CN104624183A - Preparation method of high-mechanical-strength SCR denitration catalyst - Google Patents

Preparation method of high-mechanical-strength SCR denitration catalyst Download PDF

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CN104624183A
CN104624183A CN201510044616.3A CN201510044616A CN104624183A CN 104624183 A CN104624183 A CN 104624183A CN 201510044616 A CN201510044616 A CN 201510044616A CN 104624183 A CN104624183 A CN 104624183A
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陈宗宗
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Ningbo Hi Tech Zone Xia Yuan Technology Co Ltd
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Abstract

The invention provides a preparation method of a high-mechanical-strength SCR denitration catalyst. WO3/TiO2-Al2O3 powder is adopted so that the whole framework of Al2O3 is kept, and the catalyst also has the good catalytic performance of TiO2, so that the mechanical strength is also improved under the condition that the good catalytic efficiency is guaranteed. On the other hand, a semidry-method pressing and molding process is adopted; in a pressing process, a relatively large gap is filled along the movement and deformation of the powder, and oxidized films on the surfaces of particles are crushed so that the contact area between the particles is enlarged and the attraction force is generated between atoms; the mechanical matching effect between the particles is enhanced so that a blank with certain density and strength is formed, and the mechanical strength and the production efficiency of the catalyst are greatly improved. An experiment result shows that the SCR denitration catalyst prepared by the preparation method has relatively high catalytic efficiency and mechanical strength and long service life.

Description

A kind of preparation method of high mechanical properties SCR denitration
Technical field
The present invention relates to catalyst technical field, particularly relate to a kind of preparation method of high mechanical properties SCR denitration.
Background technology
At present, China's discharged nitrous oxides total amount has reached 1,800 ten thousand tons, if do not adopted an effective measure, continuation increases by Future Ten 5 years Chinese discharged nitrous oxides, may reach more than 3,000 ten thousand tons to the year two thousand twenty.China is coal-fired big country, and coal-burning power plant is the primary emission source of nitrogen oxide, accounts for 40% of total amount, becomes the first batch of control object of country.SCR (SCR) technology is utilized to be the main flow of denitrification process in the world today by the method for the removal of nitrogen oxide in flue gas, and catalyst is the technological core of SCR denitration system, the expense of catalyst accounts for 30% ~ 55% of the initial investment of denitration engineering usually.
SCR catalyst can carry out different classification according to standards such as raw material, structure, operating temperature, purposes.By raw material classification, SCR catalyst is divided into platinum series, titanium series, vanadium is serial and mixed type is serial, and current SCR catalyst is generally and uses TiO 2the V of carrier 2o 5/ WO 3and MoO 3deng metal oxide.By textural classification, SCR catalyst is divided into board-like, corrugated and honeycomb fashion, and wherein board-like catalyst and corrugated catalyst are heterogeneous catalyst, after the destruction wearing and tearing that ash grades are suffered on its surface, can not maintain original catalytic performance, catalyst regeneration hardly may; Cellular catalyst belongs to homogeneous catalysis, with TiO 2, V 2o 5, WO 3for main component, catalyst body is all catalyst material, and after therefore the destruction wearing and tearing that ash grades are suffered on its surface, still can maintain original catalytic performance, catalyst can regenerate.Whole world major part coal-fired power plant uses honeycomb fashion and board-like catalyst, and wherein cellular catalyst recycles rate, low pressure degradation characteristic due to its strong durability, high rotproofness, high reliability, height, is widely applied.
What extensively adopt in conventional coal fired power plant technique is metal oxide catalyst, and its metal oxide mainly contains TiO 2, V 2o 5/ WO 3with MnO etc., wherein the overwhelming majority is V 2o 5/ TiO 2catalyst based.V 2o 5/ TiO 2base SCR catalyst has the advantages such as denitration efficiency is high, selective by force, moderate, the anti-poisoning capability of reaction temperature is strong, stable and reliable operation, but it uses nanoscale TiO 2as catalyst carrier, its price under high performance condition is more expensive, adopts the processing technology of coating or extruding simultaneously, makes the mechanical performance of catalyst stable not, the deficiency such as have that catalyst amount is large, cost is high and service life is short.
Summary of the invention
The technical problem that the present invention solves is the preparation method providing a kind of high mechanical properties SCR denitration, and the SCR denitration of preparation has higher catalytic efficiency and mechanical strength, long service life.
In view of this, the invention provides a kind of preparation method of high mechanical properties SCR denitration, comprise the following steps: by V 2o 5with WO 3/ TiO 2-Al 2o 3powder mixes, and stir, roasting, obtains V after drying 2o 5-WO 3/ TiO 2-Al 2o 3; To V 2o 5-WO 3/ TiO 2-Al 2o 3in add Ludox, methylcellulose, glass fiber and monoethanolamine, obtain catalyst blank after stirring, add water stir, obtain slurry; Add in semidry method compacting tool set successively and reinforce glass fibre carbon fiber composite board and described slurry, compressing, obtain catalyst base substrate; Described catalyst base substrate is crushed to honeycombed catalyst blank, after oven dry, calcining, obtains high mechanical properties SCR denitration.
Preferably, V is obtained 2o 5-WO 3/ TiO 2-Al 2o 3step in, sintering temperature is 480 ~ 520 DEG C, and roasting time is 4 ~ 8 hours.
Preferably, V is obtained 2o 5-WO 3/ TiO 2-Al 2o 3step in, sintering temperature is 500 DEG C, and roasting time is 6 hours.
Preferably, obtain in the step of slurry, the weight ratio of described water and catalyst blank is 10 ~ 16: 100.
Preferably, described WO 3/ TiO 2-Al 2o 3powder is prepared as follows: in oxalic acid solution, add ammonium paratungstate, add Al after stirring 2o 3/ TiO 2complex carrier, stirring, drying, roasting, grinding, obtain WO 3/ TiO 2-Al 2o 3powder.
Preferably, WO is obtained 3/ TiO 2-Al 2o 3in the step of powder, sintering temperature is 480 ~ 520 DEG C, and roasting time is 4 ~ 8 hours.
Preferably, described Al 2o 3/ TiO 2complex carrier is prepared as follows: by AlCl 3solution and TiCl 4solution mixes, and slowly drip ammoniacal liquor and stir, be 8 ~ 9 to pH value, centrifugation, washing precipitate, obtains Al after calcining 2o 3/ TiO 2complex carrier.
Preferably, the concentration of described ammoniacal liquor is 1 ~ 3molL -1.
Preferably, described AlCl 3solution is by aluminium flake is added 2molL -1hydrochloric acid solution in obtained, concentration is 2 ~ 3molL -1.
Preferably, described TiCl 4the concentration of solution is 2 ~ 3molL -1.
Preferably, Al is obtained 2o 3/ TiO 2in complex carrier step, calcining heat is 500 ~ 600 DEG C, and calcination time is 2 ~ 8 hours.
Preferably, Al is obtained 2o 3/ TiO 2in complex carrier step, calcining heat is 550 DEG C, and calcination time is 4 hours.
The invention provides a kind of preparation method of high mechanical properties SCR denitration, comprise the following steps: by V 2o 5with WO 3/ TiO 2-Al 2o 3powder mixes, and stir, roasting, obtains V after drying 2o 5-WO 3/ TiO 2-Al 2o 3, add Ludox, methylcellulose, glass fiber and monoethanolamine, after stirring, obtain catalyst blank, add water and stir, obtain slurry; Add in semidry method compacting tool set successively and reinforce glass fibre carbon fiber composite board and described slurry, compressing, be then crushed to honeycombed catalyst blank, after oven dry, calcining, obtain high mechanical properties SCR denitration.Compared with prior art, the present invention adopts WO 3/ TiO 2-Al 2o 3powder, it both maintained Al 2o 3overall skeleton, again there is TiO 2excellent catalytic performance, thus under the prerequisite that ensure that good catalytic efficiency, also improve mechanical strength.On the other hand, the present invention adopts the compressing technique of semidry method, in pressing process, along with the movement and distortion of powder, larger space is filled, the oxide-film of particle surface is broken, interparticle contact area increases, and makes to produce attraction between atom, and intergranular mechanical wedging action strengthens, thus form the base substrate with certain density and intensity, the mechanical strength of catalyst and production efficiency are improved greatly.Experimental result shows, SCR denitration prepared by the present invention has higher catalytic efficiency and mechanical strength, long service life.
Detailed description of the invention
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The embodiment of the invention discloses a kind of preparation method of high mechanical properties SCR denitration, comprise the following steps: by V 2o 5with WO 3/ TiO 2-Al 2o 3powder mixes, and stir, roasting, obtains V after drying 2o 5-WO 3/ TiO 2-Al 2o 3; To V 2o 5-WO 3/ TiO 2-Al 2o 3in add Ludox, methylcellulose, glass fiber and monoethanolamine, obtain catalyst blank after stirring, add water stir, obtain slurry; Add in semidry method compacting tool set successively and reinforce glass fibre carbon fiber composite board and described slurry, compressing, obtain catalyst base substrate; Described catalyst base substrate is crushed to honeycombed catalyst blank, after oven dry, calcining, obtains high mechanical properties SCR denitration.
Preferably, described WO 3/ TiO 2-Al 2o 3powder is prepared as follows: in oxalic acid solution, add ammonium paratungstate, add Al after stirring 2o 3/ TiO 2complex carrier, stirring, drying, roasting, grinding, obtain WO 3/ TiO 2-Al 2o 3powder.Preferred, described WO 3/ TiO 2-al 2o 3powder is prepared as follows: be dissolved in distilled water by oxalic acid and obtain oxalic acid solution, is dissolved in by ammonium paratungstate in oxalic acid solution, is stirred to and dissolves completely, then add Al wherein 2o 3/ TiO 2complex carrier, carries out the dipping of active component, and evaporating water after stirring continuously on thermostat water bath, obtain WO after grinding after roasting 3/ TiO 2-Al 2o 3powder.Wherein, WO is obtained 3/ TiO 2-Al 2o 3in the step of powder, sintering temperature is preferably 480 ~ 520 DEG C, is more preferably 500 DEG C; Roasting time is preferably 4 ~ 8 hours, is more preferably 6 hours.
Preparation WO 3/ TiO 2-Al 2o 3the Al adopted in powder process 2o 3/ TiO 2complex carrier preferably according to liquid-phase precipitation method preparation, comprises the following steps: by AlCl 3solution and TiCl 4solution mixes, and slowly drip ammoniacal liquor and stir, be 8 ~ 9 to pH value, centrifugation, washing precipitate, obtains Al after calcining 2o 3/ TiO 2complex carrier.Described AlCl 3solution is preferably prepared as follows: at 2molL -1hydrochloric acid solution in add aluminium flake and obtain AlCl 3solution.Described AlCl 3the concentration of solution is preferably 2 ~ 3molL -1; Described TiCl 4the concentration of solution is preferably 2 ~ 3molL -1.Obtain Al 2o 3/ TiO 2in complex carrier step, calcining heat is preferably 500 ~ 600 DEG C, is more preferably 550 DEG C; Calcination time is preferably 2 ~ 8 hours, is more preferably 4 hours.
The Al that the present invention adopts liquid-phase precipitation method to prepare 2o 3/ TiO 2composite nano-powder, as complex carrier, has unique physicochemical property, both maintained Al 2o 3overall skeleton, again there is TiO 2excellent catalytic performance, can improve its mechanical strength under the prerequisite ensureing catalyst efficiency.
Preparation WO 3/ TiO 2-Al 2o 3in powder process, the mode that dropping mode adopts ammoniacal liquor slowly to add, obtains higher apparent volume after calcining, the concentration of the ammoniacal liquor of dropping preferably adopts 1 ~ 3molL -1if ammonia concn increases, the degree of supersaturation of system increases, and the nucleus number that reaction generates instantaneously is many, and crystal grain has little time to grow up and just separates out from solution, and the primary particle obtained is less.Due to the reduction of particle size, the specific area of particle increases, and more easily flocks together, finally make the particle diameter of product increase, obtain larger apparent density in calcination process.
According to the present invention, preparation V 2o 5-WO 3/ TiO 2-Al 2in the step of O, the present invention passes through V 2o 5with WO 3/ TiO 2-Al 2o 3powder is mixed in water, then preferably stirs continuously on thermostat water bath; Sintering temperature is preferably 480 ~ 520 DEG C, is more preferably 500 DEG C, and roasting time is preferably 4 ~ 8 hours, is more preferably 6 hours.
Obtain in the step of slurry, the weight ratio of described water and catalyst blank is preferably 10 ~ 16: 100, is more preferably 16: 100.
The present invention adopts the compressing technique of semidry method, is the V of 10 ~ 16% with moisture content 2o 5-WO 3/ TiO 2-Al 2o 3powder is pressed, in pressing process, along with the movement and distortion of powder, larger space is filled, and the oxide-film of particle surface is broken, and interparticle contact area increases, make to produce attraction between atom, and intergranular mechanical wedging action strengthens, thus form the base substrate with certain density and intensity, the mechanical strength of catalyst and production efficiency are improved greatly.Compared with traditional slip coating molding technique, because semi-dry pressing moisture is about the half of slip coating molding technique, greatly reduce follow-up energy of drying required for calcining, also reduce preparation cost.
In the process preparing high mechanical properties SCR denitration, the present invention is framework material with glass fibre, with TiO 2-Al 2o 3powder is complex carrier, with V 2o 5and WO 3for active component, with Ludox, methylcellulose, glass fiber and monoethanolamine etc. for auxiliary agent.Further, adjust the weight portion of each component, Ludox is preferably 2 ~ 3 weight portions, and methylcellulose is preferably 2 ~ 3 weight portions, and glass fiber is preferably 2 ~ 3 weight portions, and monoethanolamine is preferably 2 ~ 3 weight portions.
High-mechanical property SCR denitration of the present invention, through test of many times, researchs and analyses, and does not add Al 2o 3the cellular catalyst of this technique and domestic and international existing cellular catalyst is adopted to compare, result shows, high-mechanical property SCR denitration prepared by the present invention has that mechanical strength is high, long service life, and has the advantages that catalytic efficiency is high, catalyst amount is few, cost is low.
In order to understand the present invention further, be described in detail to technical scheme provided by the invention below in conjunction with embodiment, protection scope of the present invention is not limited by the following examples.
The raw material that the embodiment of the present invention adopts and chemical reagent are commercial.
Test cellular catalyst of the present invention is purchased from health Mintech, Inc., i.e. honeycomb fashion V 2o 5-WO 3/ TiO 2catalyst.
Embodiment 1
Described high mechanical property and low cost SCR denitration catalyst, comprises the following steps:
1, the preparation of complex carrier: at 2molL -1hydrochloric acid solution in add aluminium flake and obtain AlCl 3solution, then add 2molL -1tiCl 4solution, it is 2molL that two kinds of solution mix rear slow dropping concentration -1ammoniacal liquor and in addition vigorous stirring, reach 8 to pH value.Centrifuge washing sediment, carries out drying and calcining by the solid obtained after filtration, at 550 DEG C of constant temperature 4h, obtains Al 2o 3/ TiO 2complex carrier.
2, the preparation of catalyst blank: get 8g oxalic acid and be dissolved in 160ml distilled water, obtain oxalic acid solution, gets 18g ammonium paratungstate and is dissolved in oxalic acid solution, be stirred to and dissolve completely.Al is flooded with ammonium paratungstate in the oil bath of 85 DEG C 2o 3/ TiO 2complex carrier, stirring, evaporating water.Put 100 DEG C of dry 10h in an oven.Catalyst after oven dry obtains WO after 500 DEG C of roasting 7h grind 3/ TiO 2-Al 2o 3powder.By V 2o 5with WO 3/ TiO 2-Al 2o 3powder is mixed in water, and evaporating water after stirring continuously on thermostat water bath, through 500 DEG C, the roasting post-drying of 6h obtains V 2o 5-WO 3/ TiO 2-Al 2o 3blank, grinding obtains grain diameter and is less than 100 μm, and wherein 80 μm tail over below 5%.Wherein, Al 2o 3/ TiO 2complex carrier 75g, V 2o 51.5g.
3, the preparation of catalyst base substrate: to the V that step 2 is obtained 2o 5-WO 3/ TiO 2-Al 2o 3powder adds as the Ludox (solid-state) of auxiliary agent, methylcellulose, glass fiber and monoethanolamine, again stir 14, up to evenly, obtain catalyst blank, the water adding catalyst billet weight 16% again stirs evenly, and the reinforcing glass fibre carbon fiber composite board of 150*300mm is formed in semidry method compacting tool set, add the blank stirred evenly in a mold, use the pressure of 2000MPa compressing, obtain catalyst base substrate.Wherein, V 2o 5-WO 3/ TiO 2-Al 2o 3powder 17g, Ludox 2g, methylcellulose 2g, glass fiber 2g, monoethanolamine 2g.
4, catalyst is shaping: the catalyst base substrate that step 3 is obtained is put into extruder and makes honeycombed catalyst blank, maintenance 24 hours under temperature 60 C, humidity 50% condition; Temperature 80 DEG C of dryings 3 hours, then temperature 105 DEG C of dryings 5 hours; 250 DEG C of calcinings 3 hours, then 450 DEG C of calcinings 5 hours, obtained finished catalyst.
The test of catalyst: above-mentioned 20 pieces of finished catalysts are loaded in the outer cover of steel plate of 150*150*300mm, becomes a catalyst module.Catalyst module is put into miniature coal flue gas SCR reactor, controlling ammonia nitrogen ratio is 1: 1, and obtain various working condition by change boiler power, all kinds of coal of burning and interpolation sulphur and alkali-metal amount etc., continuous firing 273h, can 92% be reached at the temperature range denitration efficiency of 350 DEG C, and without coming off, ftractureing and being out of shape, adapt to the flue gas of various working, test result is as shown in table 2.
Embodiment 2
Described high mechanical property and low cost SCR denitration catalyst, comprises the following steps:
1, the preparation of complex carrier: at 2molL -1hydrochloric acid solution in add aluminium flake and obtain AlCl 3solution, then add 2molL -1tiCl 4solution, it is 2molL that two kinds of solution mix rear slow dropping concentration -1ammoniacal liquor and in addition vigorous stirring, reach 8 to pH value.Centrifuge washing sediment, carries out drying and calcining by the solid obtained after filtration, at 550 DEG C of constant temperature 4h, obtains Al 2o 3/ TiO 2complex carrier.
2, the preparation of catalyst blank: get 7.5g oxalic acid and be dissolved in 150ml distilled water, obtain oxalic acid solution, gets 17.8g ammonium paratungstate and is dissolved in oxalic acid solution, be stirred to and dissolve completely.Al is flooded with ammonium paratungstate in the oil bath of 85 DEG C 2o 3/ TiO 2complex carrier, stirring, evaporating water.Put 100 DEG C of dry 10h in an oven.Catalyst after oven dry obtains WO after 500 DEG C of roasting 7h grind 3/ TiO 2-Al 2o 3powder.By V 2o 5with WO 3/ TiO 2-Al 2o 3powder is mixed in water, and evaporating water after stirring continuously on thermostat water bath, through 500 DEG C, the roasting post-drying of 6h obtains V 2o 5-WO 3/ TiO 2-Al 2o 3blank, grinding obtains grain diameter and is less than 100 μm, and wherein 80 μm tail over below 5%.Wherein, Al 2o 3/ TiO 2complex carrier 76g, V 2o 51.8g.
3, the preparation of catalyst base substrate: powder obtained for step 2 is added as the Ludox (solid-state) of auxiliary agent, methylcellulose, glass fiber and monoethanolamine, again stir 1 little of evenly, obtain catalyst blank, the water adding catalyst billet weight 16% again stirs evenly, and the reinforcing glass fibre carbon fiber composite board of 150*300mm is formed in semidry method compacting tool set, add the blank stirred evenly in a mold, use the pressure of 2000MPa compressing, obtain catalyst base substrate.Wherein, V 2o 5-WO 3/ TiO 2-Al 2o 3powder 20g, Ludox 2.5g, methylcellulose 2.5g, glass fiber 2.5g, monoethanolamine 2.5g.
4, catalyst is shaping: the catalyst base substrate that step 3 is obtained is put into extruder and makes honeycombed catalyst blank, maintenance 24 hours under temperature 60 C, humidity 50% condition; Temperature 80 DEG C of dryings 3 hours, then temperature 105 DEG C of dryings 5 hours; 250 DEG C of calcinings 3 hours, then 450 DEG C of calcinings 5 hours, obtained finished catalyst.
The test of catalyst: above-mentioned 20 pieces of finished catalysts are loaded in the outer cover of steel plate of 150*150*300mm, becomes a catalyst module.Catalyst module is put into miniature coal flue gas SCR reactor, controlling ammonia nitrogen ratio is 1: 1, and obtain various working condition by change boiler power, all kinds of coal of burning and interpolation sulphur and alkali-metal amount etc., continuous firing 273h, can 89% be reached at the temperature range denitration efficiency of 450 DEG C, and without coming off, ftractureing and being out of shape, adapt to the flue gas of various working, test result is as shown in table 2.
Embodiment 3
1, the preparation of complex carrier: at 2molL -1hydrochloric acid solution in add aluminium flake and obtain AlCl 3solution, then add 3molL -1tiCl 4solution, it is 3molL that two kinds of solution mix rear slow dropping concentration -1ammoniacal liquor and in addition vigorous stirring, reach 9 to pH value.Centrifuge washing sediment, carries out drying and calcining by the solid obtained after filtration, at 550 DEG C of constant temperature 4h, obtains Al 2o 3/ TiO 2complex carrier.
2, the preparation of catalyst blank: get 7.5g oxalic acid and be dissolved in 150ml distilled water, obtain oxalic acid solution, gets 17.6g ammonium paratungstate and is dissolved in oxalic acid solution, be stirred to and dissolve completely.Al is flooded with ammonium paratungstate in the oil bath of 85 DEG C 2o 3/ TiO 2complex carrier, stirring, evaporating water.Put 100 DEG C of dry 10h in an oven.Catalyst after oven dry obtains WO after 500 DEG C of roasting 7h grind 3/ TiO 2-Al 2o 3powder.By V 2o 5with WO 3/ TiO 2-Al 2o 3powder is mixed in water, and evaporating water after stirring continuously on thermostat water bath, through 500 DEG C, the roasting post-drying of 6h obtains V 2o 5-WO 3/ TiO 2-Al 2o 3blank, grinding obtains grain diameter and is less than 100 μm, and wherein 80 μm tail over below 5%.Wherein, Al 2o 3/ TiO 2complex carrier 78g, V 2o 52g.
3, the preparation of catalyst base substrate: powder obtained for step 2 is added as the Ludox (solid-state) of auxiliary agent, methylcellulose, glass fiber and monoethanolamine, again stir 1 little of evenly, obtain catalyst blank, the water adding catalyst billet weight 16% again stirs evenly, and the reinforcing glass fibre carbon fiber composite board of 150*300mm is formed in semidry method compacting tool set, add the blank stirred evenly in a mold, use the pressure of 2000MPa compressing, obtain catalyst base substrate.Wherein, V 2o 5-WO 3/ TiO 2-Al 2o 3powder 23g, Ludox 2.75g, methylcellulose 2.75g, glass fiber 2.75g, monoethanolamine 2.75g.
4, catalyst is shaping: the catalyst base substrate that step 3 is obtained is put into extruder and makes honeycombed catalyst blank, maintenance 24 hours under temperature 60 C, humidity 50% condition; Temperature 80 DEG C of dryings 3 hours, then temperature 105 DEG C of dryings 5 hours; 250 DEG C of calcinings 3 hours, then 450 DEG C of calcinings 5 hours, obtained finished catalyst.
The test of catalyst: above-mentioned 20 pieces of finished catalysts are loaded in the outer cover of steel plate of 150*150*300mm, becomes a catalyst module.Catalyst module is put into miniature coal flue gas SCR reactor, controlling ammonia nitrogen ratio is 1: 1, and obtain various working condition by change boiler power, all kinds of coal of burning and interpolation sulphur and alkali-metal amount etc., continuous firing 273h, can 88% be reached at the temperature range denitration efficiency of 420 DEG C, and without coming off, ftractureing and being out of shape, adapt to the flue gas of various working, test result is as shown in table 2.
Comparative example
V 2o 5-WO 3/ TiO 2(do not add Al 2o 3cellular catalyst) be laboratory self-control, by preparation technology described in the present invention preparation, comprise the steps:
1, TiO 2the preparation of carrier: at 2molL -1hydrochloric acid solution in add 2molL -1tiCl 4solution, mixing rear slow dropping concentration is 2molL -1ammoniacal liquor and in addition vigorous stirring, reach 9 to pH value.Centrifuge washing sediment, carries out drying and calcining by the solid obtained after filtration, at 550 DEG C of constant temperature 4h, obtains TiO 2carrier.
2, the preparation of catalyst blank: get 7.5g oxalic acid and be dissolved in 150ml distilled water, obtain oxalic acid solution, gets 17.6g ammonium paratungstate and is dissolved in oxalic acid solution, be stirred to and dissolve completely.TiO is flooded with ammonium paratungstate in the oil bath of 85 DEG C 2carrier, stirring, evaporating water.Put 100 DEG C of dry 10h in an oven.Catalyst after oven dry obtains WO after 500 DEG C of roasting 7h grind 3/ TiO 2powder.By V 2o 5with WO 3/ TiO 2powder is mixed in water, and evaporating water after stirring continuously on thermostat water bath, through 500 DEG C, the roasting post-drying of 6h obtains V 2o 5-WO 3/ TiO 2blank, grinding obtains grain diameter and is less than 100 μm, and wherein 80 μm tail over below 5%.Wherein, WO 3/ TiO 2powder 75g, V 2o 52g.
3, the preparation of catalyst base substrate: powder obtained for step 2 is added as the Ludox (solid-state) of auxiliary agent, methylcellulose, glass fiber and monoethanolamine, again stir 1 little of evenly, obtain catalyst blank, the water adding catalyst billet weight 16% again stirs evenly, and the reinforcing glass fibre carbon fiber composite board of 150*300mm is formed in semidry method compacting tool set, add the blank stirred evenly in a mold, use the pressure of 2000MPa compressing, obtain catalyst base substrate.Wherein, V 2o 5-WO 3/ TiO 2powder 18g, Ludox 2g, methylcellulose 2g, glass fiber 2g, monoethanolamine 2g.
4, catalyst is shaping: the catalyst base substrate obtained by step 3, maintenance 24 hours under temperature 60 C, humidity 50% condition; Temperature 80 DEG C of dryings 3 hours, then temperature 105 DEG C of dryings 5 hours; 250 DEG C of calcinings 3 hours, then 450 DEG C of calcinings 5 hours, obtained finished catalyst.
The performance of the catalyst of above-mentioned preparation is measured:
The test of catalyst: above-mentioned 20 pieces of finished catalysts are loaded in the outer cover of steel plate of 150*150*300mm, becomes a catalyst module.Catalyst module is put into miniature coal flue gas SCR reactor, controlling ammonia nitrogen ratio is 1: 1, and obtain various working condition by change boiler power, all kinds of coal of burning and interpolation sulphur and alkali-metal amount etc., continuous firing 273h, be 85% ~ 90% at the temperature range denitration efficiencies of 420 DEG C, without coming off, there are cracking and distortion.
High-mechanical property SCR denitration of the present invention, through test of many times, researchs and analyses, and does not add Al 2o 3the cellular catalyst of this technique (comparative example) and commercial cellular catalyst is adopted (to be purchased from health Mintech, Inc., i.e. honeycomb fashion V 2o 5-WO 3/ TiO 2catalyst) compare, result is as following table 2.
The preparation of the various catalyst of table 2 and Performance comparision thereof
Comparing result can be found out, high-mechanical property SCR denitration of the present invention has that mechanical strength is high, long service life, and the feature that catalytic efficiency is high, catalyst amount is few, cost is low.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.

Claims (10)

1. a preparation method for high mechanical properties SCR denitration, is characterized in that, comprises the following steps:
By V 2o 5with WO 3/ TiO 2-Al 2o 3powder mixes, and stir, roasting, obtains V after drying 2o 5-WO 3/ TiO 2-Al 2o 3;
To V 2o 5-WO 3/ TiO 2-Al 2o 3in add Ludox, methylcellulose, glass fiber and monoethanolamine, obtain catalyst blank after stirring, add water stir, obtain slurry;
Add in semidry method compacting tool set successively and reinforce glass fibre carbon fiber composite board and described slurry, compressing, obtain catalyst base substrate;
Described catalyst base substrate is crushed to honeycombed catalyst blank, after oven dry, calcining, obtains high mechanical properties SCR denitration.
2. preparation method according to claim 1, is characterized in that, obtains V 2o 5-WO 3/ TiO 2-Al 2o 3step in, sintering temperature is 480 ~ 520 DEG C, and roasting time is 4 ~ 8 hours.
3. preparation method according to claim 2, is characterized in that, obtains V 2o 5-WO 3/ TiO 2-Al 2o 3step in, sintering temperature is 500 DEG C, and roasting time is 6 hours.
4. preparation method according to claim 1, is characterized in that, obtains in the step of slurry, and the weight ratio of described water and catalyst blank is 10 ~ 16: 100.
5. preparation method according to claim 1, is characterized in that, described WO 3/ TiO 2-Al 2o 3powder is prepared as follows:
In oxalic acid solution, add ammonium paratungstate, after stirring, add Al 2o 3/ TiO 2complex carrier, stirring, drying, roasting, grinding, obtain WO 3/ TiO 2-Al 2o 3powder.
6. preparation method according to claim 5, is characterized in that, obtains WO 3/ TiO 2-Al 2o 3in the step of powder, sintering temperature is 480 ~ 520 DEG C, and roasting time is 4 ~ 8 hours.
7. preparation method according to claim 5, is characterized in that, described Al 2o 3/ TiO 2complex carrier is prepared as follows:
By AlCl 3solution and TiCl 4solution mixes, and slowly drip ammoniacal liquor and stir, be 8 ~ 9 to pH value, centrifugation, washing precipitate, obtains Al after calcining 2o 3/ TiO 2complex carrier.
8. preparation method according to claim 7, is characterized in that, the concentration of described ammoniacal liquor is 1 ~ 3molL -1.
9. preparation method according to claim 7, is characterized in that, obtains Al 2o 3/ TiO 2in complex carrier step, calcining heat is 500 ~ 600 DEG C, and calcination time is 2 ~ 8 hours.
10. preparation method according to claim 9, is characterized in that, obtains Al 2o 3/ TiO 2in complex carrier step, calcining heat is 550 DEG C, and calcination time is 4 hours.
CN201510044616.3A 2015-01-24 2015-01-24 Preparation method of high-mechanical-strength SCR denitration catalyst Pending CN104624183A (en)

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