CN103977790B - A kind of preparation method of diesel car tail gas refining vanadia-based SCR catalysts - Google Patents
A kind of preparation method of diesel car tail gas refining vanadia-based SCR catalysts Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of diesel car tail gas refining vanadia-based SCR catalysts.Anchoring dispersant is dissolved in deionized water by described preparation method, stirs, then adds vanadium source and tungsten source, stirring and dissolving; Then titanium source is under agitation added, ageing; Then add binding agent, stir, obtain catalyst pulp; Finally be coated on carrier by catalyst pulp, dry, roasting, obtains vanadia-based SCR catalysts, and wherein said anchoring dispersant is selected from one or more in OPEO, citric acid, tartaric acid, polyacrylic acid, hydrogen peroxide.Preparation method of the present invention adds anchoring dispersant in the preparation process of vanadia-based SCR catalysts, not only achieve the preparation technology that vanadia-based SCR catalysts " is treated different things alike ", shorten technological process, save production cost, and the vanadia-based SCR catalysts of preparation has good activity, durability and stability, has a extensive future simultaneously.
Description
Technical field
The invention belongs to catalysis technical field, relate to a kind of preparation method of catalyst, be specifically related to a kind of preparation method of diesel car tail gas refining vanadia-based SCR catalysts.
Background technology
Nitrogen oxide (NO
x) be one of pollutant topmost in air.Not only there is stronger bio-toxicity and especially stimulate respiratory system, and be one of main reason of acid rain and photochemical fog etc.Atmosphere pollution is now serious, control NO
xdischarge very urgent, countries in the world extensively put into effect law compulsion limit row.
Various NO
xin removing sulfuldioxide, NH
3-SCR becomes the market mainstream because of efficient, durable, technology maturation.Wherein vanadium base SCR is widely adopted with its good activity, excellent Sulfur tolerance, ripe technology and cheap price.In view of China's diesel oil sulfur content is high, vanadium base SCR becomes the inevitable choice of heavy-duty diesel vehicle various countries IV discharge standard because of the Sulfur tolerance of its excellence.One vapour, Yuchai, heavy vapour, Weihe River bavin etc. all determine the program.Nearly all coal-burning power plant is also because flue gas sulfur content height selects vanadium base SCR as after-treatment system.
Product ripe on market adopts metatitanic acid or titanium dioxide through dipping tungsten mostly, and dry, roasting obtains titanium tungsten powder, and titanium tungsten powder is again through vanadium impregnated, and dry, roasting obtains catalyst powder, and powder obtains catalyst pulp through defibrination.The preparation method of this vanadia-based SCR catalysts, by dipping, makes vanadium, tungsten evenly spreads in the duct of titanium dioxide, form insoluble matter make it fix by dry, roasting.This technique need prepare titanium tungsten powder, and also need further slurrying to apply, long flow path, cost are high again, simultaneously obtained vanadia-based SCR catalysts poor stability.
Directly mixed by all raw materials, namely " treating different things alike " is that Kaolinite Preparation of Catalyst is most economical, effective method.But directly mix titanium dioxide, vanadium, tungsten makes slurry, the tungsten in solution, vanadium will move with moisture evaporation, enrichment, cause disperseing uneven, easy-sintering, durability and poor stability.
Patent of invention CN102698736A discloses a kind of titanium tungsten powder that uses for carrier is by the technology of obtained slurry of sizing mixing, due to without dipping, dry, roasting, vanadyl oxalate in solution will move in dry run, causes its dispersion uneven, cannot ensure durability and stability.
Application for a patent for invention 201010274007.4 discloses a kind of use titanium dioxide, through the method directly obtaining catalyst pulp of sizing mixing, but its tungsten, vanadium all can not effectively disperse, fixing, its endurance quality more cannot ensure, and lacking dispersion means, slurry is difficult to the upper carrying capacity that primary coating reaches enough.
Summary of the invention
The object of the invention is to overcome above-mentioned deficiency existing in prior art, a kind of preparation method of diesel car tail gas refining vanadia-based SCR catalysts is provided.This preparation method adds anchoring dispersant in the preparation process of vanadia-based SCR catalysts, by sizing mixing, primary coating, dry, roasting four step forms honeycomb catalyst, during roasting, carrier and catalyst generate in honeycomb substrate simultaneously, wherein said anchoring dispersant be selected from OPEO (OP-10), citric acid, tartaric acid, polyacrylic acid, hydrogen peroxide one or both.Described preparation method's raw material is cheap, technique is simple, the cycle is short, and thus production cost is low; And obtained vanadia-based SCR catalysts has good activity, durability and stability simultaneously.
In order to realize foregoing invention object, the invention provides following technical scheme:
The preparation method of diesel car tail gas refining vanadia-based SCR catalysts of the present invention, comprises the steps:
(1) be dissolved in deionized water by anchoring dispersant, stir, then add vanadium source and tungsten source, stirring and dissolving, obtains mixed liquor;
(2) in step (1) gained mixed liquor, add titanium source, ageing under stirring, obtain suspension;
(3) in step (2) gained suspension, add binding agent, stir, obtain catalyst pulp;
(4) be coated on carrier by step (3) gained slurry, dry, roasting, obtains diesel car tail gas refining vanadia-based SCR catalysts.
Wherein, in described step (1), anchoring dispersant is selected from any one or a few in OPEO, citric acid, tartaric acid, polyacrylic acid, hydrogen peroxide.
Applicant is through repeatedly testing, find in preparation method of the present invention, add described anchoring dispersant, anchoring dispersant energy and tungsten, vanadium bonding, and be combined with titanium dioxide by absorption, coordination, make the vanadium in solution, tungsten is evenly dispersed, be fixed in titanium dioxide duct, do not move in dry run, thus ensure that tungsten, vanadium are dispersed on the titanium dioxide; Meanwhile, this anchoring dispersant also has peptizaiton to titanium dioxide, and make slurry fluidity good, not stratified, primary coating amount can more than 210g/L.Anchoring dispersant add the activity, durability and the stability that ensure that gained vanadia-based SCR catalysts.
Preferably, preparation method of the present invention by weight, comprises the steps:
(1) be dissolved in 20 ~ 35 parts of deionized waters by 0.5 ~ 3 part of anchoring dispersant, stir, then add 0.5 ~ 1.3 part of vanadium source and 0.6 ~ 1.5 part of tungsten source, stirring and dissolving, obtains mixed liquor;
(2) in step (1) gained mixed liquor, add 13 ~ 30 parts of titanium sources under stirring, ageing, obtains suspension;
(3) in step (2) gained suspension, add 2 ~ 6 parts of binding agents, stir, obtain catalyst pulp;
(4) be coated on carrier cordierite ceramic by step (3) gained slurry, dry, roasting, obtains diesel car tail gas refining vanadia-based SCR catalysts.
Wherein, in described step (1), anchoring dispersant is selected from any one or a few in OPEO (OP-10), citric acid, tartaric acid, polyacrylic acid, hydrogen peroxide.
Preferably, in described step (1), anchoring dispersant is made up of by weight for 2:1 citric acid and polyacrylic acid.Preferred by this, obtained vanadia-based SCR catalysts is active and durability is best.
Preferably, in described step (1), vanadium source is selected from any one or a few in ammonium vanadate, vanadic sulfate, vanadic anhydride, vanadium oxytrichloride, vanadium tetraoxide.
Preferably, in described step (1), tungsten source is selected from any one or a few in ammonium metatungstate, ammonium tungstate, ammonium paratungstate.
Preferably, in described step (2), titanium source is metatitanic acid and/or titanium dioxide.
Preferably, in described step (3), binding agent is selected from any one or a few in boehmite, Alumina gel, Ludox, zirconium colloidal sol, acetic acid zirconium.
Preferably, in above-mentioned preparation method, in described step (2), the temperature of ageing is 50 ~ 90 DEG C, and the time is 0.5 ~ 5h; When Aging Temperature is lower than 50 DEG C or higher than 90 DEG C, digestion time, lower than 0.5h or higher than 5h, all can affect the mobility of slurry and the activity of vanadia-based SCR catalysts.Further preferably, the temperature of described ageing is 50 ~ 60 DEG C, and the time is 0.5 ~ 2h; Preferably, the temperature of described ageing is 50 DEG C to the best, and the time is 2h.
Preferably, in above-mentioned preparation method, in described step (4), the temperature of roasting is 250 ~ 650 DEG C, and the time is 0.5 ~ 5h; When sintering temperature is lower than 250 DEG C or higher than 650 DEG C, roasting time, lower than 0.5h or higher than 5h, all can reduce activity and the endurance quality of vanadia-based SCR catalysts.Further preferably, the temperature of described roasting is 250 ~ 300 DEG C, and the time is 1 ~ 2h; Preferably, the temperature of described roasting is 300 DEG C to the best, and the time is 1h.
Preferably, adopt automatic coating machine to be coated on carrier cordierite ceramic by slurry in described step (4), coating number of times is 1 time.Owing to adding anchoring dispersant in the preparation process of vanadia-based SCR catalysts, this anchoring dispersant has peptizaiton to titanium dioxide, make slurry fluidity good, not stratified, primary coating can more than 210g/L, therefore the present invention preferably adopts automatic coating machine to be coated on carrier cordierite ceramic by slurry, and coating number of times is 1 time.
Compared with prior art, beneficial effect of the present invention:
(1) the present invention is in the preparation method of vanadia-based SCR catalysts, add anchoring dispersant, anchoring dispersant energy and tungsten, vanadium bonding, and be combined with titanium dioxide by absorption, coordination, make the vanadium in solution, tungsten is evenly dispersed, be fixed in titanium dioxide duct, do not move in dry run, thus ensure that tungsten, vanadium are dispersed on the titanium dioxide, achieve " treating different things alike " preparation activity and good endurance, and the reliable vanadia-based SCR catalysts of stability.Experiment shows, vanadia-based SCR catalysts prepared by the inventive method is to NO
xcompared with commercial catalysts prepared by variance and the traditional handicraft of conversion ratio, high temperature section is 0.58 times, and low-temperature zone is only 0.4 times.
(2) the present invention is in the preparation method of vanadia-based SCR catalysts, add anchoring dispersant, anchoring dispersant also has peptizaiton to titanium dioxide, make slurry fluidity good, not stratified, primary coating can more than 210g/L, adopt primary coating technique, effectively reduce repetitive coatings, cordierite carrier that drying, roasting cause is damaged.
(3) preparation method of the present invention is with short production cycle, raw material cheap, and manufacturing cost significantly reduces than traditional handicraft.
(4) preparation method of the present invention does not produce solid, liquid wastes, and post processing expense is low.
Detailed description of the invention
Below in conjunction with test example and detailed description of the invention, the present invention is described in further detail.But this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following embodiment, all technology realized based on content of the present invention all belong to scope of the present invention.
Embodiment 1
1kg citric acid, 0.5kg polyacrylic acid are dissolved in 25kg deionized water, stir; Add 0.97kg ammonium vanadate (NH
4vO
3) and 1.06kg ammonium metatungstate, stirring and dissolving, obtains mixed liquor; Add 20.20kg titanium dioxide under stirring, at 50 DEG C, ageing 2h, obtains suspension; Add 4.2kg Ludox (SiO in Ludox
2content is 25%, stirs, and obtains catalyst pulp.
Obtained catalyst pulp is coated on carrier cordierite ceramic by coating machine, dry 1h at 80 DEG C; Finally roasting 1h at 300 DEG C, to obtain final product.
Comparative example 1: adopt oxalic acid to replace citric acid and polyacrylic acid (ammonium vanadate itself is water insoluble, and oxalic acid combines rear i.e. water soluble), remaining reaction condition all with above-described embodiment 1, to obtain final product.
The vanadia-based SCR catalysts that the present embodiment 1 and comparative example 1 obtain is carried out the investigation of NOx removal efficiency on fixed bed reactors.The catalyst size used is 1*1in, 400cpsi; Reflection gaseous mixture consists of: [NO]=[NH
3]=500ppm, [O
2]=10%, [H
2o]=8%, N
2as Balance Air, air speed is 40000h
-1, reaction temperature is 200 ~ 500 DEG C; Gas component all uses infrared detection.
Vanadia-based SCR catalysts prepared by embodiment 1 and comparative example 1 is to NO
xconversion ratio as shown in table 1.Letter inside bracket represents state, and wherein f represents fresh, and a represents aging sample; Aging condition is: temperature 600 DEG C, moisture content 5%, air speed 40000h
-1.
Vanadia-based SCR catalysts prepared by table 1 embodiment 1 and comparative example 1 is to NO
xconversion ratio
As can be seen from Table 1, fresh, the aging sample of vanadia-based SCR catalysts prepared by embodiment 1 all has good activity, full temperature section balancing performance, and fresh ageing properties is balanced; And do not add vanadia-based SCR catalysts prepared by anchoring dispersant only in fresh sample low temperature active better, high temperature section is poor, and aging rear full temperature section is all obviously deteriorated.Show, not only increase the activity of vanadia-based SCR catalysts after adding anchoring dispersant, improve its durability simultaneously.
Embodiment 2
2.0kg tartaric acid is dissolved in 30kg deionized water, stirs; Add 0.5kg vanadic sulfate and 0.7kg ammonium paratungstate, stirring and dissolving, obtains mixed liquor; Add 15kg metatitanic acid under stirring, at 90 DEG C, ageing 0.5h, obtains suspension; Add 3kg zirconium colloidal sol (in zirconium colloidal sol, zirconium dioxide content is 10%), stir, obtain catalyst pulp.
Obtained catalyst pulp is coated on carrier cordierite ceramic by coating machine, dry 1h at 80 DEG C; Finally roasting 0.5h at 650 DEG C, to obtain final product.
Comparative example 2: adopt oxalic acid to replace tartaric acid, remaining reaction condition all with above-described embodiment 2, to obtain final product.
The vanadia-based SCR catalysts that embodiment 2 and comparative example 2 obtain respectively is carried out NO on fixed bed reactors
xremoval efficiency is investigated, and condition of investigating is with embodiment 1.Result is as shown in table 2.
Vanadia-based SCR catalysts prepared by table 2 embodiment 2 and comparative example 2 is to NO
xconversion ratio
As can be seen from Table 2, catalyst fresh sample performance and the comparative example 2 of embodiment 2 preparation are basically identical, but aging rear activity is obviously better than comparative example 2.
Embodiment 3
1.2kgOP-10,1.8kg hydrogen peroxide is dissolved in 35kg deionized water, stirs; Add 1.2kg vanadic anhydride and 1.5kg ammonium tungstate, stirring and dissolving, obtains mixed liquor; Add 28kg metatitanic acid under stirring, at 70 DEG C, ageing 3h, obtains suspension; Add 6kg Alumina gel, stir, obtain catalyst pulp.
Obtained catalyst pulp is coated on carrier cordierite ceramic by coating machine, dry 0.5h at 150 DEG C; Finally roasting 5h at 250 DEG C, to obtain final product.
Comparative example 3: adopt oxalic acid to replace OP-10 and hydrogen peroxide, remaining reaction condition all with above-described embodiment 3, to obtain final product.
The vanadia-based SCR catalysts that embodiment 3 and comparative example 3 obtain respectively is carried out NO on fixed bed reactors
xremoval efficiency is investigated, and condition of investigating is with embodiment 1.Result is as shown in table 3.
Vanadia-based SCR catalysts prepared by table 3 embodiment 3 and comparative example 3 is to NO
xconversion ratio
As can be seen from Table 3, the fresh sample cryogenic property of catalyst that embodiment 3 obtains slightly is worse than comparative example 3, but its high-temperature behavior has more significantly advantage.And after the obtained catalyst ageing of comparative example 3 degradation apparently higher than embodiment 3.
Embodiment 4
0.8kg hydrogen peroxide, 1kg polyacrylic acid are dissolved in 20kg deionized water, stir; Add 0.4kg vanadium oxytrichloride, 0.3kg vanadium tetraoxide and 0.9kg ammonium tungstate, stirring and dissolving, obtains mixed liquor; Add 7kg metatitanic acid, 6kg titanium dioxide under stirring, at 60 DEG C, ageing 4h, obtains suspension; Add 2kg acetic acid zirconium, stir, obtain catalyst pulp.
Obtained catalyst pulp is coated on carrier cordierite ceramic by coating machine, dry 0.8h at 100 DEG C; Finally roasting 2h at 500 DEG C, to obtain final product.
Comparative example 4: adopt oxalic acid to replace hydrogen peroxide and polyacrylic acid, remaining reaction condition all with above-described embodiment 4, to obtain final product.
The vanadia-based SCR catalysts that embodiment 4 and comparative example 4 obtain respectively is carried out NO on fixed bed reactors
xremoval efficiency is investigated, and condition of investigating is with embodiment 1.Result is as shown in table 4.
Vanadia-based SCR catalysts prepared by table 4 embodiment 4 and comparative example 4 is to NO
xconversion ratio
As can be seen from Table 4, the fresh sample of catalyst that embodiment 4 is obtained and aging sample performance are all better than comparative example 4.
Embodiment 5
0.5kg hydrogen peroxide, 0.6kg tartaric acid and 0.4kgOP-10 are dissolved in 25kg deionized water, stir; Add 0.9kg vanadic anhydride and 1kg ammonium metatungstate, stirring and dissolving, obtains mixed liquor; Add 18kg titanium dioxide under stirring, at 80 DEG C, ageing 2.5h, obtains suspension; Add 5kg boehmite, stir, obtain catalyst pulp.
Obtained catalyst pulp is coated on carrier cordierite ceramic by coating machine, dry 1h at 80 DEG C; Finally roasting 2.5h at 400 DEG C, to obtain final product.
Comparative example 5: adopt oxalic acid to replace hydrogen peroxide, tartaric acid and OP-10, remaining reaction condition all with above-described embodiment 5, to obtain final product.
The vanadia-based SCR catalysts that embodiment 5 and comparative example 5 obtain respectively is carried out NO on fixed bed reactors
xremoval efficiency is investigated, and condition of investigating is with embodiment 1.Result is as shown in table 5.
Vanadia-based SCR catalysts prepared by table 5 embodiment 5 and comparative example 5 is to NO
xconversion ratio
As can be seen from Table 5, the fresh sample of the catalyst that embodiment 5 is obtained and aging sample performance are all better than comparative example 5.
According to the data in table 1 ~ 5, in the preparation process of vanadia-based SCR catalysts, add anchoring dispersant, can realize " treating different things alike ", shorten production procedure, simultaneously obtained vanadia-based SCR catalysts is compared with the catalyst adopting oxalic acid to replace anchoring dispersant obtained, and it is active and durability is better.The vanadia-based SCR catalysts effect wherein prepared by method described in embodiment 1 is best, all has good activity to fresh, aging sample, full temperature section balancing performance, and fresh ageing properties is balanced.
Embodiment 6
The basis of embodiment 1 changes composition and the consumption of anchoring dispersant, and remaining reaction condition is all with embodiment 1, and the composition of investigation anchoring dispersant and consumption are on the impact of vanadia-based SCR catalysts performance, and wherein the preparation method of vanadia-based SCR catalysts is:
Catalyst A: 0.6kg tartaric acid, 0.4kgOP-10;
Catalyst B: 0.5kg hydrogen peroxide, 1kgOP-10;
Catalyst C:1kg citric acid, 0.5kg tartaric acid;
Catalyst D:1kg citric acid, 1kg polyacrylic acid;
Catalyst E:1.5kg citric acid, 0.5kg polyacrylic acid.
Vanadia-based SCR catalysts A ~ F that embodiment 1 and the present embodiment 6 are prepared respectively is carried out NO on fixed bed reactors
xremoval efficiency is investigated, and condition of investigating is with embodiment 1.Result is as shown in table 6.
Vanadia-based SCR catalysts prepared by table 6 embodiment 1 and embodiment 6 is to NO
xconversion ratio
As can be seen from Table 6, the vanadia-based SCR catalysts of embodiment 1 preparation and the vanadia-based SCR catalysts of embodiment 6 preparation all have well active and durability.But vanadia-based SCR catalysts prepared by embodiment 1 all has good activity to fresh, aging sample, full temperature section balancing performance, fresh, aging sample balancing performance; And high-temperature behavior is good in catalyst A, cryogenic property is general; In catalyst B, C, low temperature is good, and high-temperature behavior is general; D high-temperature behavior is good, and middle low temperature is general; The full temperature section of E is balanced, but conversion ratio is not high.It can thus be appreciated that the vanadia-based SCR catalysts performance prepared by the method described in embodiment 1 is best, also that is to say, described anchoring dispersant consists of best preferred version of the present invention by citric acid and polyacrylic acid by weight for 2:1.
Test example 1
Vanadia-based SCR catalysts embodiment 1 prepared carries out stand NO
xremoval efficiency is tested, and operating mode is ETC circulation and ESC circulation.Used catalyst prime is 267*152cm, 400cpsi; Rear class is 267*101cm, 400cpsi; Engine is Weihe River bavin WP7, and discharge capacity is 7.14L; Infrared-gas pond is used quantitatively to detect tail gas.Carry out Operation mode cycle to vanadia-based SCR catalysts aging, the time is 500h; Aging complete after carry out ETC circulation, ESC state of cyclic operation test, its NO
xremoval efficiency is as shown in table 7.
Fresh, the aging nitrogen oxide emission contrast of vanadia-based SCR catalysts stand prepared by table 7 embodiment 1
As shown in Table 7, fresh, aging sample ETC, ESC cycle bleeder amount of vanadia-based SCR catalysts of preparing of the present invention is lower than state IV emission limit.
Comparative example 1
Prepare 10, full-page proof by method described in embodiment 1, be of a size of 267*152cm/400cpsi, volume is 1 ~ No. 10.
Get commercial catalysts 10 prepared by conventional method, be of a size of 267*152cm/400cpsi, volume is 1 ~ No. 10, is labeled as catalyst I.Its preparation method is see the comparative example of patent of invention CN103263912A: be dissolved in by 1.303kg oxalic acid in 8kg deionized water, and after dissolving oxalic acid is complete, add 0.771kg ammonium metavanadate, 50 DEG C of heating water baths stir 1 hour, obtain blue solution.Add water adjustment liquor capacity to 17.46L, then by joining in 19.4kg titanium silicon tungsten powder in this solution, stirring 1 ~ 3 hour, obtaining blue powder.Put into baking oven, dry 2h in 70 DEG C, 120 DEG C are dried 24h; Then at 550 DEG C of roasting 3h, catalyst powder is obtained; This powder is again through slurrying, and coating, dry, 600 DEG C of roasting 2h, obtain catalyst I.
The method described in patent of invention CN102698736A embodiment 4 is adopted to prepare sample: to take 6g oxalic acid soluble in water, be heated to dissolve completely at 80 DEG C, be mixed with the oxalic acid aqueous solution of 6%.In oxalic acid solution, adding 0.257g ammonium metavanadate, at 80 DEG C of constant temperature down to dissolving completely, stirring 0.5h.12.614g cerous nitrate is added again, at 80 DEG C of constant temperature down to dissolving completely in above-mentioned solution.Terbium nitrate 12.383g is added again, at 80 DEG C of constant temperature down to dissolving completely in above-mentioned solution.Erbium nitrate 11.589g is added again, at 80 DEG C of constant temperature down to dissolving completely in above-mentioned solution.In above-mentioned solution, adding zirconyl nitrate 10.845g again, at 80 DEG C of constant temperature down to dissolving completely, stirring 0.5h.In system, add 200ml water, then add tungsten titanium valve 83g, stir 0.5h at 80 DEG C of constant temperature.Add the Alumina gel of mixed liquor volume 10% more wherein as binding agent, stirred at ambient temperature 2h, obtains slurry.By blank cordierite honeycomb ceramic carrier dipping in the slurry, take out the raffinate in after-blow clear opening road, at 120 DEG C of dry 1.5h, then at 450 DEG C of roasting 5h, obtain catalyst (2%) V
2o
5-(5%) CeO
2-(5%) Er
2o
3-(5%) Tb
2o
3-(5%) ZrO
2-(8.3%) WO
3-(74.7%) TiO
2, be labeled as catalyst I I.
The method described in application for a patent for invention 201010274007.4 embodiment 3 is adopted to prepare sample: to take 4.67g oxalic acid soluble in water, be heated to dissolve completely at 60 DEG C, be mixed with the oxalic acid aqueous solution of 8%.In oxalic acid solution, adding 6g vanadic anhydride, at 60 DEG C of constant temperature down to dissolving completely, stirring 0.5h.In above-mentioned solution, adding acetic acid zirconium 11.7g again, at 60 DEG C of constant temperature down to dissolving completely, stirring 0.5h.In system, add 200ml water, continue to add tungsten titanium valve 100g, namely add the tungstic acid of 8-10g and the titanium dioxide of 90-92g, be stirred at 60 DEG C of constant temperature and dissolve completely.Add the methylcellulose of mixed solution quality 25% more wherein, as binding agent, stirred at ambient temperature 2h, to dissolving completely, obtains slurry.By blank cordierite honeycomb ceramic carrier dipping in the slurry, take out the raffinate in after-blow clear opening road, at 150 DEG C of dry 1h, then obtain catalyst at 550 DEG C of roasting 3h, be labeled as catalyst I II.
Catalyst I ~ III prepared by the vanadia-based SCR catalysts prepare embodiment 1 and comparative example 1 carries out NO on fixed bed reactors
xremoval efficiency is investigated, and condition of investigating is with embodiment 1.Result is as shown in table 8.
Catalyst prepared by table 8 embodiment 1 and comparative example 1 is to NO
xconversion ratio
According to shown in table 8, catalyst activity prepared by embodiment 1 and endurance quality are slightly better than catalyst I, are obviously better than catalyst I I that described in CN102698736A and 201010274007.4 prepared by method and III.
Catalyst I prepared by the vanadia-based SCR catalysts prepare embodiment 1 and comparative example 1 carries out NO on fixed bed reactors
xremoval efficiency is investigated, and condition of investigating is with embodiment 1.To NO at calculating its 250 DEG C, 500 DEG C
xconversion ratio variance, result is as shown in table 9.
Table 9 different catalysts is to NO
xthe stability of conversion ratio
As can be seen from Table 9, the vanadia-based SCR catalysts prepared of the present invention is to NO
xthe variance of conversion ratio is significantly less than catalyst I, and the stability of vanadia-based SCR catalysts that namely prepared by the present invention is obviously better than commercial catalysts I prepared by traditional handicraft.
To sum up, the present invention adds a certain amount of anchoring dispersant in the preparation process of vanadia-based SCR catalysts, not only achieve the preparation technology that vanadia-based SCR catalysts " is treated different things alike ", shorten technological process, save production cost, vanadia-based SCR catalysts activity, durability and the good stability prepared, have a extensive future simultaneously.
Claims (10)
1. a preparation method for diesel car tail gas refining vanadia-based SCR catalysts, is characterized in that, comprises the steps:
(1) be dissolved in deionized water by anchoring dispersant, stir, then add vanadium source and tungsten source, stirring and dissolving, obtains mixed liquor;
(2) in step (1) gained mixed liquor, add titanium source, ageing under stirring, obtain suspension;
(3) in step (2) gained suspension, add binding agent, stir, obtain catalyst pulp;
(4) be coated on carrier by step (3) gained slurry, dry, roasting, obtains diesel car tail gas refining vanadia-based SCR catalysts;
Wherein, in described step (1), anchoring dispersant is selected from any one or a few in OPEO, citric acid, tartaric acid, polyacrylic acid, hydrogen peroxide.
2. preparation method according to claim 1, is characterized in that, by weight, comprises the steps:
(1) be dissolved in 20 ~ 35 parts of deionized waters by 0.5 ~ 3 part of anchoring dispersant, stir, then add 0.5 ~ 1.3 part of vanadium source and 0.6 ~ 1.5 part of tungsten source, stirring and dissolving, obtains mixed liquor;
(2) in step (1) gained mixed liquor, add 13 ~ 30 parts of titanium sources under stirring, ageing, obtains suspension;
(3) in step (2) gained suspension, add 2 ~ 6 parts of binding agents, stir, obtain catalyst pulp;
(4) be coated on carrier cordierite ceramic by step (3) gained slurry, dry, roasting, obtains diesel car tail gas refining vanadia-based SCR catalysts;
Wherein, in described step (1), anchoring dispersant is selected from any one or a few in OPEO, citric acid, tartaric acid, polyacrylic acid, hydrogen peroxide.
3. preparation method according to claim 2, is characterized in that: in described step (1), anchoring dispersant is made up of by weight for 2:1 citric acid and polyacrylic acid.
4. preparation method according to claim 2, is characterized in that: in described step (1), vanadium source is selected from any one or a few in ammonium vanadate, vanadic sulfate, vanadic anhydride, vanadium oxytrichloride, vanadium tetraoxide.
5. preparation method according to claim 2, is characterized in that: in described step (1), tungsten source is selected from any one or a few in ammonium metatungstate, ammonium tungstate, ammonium paratungstate.
6. preparation method according to claim 2, is characterized in that: in described step (2), titanium source is selected from metatitanic acid and/or titanium dioxide.
7. preparation method according to claim 2, is characterized in that: in described step (3), binding agent is selected from any one or a few in boehmite, Alumina gel, Ludox, zirconium colloidal sol, acetic acid zirconium.
8. preparation method according to claim 2, is characterized in that: in described step (2), the temperature of ageing is 50 ~ 90 DEG C, and the time is 0.5 ~ 5h.
9. preparation method according to claim 2, is characterized in that: in described step (4), the temperature of roasting is 250 ~ 650 DEG C, and the time is 0.5 ~ 5h.
10. preparation method according to claim 2, is characterized in that: adopt automatic coating machine to be coated on carrier cordierite ceramic by slurry in described step (4), and coating number of times is 1 time.
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| CN201410247611.6A CN103977790B (en) | 2014-06-06 | 2014-06-06 | A kind of preparation method of diesel car tail gas refining vanadia-based SCR catalysts |
| PCT/CN2015/075250 WO2015184911A1 (en) | 2014-06-06 | 2015-03-27 | Process for preparing vanadium-base scr catalyst coating for purifying tail gas of diesel vehicle |
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| CN201410247611.6A CN103977790B (en) | 2014-06-06 | 2014-06-06 | A kind of preparation method of diesel car tail gas refining vanadia-based SCR catalysts |
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| CN103977790B (en) * | 2014-06-06 | 2016-04-06 | 中自环保科技股份有限公司 | A kind of preparation method of diesel car tail gas refining vanadia-based SCR catalysts |
| CN104475120B (en) * | 2014-12-03 | 2017-06-06 | 天津大学 | Use for diesel engine cobalt vanadium binary oxide type SCR supported catalyst |
| WO2016188989A1 (en) | 2015-05-26 | 2016-12-01 | Treibacher Industrie Ag | Process for the preparation of titania/metal vanadate based catalyst compositions |
| CN109225203B (en) * | 2018-09-30 | 2019-12-17 | 中自环保科技股份有限公司 | preparation method of vanadium-based oxide SCR catalyst and catalyst prepared by preparation method |
| CN111036251B (en) * | 2019-11-22 | 2022-07-08 | 大唐南京环保科技有限责任公司 | High-wear-resistance flat plate type denitration and demercuration catalyst and preparation method thereof |
| CN112516995A (en) * | 2020-12-09 | 2021-03-19 | 安徽艾可蓝环保股份有限公司 | Novel vanadium-based SCR catalyst and preparation method and application thereof |
| CN113318752B (en) * | 2021-07-06 | 2024-01-12 | 无锡格雷斯环保科技有限公司 | Vanadium-tungsten-titanium system industrial denitration catalyst and preparation method and device thereof |
| CN113499768A (en) * | 2021-07-09 | 2021-10-15 | 安徽元琛环保科技股份有限公司 | Preparation method of coating type high-strength denitration catalyst and prepared denitration catalyst |
| CN114832807A (en) * | 2022-06-02 | 2022-08-02 | 东方凯特瑞(成都)环保科技有限公司 | SCR denitration catalyst and preparation method thereof |
| CN117380255B (en) * | 2023-12-05 | 2024-02-27 | 河北华特汽车部件有限公司 | Preparation method and application of catalyst for purifying nitrogen oxides |
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