is bentonite, diatomite, kaolinic wherein a kind of or its mixture.
3. the preparation method of structured flue gas denitration catalyst according to claim 1 and 2, is characterized in that wherein a kind of or its mixture that the plasticizer in described step (1) is polyvinyl alcohol, polyethylene glycol, polyethylene glycol oxide, carboxymethyl cellulose, hydroxypropyl methylcellulose.
4. the preparation method of structured flue gas denitration catalyst according to claim 1, is characterized in that wherein a kind of or its mixture that the lubricating auxiliary agent in described step (2) is monoethanolamine, glycerine, tung oil.
5. according to the preparation method of the arbitrary described structured flue gas denitration catalyst of claim 1-4, it is characterized in that the pug kneading pressure in described step (2) is 0.12-3.00MPa, kneading time is 1-10h.
6. according to the preparation method of the arbitrary described structured flue gas denitration catalyst of claim 1-5, it is characterized in that the pug moisture content in described step (2) is 30-45%.
7. the preparation method of structured flue gas denitration catalyst according to claim 1, is characterized in that in described step (3) after press filtration that the particle diameter of pug is less than or equal to 60 orders.
8. the preparation method of structured flue gas denitration catalyst according to claim 1, is characterized in that the wire netting in described step (3) is stainless (steel) wire.
9. the preparation method of structured flue gas denitration catalyst according to claim 1, is characterized in that the time of freeze-day with constant temperature in described step (4) is 0-300min.
10. the preparation method of structured flue gas denitration catalyst according to claim 1, is characterized in that in the oxygenous atmosphere in described step (4), oxygen content is 0.5-30%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1440789A (en) * | 1972-10-30 | 1976-06-23 | Mitsubishi Heavy Ind Ltd | Process for preparing catalysts |
| CN1475305A (en) * | 2003-07-11 | 2004-02-18 | 中国科学院山西煤炭化学研究所 | Catalyst for desulfurizing and denitrating at the same time and its application method |
| CN102166514A (en) * | 2010-02-26 | 2011-08-31 | 中国大唐集团科技工程有限公司 | Preparation method of structured flue gas denitration catalyst, prepared catalyst and application of catalyst |
-
2013
- 2013-09-17 CN CN201310424217.0A patent/CN103464139B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1440789A (en) * | 1972-10-30 | 1976-06-23 | Mitsubishi Heavy Ind Ltd | Process for preparing catalysts |
| CN1475305A (en) * | 2003-07-11 | 2004-02-18 | 中国科学院山西煤炭化学研究所 | Catalyst for desulfurizing and denitrating at the same time and its application method |
| CN102166514A (en) * | 2010-02-26 | 2011-08-31 | 中国大唐集团科技工程有限公司 | Preparation method of structured flue gas denitration catalyst, prepared catalyst and application of catalyst |
Non-Patent Citations (2)
| Title |
|---|
| PIO FORZATTI ET AL.: "Preparation and characterization of extruded monolithic ceramic catalysts", 《CATALYSIS TODAY》, vol. 41, 31 December 1998 (1998-12-31) * |
| 顾卫荣 等: "燃煤烟气脱硝技术的研究进展", 《化工进展》, vol. 31, no. 9, 31 December 2012 (2012-12-31) * |
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