CN103769224B - A kind of denitrating catalyst and preparation method thereof - Google Patents
A kind of denitrating catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a kind of denitrating catalyst and preparation method thereof, and described preparation method comprises the steps: that (1) preparation mass concentration is the polyacrylamide solution of 0.15% ~ 0.5%; (2) one section, denitrating catalyst monomer end is immersed in the solution prepared by step (1); (3) take out monomer and blow off duct liquid by compress wind, then drying, roasting process obtain denitrating catalyst.The end face strength of denitrating catalyst prepared by the method and wearability are all greatly improved, and can be applied in and be equipped with on the high dust fire coal boiler fume SCR treating apparatus of acoustic wave ash ejector.
Description
Technical field
The present invention relates to a kind of denitrating catalyst and preparation method thereof, relate in particular to the denitrating catalyst and preparation method thereof of a kind of end face through intensive treatment.
Background technology
SCR (SCR) is a kind of flue-gas denitration process technology of maturation, is widely used in the fume treatment of power plant coal-burning boiler.This technique is with NH
3as reducing agent, in the presence of a catalyst, the NOx in flue gas is optionally reduced to nitrogen.
The key of SCR denitration technique is catalyst.Nowadays the catalyst of commercial Application mostly is with TiO
2for matrix, with the oxide of tungsten and vanadium for active component.Moulding process more options direct extrusion molding.The type catalyst is homogeneous catalysis, and monolith all has catalytic activity.But, containing a large amount of dust in fire coal boiler fume, this will produce abrasion to honeycomb (or ripple) catalyst, wherein end, catalyst windward side is particularly serious, in addition, the change in flow of operating mode downstream and the operation of acoustic wave ash ejector, all can make catalyst shake in modular tank, now, the impact that is subject to of catalyst end is also maximum.
After the abrasion of catalyst and crack damage reach certain degree, need to change catalyst, thus shorten the service life of catalyst.A kind of selective catalytic reduction catalyst for flue gas denitration is disclosed in CN101428240A, the method, by containing after the dry monomer sawing of catalyst component, obtains: end, monomer one end is flood 5-12 second in the aluminum saline solution of 1.41-1.45kg/L in density by (1) according to the following steps; (2) with blower fan air blowing 15-25 second, the hardening bath of monomer impregnated end excess surface is blown clean; (3) monomer after dipping hardening bath is placed on calcining in calcining furnace and carries out cure process, obtained catalyst, described aluminium salt is aluminium dihydrogen phosphate.CN101516509A discloses a kind of preparation method of catalyst, the method is to the end face part of the carrier structure body of carried catalyst composition, carry out following operation successively, (1) impregnated in by the molal quantity of metal is operation in the aqueous metal salt of 2.7 ~ 3.88 mol/L, (2) operation of its drying is made, (3) again impregnated in by the molal quantity of metal is operation in the aqueous metal salt that the metal species of 2.7 ~ 3.88 mol/L is identical with aforementioned metal saline solution, and (4) carry out burning till process, make the operation that catalyst end face solidifies.The method announced in above-mentioned patent can the end face strength of raising catalyst in various degree and wearability, but the effect improved is all more limited; In addition, the former also also exists, and the high and concentration range of required maceration extract mass fraction is little to be waited not enough, and cause operating restive, poor repeatability, the latter exists needs double-steeping, complex procedures, high in cost of production shortcoming.
With TiO
2for the Integral forming type denitrating catalyst of matrix is widely used, have good catalytic effect, but have resistance to compression and the low shortcoming of shock strength, especially catalyst end face is subject to the double influence that airflow scouring and sonic soot blowing concussion are impacted.Therefore, develop and there is strengthening end face, and simple to operate, that cost is low method for preparing catalyst is extremely important.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of denitrating catalyst and preparation method thereof.The end face strength of denitrating catalyst prepared by the method and wearability are all greatly improved, and can be applied in and be equipped with on the high dust fire coal boiler fume SCR treating apparatus of acoustic wave ash ejector.
A preparation method for denitrating catalyst, comprises the steps:
(1) preparing mass concentration is the polyacrylamide solution of 0.15% ~ 0.5%;
(2) one section, denitrating catalyst monomer end is immersed in the solution prepared by step (1);
(3) take out monomer and blow off duct liquid by compress wind, then drying, roasting process obtain denitrating catalyst.
Control mixing speed in polyacrylamide solution process for preparation described in the inventive method not higher than 600 revs/min, preferred mixing speed is 400 ~ 600 revs/min.
Out of stock catalyst monomer described in the inventive method is with TiO
2for main base, be active component with the oxide of tungsten and vanadium and the necessary binding agent of doping and extrusion aid, extrude through honeycomb moulding equipment, obtain after dry and roasting.
In the inventive method, dipping process catalyst end immersion depth is 15-30mm, and during dipping, the time of staying is not less than 10 seconds.
In the inventive method, baking temperature is 100-120 DEG C, and drying time is 2 ~ 12 hours, preferably 3 ~ 6 hours.
In the present invention, sintering temperature is 400-600 DEG C, constant temperature time 3 ~ 15 hours, preferably 4 ~ 8 hours.
A kind of denitrating catalyst, adopts the preparation method of above-mentioned denitrating catalyst to be prepared.
Compared with prior art, a kind of denitrating catalyst of the present invention and preparation method thereof tool has the following advantages:
(1) denitrating catalyst that prepared by the inventive method is compared conventional denitrating catalyst (equally through end face intensive treatment) and is had higher end face strength and wearability, end face strength reaches as high as 1.18MPa, the basic flawless of end face, denuding loss late minimum is 3.96%, can be applicable on the SCR treating apparatus of various working condition;
(2) polyacrylamide used in the inventive method is traditional industry raw material, the inorganic adhesive adopted compared to existing technology or Organic adhesive have the low and polyacrylamide solution mass concentration wide ranges of polyacrylamide amine content in be suitable for maceration extract, operating process is simple, be easy to control, cost is low, single-steeping just can significantly improve end face strength and wearability, and reproducible, and end face is all flawless;
(3) found by research, the end face strengthening effect of stirring condition to out of stock catalyst that polyacrylamide polymers adopts in dissolving process for preparation has material impact, and the speed of agitator adopted in the inventive method can improve the effect of end face strengthening further lower than 600 revs/min.
Detailed description of the invention
Further illustrate functions and effects of the present invention below in conjunction with embodiment, but described embodiment should not be construed as limitation of the scope of the invention.
Embodiment 1
Prepared by catalyst monomer: by the weight content of catalyst containing TiO
2be 75%, the oxide of tungsten and vanadium is 5%, and all the other are necessary binding agent and extrusion aid.Add appropriate distilled water after being mixed by all materials, be mixed into uniform pug, pug by the extrusion molding of honeycomb grinding tool, cuts into catalyst monomer finally by after oven dry and roasting after practicing system and ageing.The porosity of prepared catalyst monomer is 70%, and wall thickness is 1.5mm.Maceration extract configures: take 0.5g polyacrylamide in 300g water, and 400 revs/min are stirred 1 hour, and solid all dissolves.Catalyst soakage: for the ease of examining or check the invigoration effect of this maceration extract to catalyst, according to the requirement cutting catalyst sample of standard GB/T/T1964-1996 " porous ceramics compressive strength test method ", specification is the cylinder of diameter 20mm height 20mm, and often organizing sample is 5.Catalyst sample is positioned in maceration extract completely and takes out after 10 seconds, blow off the liquid in internal gutter by compress wind.Catalyst is dried: be positioned over by catalyst in climatic chamber, temperature is 110 DEG C, and humidity is 75% ~ 95%, and drying time is 4 hours.Catalyst roasting: under the catalyst after oven dry is positioned over air atmosphere, temperature is 500 DEG C, roasting 5 hours.
Embodiment 2
Except dip time is 15 seconds, other are identical with embodiment 1.
Embodiment 3
Except drying time is 2 hours, other are identical with embodiment 1.
Embodiment 4
The preparation of catalyst monomer is with embodiment 1.Maceration extract configures: take 1.0g polyacrylamide in 300g water, and 500 revs/min are stirred 1 hour, and solid all dissolves.The process of catalyst soakage, oven dry and roasting and parameter are with embodiment 1.
Embodiment 5
The preparation of catalyst monomer is with embodiment 1.Maceration extract configures: take 1.5g polyacrylamide in 300g water, and 600 revs/min are stirred 1 hour, and solid all dissolves.The process of catalyst soakage, oven dry and roasting and parameter are with embodiment 1.
Comparative example 1
Except dip time is 5 seconds, other are identical with embodiment 1.
Comparative example 2
The preparation of catalyst monomer with embodiment 1, but does not have the processing procedures such as follow-up dipping, oven dry and roasting.
Comparative example 3
Except the equipment of dipping liquid stir speed (S.S.) is 1000 revs/min, other are identical with embodiment 1.
Comparative example 4
The method of Kaolinite Preparation of Catalyst monomer is with embodiment 1.
According to the requirement cutting catalyst sample of standard GB/T/T1964-1996 " porous ceramics compressive strength test method ".
Catalyst sample being immersed in density by CN101428240A method is in the phosphate dihydrogen aluminum solution of 1.43kg/L 10 seconds, takes out monomer static 8 seconds, and with compressing wind 20 seconds, roasting 4 hours at finally monomer being positioned over 500 DEG C.
In order to investigate the raising ratio of catalyst compression strength, experiment 1 is set.
Experiment 1:
According to the requirement cutting catalyst sample of standard GB/T/T1964-1996 " porous ceramics compressive strength test method ", sample is lain on compressive strength tester test platform, measure normal-temperature catalyst compression strength by on-load pressure.The digital display engineering material compressive strength instrument that the tester that this experiment uses is produced for Xiang Tan Xiang Yi Instrument Ltd..
Weight before the coating of record carrier sample and after roasting, in table 1:
Table 1 intensity test result
| Catalyst is numbered | Catalyst compression strength, MPa |
| Embodiment 1 | 0.89 |
| Embodiment 2 | 0.90 |
| Embodiment 3 | 0.87 |
| Embodiment 4 | 1.17 |
| Embodiment 5 | 1.18 |
| Comparative example 1 | 0.72 |
| Comparative example 2 | 0.65 |
| Comparative example 3 | 0.69 |
| Comparative example 4 | 0.68 |
As can be seen from the above table, the catalyst sample compression strength of the preparation of this patent method is adopted generally to be improved, along with the increase of polyacrylamide addition, required mixing speed also needs to improve, and it just can be made to be uniformly dispersed, but, as can be seen from comparative example 2, when mixing speed is too high, too much bubble can be caused, affect the raising of compression strength.The raising of compression strength is conducive to preventing catalyst module from disguising and fills out and cause damage in sonic soot blowing process, thus the service life of extending catalyst.
In order to investigate the wear-corrosion resistance of catalyst, experiment 2 is set.
Experiment 2
Be positioned in catalyst test apparatus by embodiment 1 ~ 8 and comparative example 1 ~ 3, air inlet dust concentration is 1.5g/L, and air speed is 50000h
-1, the flue gas abrasion time is 8 hours.Record each sample crackle and abrasion loss amount are in following table:
Abrasion loss late (%) is after 8 hours abrasion tests, the ratio of sample loss quality and sample person's quality.
Table 2 catalyst abrasion experimental result
| Numbering | End capacity check situation | Abrasion loss late, % |
| Embodiment 1 | Nothing | 5.42 |
| Embodiment 2 | Nothing | 5.16 |
| Embodiment 3 | Nothing | 5.77 |
| Embodiment 4 | Nothing | 4.02 |
| Embodiment 5 | Nothing | 3.96 |
| Comparative example 1 | Nothing | 6.18 |
| Comparative example 2 | There is crackle | 11.21 |
| Comparative example 3 | Blind crack | 6.52 |
| Comparative example 4 | Blind crack | 7.68 |
As can be seen from the above table, the catalyst sample prepared by this patent has the advantage that compression strength is high and wear-corrosion resistance is good.
The above is only this patent preferred embodiment, not any pro forma restriction is done to this patent, professional can be changed as the case may be and be revised, but, everyly do not depart from the simple modification that technical solution of the present invention content carries out and still belong in the scope of technical solution of the present invention.
Claims (9)
1. the preparation method of a denitrating catalyst, it is characterized in that: comprise the steps: that (1) preparation mass concentration is the polyacrylamide solution of 0.15% ~ 0.5%, control mixing speed in described polyacrylamide solution process for preparation not higher than 600 revs/min; (2) one section, denitrating catalyst monomer end is immersed in the solution prepared by step (1); (3) take out monomer and blow off duct liquid by compress wind, then drying, roasting process obtain denitrating catalyst.
2. method according to claim 1, is characterized in that: in described polyacrylamide solution process for preparation, mixing speed is 400 ~ 600 revs/min.
3. method according to claim 1, is characterized in that: described denitrating catalyst monomer is with TiO
2for main base, be active component with the oxide of tungsten and vanadium and the necessary binding agent of doping and extrusion aid, extrude through honeycomb moulding equipment, obtain after dry and roasting.
4. method according to claim 1, is characterized in that: dipping process catalyst end immersion depth is 15-30mm, and during dipping, the time of staying is not less than 10 seconds.
5. method according to claim 1, is characterized in that: described baking temperature is 100-120 DEG C, and drying time is 2 ~ 12 hours.
6. method according to claim 1 or 5, is characterized in that: described drying time is 3 ~ 6 hours.
7. method according to claim 1, is characterized in that: described sintering temperature is 400-600 DEG C, roasting time 3 ~ 15 hours.
8. the method according to claim 1 or 7, is characterized in that: described roasting time is 4 ~ 8 hours.
9. a denitrating catalyst, is characterized in that: adopt either method in claim 1-8 to be prepared.
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| CN101474565A (en) * | 2009-01-06 | 2009-07-08 | 上海瀛正科技有限公司 | Honeycomb type SCR denitration catalyst as well as preparation method thereof and equipment |
| CN101947443A (en) * | 2010-09-03 | 2011-01-19 | 浙江省环境保护科学设计研究院 | Cellular Mn-Ti-based catalyst for low-temperature selective catalytic reduction denitration reaction and preparation method and using method |
| CN102380370A (en) * | 2011-10-08 | 2012-03-21 | 浙江天蓝环保技术股份有限公司 | Monolithic cellular catalyst for SCR smoke denitration and preparation technology thereof |
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| US20070149394A1 (en) * | 2005-12-22 | 2007-06-28 | Foster Wheeler Energy Corporation | Catalyst, a method of using a catalyst, and an arrangement including a catalyst, for controlling NO and/or CO emissions from a combustion system without using external reagent |
| CN101428240A (en) * | 2008-12-09 | 2009-05-13 | 成都东方凯特瑞环保催化剂有限责任公司 | Selective catalytic reduction flue gas denitration catalyst and production method thereof |
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| CN101947443A (en) * | 2010-09-03 | 2011-01-19 | 浙江省环境保护科学设计研究院 | Cellular Mn-Ti-based catalyst for low-temperature selective catalytic reduction denitration reaction and preparation method and using method |
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