CN101428240B - Selective catalytic reduction flue gas denitration catalyst and production method thereof - Google Patents
Selective catalytic reduction flue gas denitration catalyst and production method thereof Download PDFInfo
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- CN101428240B CN101428240B CN200810147802XA CN200810147802A CN101428240B CN 101428240 B CN101428240 B CN 101428240B CN 200810147802X A CN200810147802X A CN 200810147802XA CN 200810147802 A CN200810147802 A CN 200810147802A CN 101428240 B CN101428240 B CN 101428240B
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Abstract
The invention relates to a gas denitration catalyst, in particular to a honeycomb denitration catalyst based on the selective catalytic reduction (SCR) technique, and a production method thereof. After a drying monomer with the catalyst composition is sawed, the catalyst is prepared through the following steps: (1) one end part of the monomer is put in an aluminum salt water solution with the density being 1.41-1.45kg/L for being impregnated about 5-12 seconds; (2) a blower is used to blow for 15-25 seconds, so as to blow off superfluous hardening liquid on the surface of the impregnated end part of the monomer; and (3) the monomer after being impregnated in the hardening liquid is calcined in a calciner and hardened. Therefore, the production process of the invention is simple and costs little, and the abrasion strength of the catalyst improved.
Description
Technical field
Selective catalytic reduction catalyst for flue gas denitration and manufacture method, be about higher waste gas (being flue gas) of dust content such as power plant coal-burning boiler waste gas, cement plant stove waste gas, waste incineration furnace exhausts, based on the honeycomb fashion denitrating catalyst of SCR (SCR) technology, and its manufacture method.
Background technology
At present, SCR (SCR) technology is the most successful and most widely used technology of NOx in the flue gas that produces such as power plant coal-burning boiler, cement plant stove, incinerator.Wherein, denitrating catalyst is core, a key component of implementing this technology, and the honeycomb fashion denitrating catalyst is one of main product form of denitrating catalyst.
The base material of honeycomb fashion denitrating catalyst is TiO
2(titanium dioxide), active component are V
2O
5, WO
3, the monolithic extruded moulding of honeycomb monomer, entire body has catalytic activity, and microcosmic is a pore structure, under the effect of reducing agent ammonia nitrogen oxide (NOx) noxious pollutant in the catalyst flue gas of flowing through is realized SCR, generates harmless nitrogen G﹠W.
But, in above-mentioned flue gas, except that containing noxious pollutants such as nitrogen oxide, also contain a large amount of dust.Flow into end at the flue gas of catalyst, these dust will wash away and denudes long-term, the frequent generation in the top layer, end of catalyst, wear and tear and break and the top layer catalyst component peels off thereby cause the catalyst flue gas to flow into end.Like this, along with the passing of running time, will influence the mechanical strength and the denitration efficiency of catalyst, and can shorten the service life of catalyst.
Flow into the end wearing and tearing for reducing the catalyst flue gas, international application no PCT/JP2007/068061 discloses the patent " manufacture method of catalyst and the catalyst that utilizes this method to produce " of Hitachi Zosen Corporation's application, the manufacture method of this catalyst is that the end face part that will contain the carrier structure body of catalyst component soaks in ammonium metatungstate or ammonium metavanadate solution, dry, immersion again, roasting then makes the sclerosis of catalyst end face.The catalyst that makes has by this method improved the tear strength of catalyst end face, obtained good result, it is to be overcome that but it also exists following defective to have: 1, this method needs before dry and after dry the catalyst structure end face respectively once to be soaked, carry out the roasting cure process again, somely the catalyst structure end face is not soaked again after dry, the wearing depth of 1mm can appear in the catalyst end face during use, like this manufacturing process's complexity; 2, soak used ammonium metatungstate, ammonium metavanadate solution and cost an arm and a leg, the catalyst cost that produces is higher; 3, to expect desirable tear strength, because the restriction of ammonium metatungstate, ammonium metavanadate solution characteristic need to carry out drying with electric furnace or winding-up hot-air when the dry catalyst structure, and drying time is long, also caused manufacturing process's complexity, production cost improves.
Summary of the invention
The problem to be solved in the present invention is exactly to provide at above deficiency that a kind of manufacturing process is simple, cost is lower, and the catalyst that improves of tear strength, and its manufacture method.Its technical scheme is as follows:
Catalyst of the present invention is with after containing the dry monomer sawing of catalyst component, makes according to the following steps:
(1) be dipping 5-12 second in the aluminum saline solution of 1.41-1.45kg/L with monomer one end end in density;
(2) with blower fan air blowing 15-25 second, the hardening bath that it is unnecessary that monomer floods end surface is blown clean;
(3) will flood monomer after the hardening bath and be placed in the calcining furnace calcining and carry out cure process, make catalyst.
For the scuff resistance that improves catalyst and guarantee that the sclerosis end does not produce micro-crack, remain in the 1.41-1.45kg/L scope as the aluminium dihydrogen phosphate aqueous solution density of hardening bath and to be advisable.If density is lower than lower limit, active ingredient concentration is low excessively in the hardening bath, and big water gaging is evaporated the thermal stress that is produced and can makes sclerosis end generation micro-crack in the high temperature hardening process, and it is little that scuff resistance is improved; If density surpasses higher limit, active ingredient excessive concentration in the hardening bath is because catalyst component (TiO
2, V
2O
5, WO
3) with the shrinkage factor difference of hardening bath active ingredient in the high-temperature calcination process, sclerosis end also can produce micro-crack, though cross when low seriously not as hardening bath density, also will influence the improvement of scuff resistance.Therefore, to remain in the 1.41-1.45kg/L scope be appropriate to hardening bath density.
Simultaneously, improve the scuff resistance of catalyst and guarantee that the sclerosis end does not produce micro-crack, the dip time of catalyst monomer end in hardening bath remains on 5-12 and is advisable second.If dip time is lower than 5 seconds, hardening bath does not infiltrate in the catalyst pores as yet fully, and the wear-resisting intensity of catalyst improves not obvious; If dip time surpasses 12 seconds, hardening bath surplus in the catalyst pores then, the thermal stress that superfluous hardening bath is evaporated generation in the high temperature hardening process can make the sclerosis end produce micro-crack equally.
Also must blow clean after dipping is finished, otherwise in the high-temperature calcination process, can produce micro-crack because hardening end office's portion's hardening bath excessive concentration with the air blower unnecessary hardening bath that end surfaces assembles that will harden.But the blower fan gassing time is long, can part water blow away in the hardening bath of catalyst inside with infiltrating, be equivalent to improve the density of hardening bath, and making the sclerosis end in the high-temperature calcination process, produce micro-crack.Experiment showed, that gassing time is advisable with 15-25 second.
Compared with prior art the present invention has following beneficial effect:
1, aluminium dihydrogen phosphate is a kind of inorganic binder, utilize it to make hardening bath, active ingredient in the hardening bath is bonded in the surface of catalyst monomer sclerosis end and embeds in the internal void by dipping and calcining cure process operation, before catalyst being carried out drying, only need dipping once can reach desirable anti-wear performance, simplified operation, reduced production cost, the catalyst monomer that contains any catalyst component all has been suitable for;
2, the biphosphate aluminum feedstock is cheap is easy to get, and is made into the cost of hardening bath only for using ammonium metatungstate, ammonium metavanadate aqueous solution as 1/5 to 1/6 of hardening bath cost with it;
When 3, the present invention carried out drying after to catalyst soakage, only need blow the wind that need not heat to catalyst monomer dipping end surface, the unnecessary hardening bath in surface were blown off get final product, and drying time is short, saves time, and saves production cost;
4, quicken the abrasion contrast test by catalyst being carried out dust, the result proves: the catalyst that adopts the inventive method to make almost be can't see the wearing and tearing that caused by dust at catalyst monomer end surface, greatest wear only is about 0.1mm, abrasion rate major part is below 8%, maximum abrasion rate is below 11%, and the sclerosis end does not almost have or only have a small amount of micro-crack.Improve than the catalyst abrasion intensity of producing as hardening bath, can be used in the denitrating flue gas that contains a large amount of dust and unlikely generation wearing and tearing with ammonium metatungstate, ammonium metavanadate aqueous solution.
The specific embodiment
Below, according to embodiment the present invention is specified, but scope of the present invention is not limited to following embodiment:
Embodiment 1
To contain catalyst component (TiO
2, V
2O
5, WO
3) dry monomer (this drying monomer is to contain catalyst component (TiO
2, V
2O
5, WO
3) and the kneading group of liquid substance be squeezed into the honeycomb monomer, fully dry and get under 115 ℃ of conditions, its manufacture method is a prior art.) after sawing becomes specific length (according to the different requirements of different denitration engineering project flue gas conditions, generally being 600-1300mm), follow these steps to make catalyst:
(1) be dipping 7 seconds in the aluminium dihydrogen phosphate hardening bath of 1.43kg/L with monomer one end end 20--30mm in density;
(2) take out monomer, left standstill 8 seconds;
(3) blew 20 seconds with the compressed air blower fan, the hardening bath that it is unnecessary that monomer floods end surface is blown clean;
(4) will flood monomer after the hardening bath and be placed on and be warming up to 500 ℃ of calcinings in the calcining furnace and carried out cure process in 4 hours, make catalyst.
Embodiment 2
Hardening bath density is adjusted into 1.45kg/L, and other conditions are the same with embodiment 1 with cure process, make catalyst.
Embodiment 3
Hardening bath density is adjusted into 1.42kg/L, and other conditions are the same with embodiment 1 with cure process, make catalyst.
Embodiment 4
Hardening bath density is adjusted into 1.41kg/L, and other conditions are the same with embodiment 1 with cure process, make catalyst.
Embodiment 5
Dip time is adjusted into 5 seconds, and other conditions are the same with embodiment 1 with cure process, make catalyst.
Embodiment 6
Dip time is adjusted into 9 seconds, and other conditions are the same with embodiment 1 with cure process, make catalyst.
Embodiment 7
Dip time is adjusted into 11 seconds, and other conditions are the same with embodiment 1 with cure process, make catalyst.
Embodiment 8
The blower fan gassing time is adjusted into 15 seconds, and other conditions are the same with embodiment 1 with cure process, make catalyst.
Embodiment 9
The blower fan gassing time is adjusted into 18 seconds, and other conditions are the same with embodiment 1 with cure process, make catalyst.
Embodiment 10
The blower fan gassing time is adjusted into 25 seconds, and other conditions are the same with embodiment 1 with cure process, make catalyst.
Comparative example 1 (hardening bath density is lower than the requirement of regulation density range lower limit)
Hardening bath density is adjusted into 1.35kg/L, and other conditions are the same with embodiment 1 with cure process, make catalyst.
Comparative example 2 (hardening bath density is higher than the regulation density range upper limit and requires)
Hardening bath density is adjusted into 1.49kg/L, and other conditions are the same with embodiment 1 with cure process, make catalyst.
Comparative example 3 (the sclerosis dip time does not satisfy regulation dip time lower limit and requires)
Dip time is adjusted into 3 seconds, and other conditions are the same with embodiment 1 with cure process, make catalyst.
Comparative example 4 (the blower fan gassing time does not satisfy regulation gassing time lower limit and requires)
The blower fan gassing time is adjusted into 10 seconds, and other conditions are the same with embodiment 1 with cure process, make catalyst.
Comparative example 5 (the directly high-temperature calcination without the end dipping after the monomer drying sawing)
Catalyst component (TiO will be contained after the dry sawing
2, V
2O
5, WO
3) the honeycomb monomer, dipping operation in obstructed peroxophosphoric acid aluminum dihydrogen aqueous solution end directly is placed on and is warming up to 500 ℃ of calcinings 4 hours in the calcining furnace, makes catalyst.
Comparative example 6 (making hardening bath with ammonium metavanadate aqueous solution, ammonium metatungstate aqueous solution substitutes)
Contained the honeycomb monomer of catalyst component after 3 hours with extrusion modling and through calcining under 40 minutes, 500 ℃ conditions of 170 ℃ of dryings, dipping is 30 minutes in the ammonium metavanadate aqueous solution of 3.88 gram molecules/L, takes out monomer under 220 ℃ of conditions dry 2 hours.Dried monomer end 10mm was flooded for 5 seconds in the ammonium metatungstate aqueous solution of 3.88 gram molecules/L, take out monomer under 220 ℃ of conditions dry 2 hours.After repeated impregnations ammonium metatungstate aqueous solution and dry the processing, monomer was placed under 400 ℃ of conditions calcining 30 minutes, carry out the cure process of catalyst end face and make catalyst.
To be placed in the air testing device that contains dust according to the catalyst that embodiment 1～10 and comparative example 1～6 are made, above-mentioned catalyst is carried out dust wash away accelerated wear test, and more various catalyst is washed away abraded depth (mm) and the abrasion rate (loss in weight %) that the back is produced by dust.
In above-mentioned abrasion test, the compressed air flow velocity LV of inflow catalyst sclerosis end is 40m/s, dust content is 110g/m3, temperature is a room temperature, the flushing time that catalyst is exposed in the compressed air that contains dust is 30 minutes, and this time is decided to be equivalent to catalyst under actual flue gas processing device situation 2000 hours flushing time.
Result of the test
Sclerosis end micro-crack situation before above-mentioned various catalyst abrasion result of the tests and the abrasion is listed in following table 1:
Table 1: various catalyst abrasion result of the tests
| Example | The end wear degree of depth (mm) | Abrasion rate (loss in weight %) | Sclerosis end micro-crack situation before the abrasion |
| Embodiment 1 | Almost do not have | 7.58 | Almost do not have |
| Embodiment 2 | Almost do not have | 7.43 | Minute quantity |
| Embodiment 3 | Almost do not have | 7.65 | Almost do not have |
| Embodiment 4 | 0.1mm below | 7.88 | Minute quantity |
| Embodiment 5 | About 0.1mm | 10.47 | On a small quantity |
| Embodiment 6 | Almost do not have | 7.35 | Almost do not have |
| Embodiment 7 | Almost do not have | 7.68 | Almost do not have |
| Embodiment 8 | About 0.1mm | 10.26 | On a small quantity |
| Embodiment 9 | Almost do not have | 7.90 | Almost do not have |
| Embodiment 10 | 0.1mm below | 8.01 | Minute quantity |
| Comparative example 1 | 0.1mm more than | 14.65 | In a large number |
| Comparative example 2 | 0.1mm more than | 13.61 | More |
| Comparative example 3 | 0.1mm more than | 14.88 | In a large number |
| Comparative example 4 | 0.1mm more than | 14.12 | More |
| Comparative example 5 | 0.5mm more than | 20.48 | There is not the sclerosis end |
| Comparative example 6 | Almost do not have | 8.05 | Almost do not have |
As shown in table 1, the catalyst that utilizes the embodiment of the invention 1～10 to produce, almost can't see the wearing and tearing that cause by dust at catalyst monomer end surface, greatest wear only is about 0.1mm, abrasion rate major part is below 8%, maximum abrasion rate is below 11%, and the sclerosis end does not almost have or only have a small amount of micro-crack.At the comparative example 1,2 that aluminium dihydrogen phosphate aqueous solution density is adjusted into 1.35kg/L, 1.49kg/L, perhaps dip time is reduced to 3 seconds comparative example 3, perhaps the blower fan gassing time is reduced in 10 seconds the comparative example 4, the above wearing and tearing of 0.1mm have all been seen, the abrasion rate has surpassed 13%, and the sclerosis end produces more or a large amount of micro-cracks.But in the comparative example 5 that catalyst monomer end face is not handled through the dipping hardening bath, end wear reaches more than the 0.5mm, and the abrasion rate reaches more than 20%.And substituting in the comparative example 6 of aluminium dihydrogen phosphate aqueous solution as hardening bath with ammonium metavanadate aqueous solution and ammonium metatungstate aqueous solution, the situation that wearing depth, abrasion rate and the sclerosis end that can see the catalyst end face produces micro-crack all with embodiment 1-3,6-7 and 9 suitable.Can confirm according to above-mentioned test, utilize method of the present invention can make the catalyst that tear strength improves.And can confirm that the density of maceration extract is advisable in 5-12 second, blower fan gassing time at 1.41-1.45kg/L, dip time in 15-25 scope second.
Claims (2)
1. selective catalytic reduction catalyst for flue gas denitration is characterized in that it is with after containing the dry monomer sawing of catalyst component, makes according to the following steps:
(1) be dipping 5-12 second in the aluminium dihydrogen phosphate aqueous solution of 1.41-1.45kg/L with monomer one end end in density;
(2) with blower fan air blowing 15-25 second, the hardening bath that it is unnecessary that monomer floods end surface is blown clean;
(3) will flood monomer after the hardening bath and be placed in the calcining furnace calcining and carry out cure process, make catalyst.
2. the manufacture method of a selective catalytic reduction catalyst for flue gas denitration is characterized in that may further comprise the steps:
(1) will contain the dry monomer sawing of catalyst component after, be dipping 5-12 second in the aluminium dihydrogen phosphate aqueous solution of 1.41-1.45kg/L with monomer one end end in density;
(2) with blower fan air blowing 15-25 second, the hardening bath that it is unnecessary that monomer floods end surface is blown clean;
(3) will flood monomer after the hardening bath and be placed in the calcining furnace calcining and carry out cure process, make catalyst.
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| CN103769240B (en) * | 2012-10-25 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of preparation method of denitrifying catalyst with selective catalytic reduction |
| CN103008017B (en) * | 2012-12-03 | 2014-09-17 | 浙江天蓝环保技术股份有限公司 | Hardening liquid used for strengthening top of low temperature SCR denitration catalyst module and application thereof |
| CN103316717A (en) * | 2013-06-18 | 2013-09-25 | 浙江德创环保科技股份有限公司 | SCR (Selective Catalytic Reduction) denitration catalyst module hardening liquid |
| CN103316718A (en) * | 2013-06-18 | 2013-09-25 | 浙江德创环保科技股份有限公司 | Process for hardening honeycomb type SCR (Selective Catalytic Reduction) denitration catalyst module |
| CN105498538B (en) * | 2016-01-18 | 2019-02-01 | 北京国电龙源环保工程有限公司 | A kind of regenerated liquid and regeneration method for repairing useless denitrating catalyst mechanical performance |
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| CN110671174A (en) * | 2019-10-29 | 2020-01-10 | 中船动力研究院有限公司 | Low-pressure selective catalytic reduction system and control device thereof |
| CN113181975B (en) * | 2021-04-28 | 2023-05-23 | 江苏峰业环境科技集团股份有限公司 | Self-fluid-supplementing balanced denitration catalyst end hardening device and hardening process |
| CN113289609B (en) * | 2021-06-09 | 2023-07-14 | 大唐南京环保科技有限责任公司 | High-wear-resistance wide-temperature denitration catalyst and preparation method and application thereof |
| CN114713292A (en) * | 2022-05-05 | 2022-07-08 | 安徽工程大学 | End face treating agent, preparation method and application thereof, and end face treatment method after catalyst regeneration |
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Address after: Vuko west two road 610045 Sichuan city of Chengdu Province, No. 2 Patentee after: Oriental kaitrey (Chengdu) Environmental Protection Technology Co.,Ltd. Address before: Vuko west two road 610045 Sichuan city of Chengdu Province, No. 2 Patentee before: CHENGDU DONGFANG KWH ENVIRONMENTAL PROTECTION CATALYSTS Co.,Ltd. |