CN103977790A - Preparation method of vanadium-base SCR (Selective Catalytic Reduction) catalyst for purifying tail gas of diesel vehicle - Google Patents
Preparation method of vanadium-base SCR (Selective Catalytic Reduction) catalyst for purifying tail gas of diesel vehicle Download PDFInfo
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- CN103977790A CN103977790A CN201410247611.6A CN201410247611A CN103977790A CN 103977790 A CN103977790 A CN 103977790A CN 201410247611 A CN201410247611 A CN 201410247611A CN 103977790 A CN103977790 A CN 103977790A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
Abstract
The invention discloses a preparation method of a vanadium-base SCR (Selective Catalytic Reduction) catalyst for purifying tail gas of a diesel vehicle. The preparation method comprises the following steps: dissolving an anchoring dispersing agent into deionized water, uniformly stirring, adding a vanadium source and a tungsten source, and stirring until the vanadium source and the tungsten source are dissolved, wherein the anchoring dispersing agent is selected from one or more of polyoxyethylene octylphenol ether, citric acid, tartaric acid, polyacrylic acid and hydrogen peroxide; adding a titanium source while stirring, and ageing; adding a bonding agent, and uniformly stirring, so as to obtain catalyst slurry; finally, coating a carrier by the catalyst slurry, and drying and roasting, so as to obtain the vanadium-base SCR catalyst. The preparation method has the beneficial effects that the anchoring dispersing agent is added in a preparation process of the vanadium-base SCR catalyst, so that a 'one-pot procedure' preparation process of the vanadium-base SCR catalyst is realized, the technological process is shortened, the production cost is lowered, and the prepared vanadium-base SCR catalyst has good activity, durability and stability and a wide application prospect.
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 vanadium base SCR catalyst.
Background technology
Nitrogen oxide (NO
x) be one of topmost pollutant in atmosphere.Not only having stronger bio-toxicity especially stimulates respiratory system, and is one of main reason of acid rain and photochemical fog etc.Atmosphere pollution is now serious, controls NO
xdischarge very urgent, law compulsion limit row is extensively put into effect in countries in the world.
Various NO
xremove in technology 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 resistance to sulphur, 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 resistance to sulphur of its excellence.One vapour, Yuchai, heavy vapour, Weihe River bavin etc. have all been determined this scheme.Nearly all coal-burning power plant also selects vanadium base SCR as after-treatment system because flue gas sulfur content is high.
On market, ripe product adopts metatitanic acid or titanium dioxide through dipping tungsten mostly, and dry, roasting makes titanium tungsten powder, and titanium tungsten powder is again through vanadium impregnated, and dry, roasting makes catalyst powder, and powder makes catalyst pulp through defibrination.The preparation method of this vanadium base SCR catalyst, by dipping, evenly spreads in the duct of titanium dioxide vanadium, tungsten, forms insoluble matter it is fixed by dry, roasting.This technique need be prepared titanium tungsten powder, also needs further slurrying to apply again, and long flow path, cost are high, the vanadium base SCR poor catalyst stability simultaneously making.
Directly all raw materials are mixed, " treating different things alike " is that Kaolinite Preparation of Catalyst is most economical, effective method.But directly mix titanium dioxide, vanadium, tungsten, make slurry, the tungsten in solution, vanadium will move with moisture evaporation, enrichment, cause disperseing inhomogeneous, easy-sintering, durability and poor stability.
Patent of invention CN102698736A discloses a kind of titanium tungsten powder that uses for carrier makes the technology of slurry by sizing mixing, and due to without dipping, is dried, roasting, oxalic acid vanadyl in solution will move in dry run, causes its dispersion inhomogeneous, cannot guarantee durability and stability.
Application for a patent for invention 201010274007.4 discloses a kind of use titanium dioxide, through sizing mixing, directly make the method for catalyst pulp, but its tungsten, vanadium all can not effectively disperse, fixing, its endurance quality more cannot guarantee, and lack dispersion means, slurry is difficult to primary coating and reaches enough upper carrying capacity.
Summary of the invention
The object of the invention is to overcome existing above-mentioned deficiency in prior art, a kind of preparation method of diesel car tail gas refining vanadium base SCR catalyst is provided.This preparation method adds anchoring dispersant in the preparation process of vanadium base SCR catalyst, by sizing mixing, primary coating, dry, roasting four steps form honeycomb catalyst, during roasting, carrier and catalyst generate in honeycomb substrate simultaneously, and wherein said anchoring dispersant is selected from one or both in OPEO (OP-10), citric acid, tartaric acid, polyacrylic acid, hydrogen peroxide.Described preparation method's raw material is cheap, technique is simple, the cycle is short, thereby production cost is low; And the vanadium base SCR catalyst making 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 vanadium base SCR catalyst of the present invention, comprises the steps:
(1) anchoring dispersant is dissolved in deionized water, stirs, then add He Wu source, vanadium source, stirring and dissolving, obtains mixed liquor;
(2) under stirring, in step (1) gained mixed liquor, add titanium source, ageing, obtains suspension;
(3) in step (2) gained suspension, add binding agent, stir, obtain catalyst pulp;
(4) step (3) gained slurry is coated on carrier, dry, roasting, obtains diesel car tail gas refining vanadium base SCR catalyst.
Wherein, the middle anchoring dispersant of described step (1) is selected from any one or a few in OPEO, citric acid, tartaric acid, polyacrylic acid, hydrogen peroxide.
Applicant is through experiment repeatedly, discovery adds described anchoring dispersant in preparation method of the present invention, anchoring dispersant energy and tungsten, vanadium bonding, and be combined with titanium dioxide by absorption, coordination, make vanadium, tungsten in solution be evenly dispersed, be fixed in titanium dioxide duct, in dry run, do not move, thereby guaranteed that tungsten, vanadium are dispersed on titanium dioxide; Meanwhile, this anchoring dispersant also has peptizaiton to titanium dioxide, makes slurry fluidity good, not stratified, and primary coating amount can surpass 210g/L.Anchoring dispersant add activity, durability and the stability that has guaranteed gained vanadium base SCR catalyst.
Preferably, preparation method of the present invention by weight, comprises the steps:
(1) 0.5～3 part of anchoring dispersant is dissolved in 20～35 parts of deionized waters, stirs, 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) under stirring, in step (1) gained mixed liquor, add 13～30 parts of titanium sources, ageing, obtains suspension;
(3) in step (2) gained suspension, add 2～6 parts of binding agents, stir, obtain catalyst pulp;
(4) step (3) gained slurry is coated on carrier cordierite ceramic, dry, roasting, obtains diesel car tail gas refining vanadium base SCR catalyst.
Wherein, the middle anchoring dispersant of described step (1) 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 by citric acid and polyacrylic acid by weight forming for 2:1.Preferred by this, obtained vanadium base SCR catalyst activity and durability are best.
Preferably, the middle vanadium of described step (1) source is selected from any one or a few in ammonium vanadate, vanadic sulfate, vanadic anhydride, vanadium oxytrichloride, vanadium tetraoxide.
Preferably, the middle tungsten of described step (1) 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, the middle binding agent of described step (3) is selected from any one or a few in boehmite, aluminium colloidal sol, Ludox, zirconium colloidal sol, acetic acid zirconium.
Preferably, in above-mentioned preparation method, in described step (2), the temperature of ageing is 50～90 ℃, and the time is 0.5～5h; When Aging Temperature is lower than 50 ℃ or higher than 90 ℃, digestion time, lower than 0.5h or higher than 5h, all can affect the mobility of slurry and the activity of vanadium base SCR catalyst.Further preferably, the temperature of described ageing is 50～60 ℃, and the time is 0.5～2h; Preferably, the temperature of described ageing is 50 ℃ 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 ℃, and the time is 0.5～5h; When sintering temperature is lower than 250 ℃ or higher than 650 ℃, roasting time, lower than 0.5h or higher than 5h, all can reduce activity and the endurance quality of vanadium base SCR catalyst.Further preferably, the temperature of described roasting is 250～300 ℃, and the time is 1～2h; Preferably, the temperature of described roasting is 300 ℃ to the best, and the time is 1h.
Preferably, adopt automatic coating machine that slurry is coated on carrier cordierite ceramic in described step (4), applying number of times is 1 time.Owing to having added anchoring dispersant in the preparation process at vanadium base SCR catalyst, this anchoring dispersant has peptizaiton to titanium dioxide, make slurry fluidity good, not stratified, primary coating can surpass 210g/L, therefore the present invention preferably adopts automatic coating machine that slurry is coated on carrier cordierite ceramic, and applying 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 vanadium base SCR catalyst, add anchoring dispersant, anchoring dispersant energy and tungsten, vanadium bonding, and be combined with titanium dioxide by absorption, coordination, make vanadium, tungsten in solution be evenly dispersed, be fixed in titanium dioxide duct, in dry run, do not move, thereby guaranteed that tungsten, vanadium are dispersed on titanium dioxide, realized " treating different things alike " and prepared activity and good endurance, and the reliable vanadium base of stability SCR catalyst.Experiment shows, vanadium base SCR catalyst prepared by the inventive method is to NO
xthe commercial catalysts that the variance of conversion ratio is prepared with traditional handicraft is compared, and 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 vanadium base SCR catalyst, add anchoring dispersant, anchoring dispersant also has peptizaiton to titanium dioxide, make slurry fluidity good, not stratified, primary coating can surpass 210g/L, adopt primary coating technique, the cordierite carrier that effectively reduce repetitive coatings, be dried, roasting causes is damaged.
(3) preparation method of the present invention is with short production cycle, raw material is 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.
The specific embodiment
Below in conjunction with test example and the specific embodiment, the present invention is described in further detail.But this should be interpreted as to the scope of the above-mentioned theme of the present invention only limits to following embodiment, all technology realizing 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; Under stirring, add 20.20kg titanium dioxide, at 50 ℃, ageing 2h, obtains suspension; Add 4.2kg Ludox (SiO in Ludox
2content is 25%, stirs, and obtains catalyst pulp.
The catalyst pulp making is coated on carrier cordierite ceramic to dry 1h at 80 ℃ by coating machine; Finally roasting 1h at 300 ℃, obtains.
Comparative example 1: adopt oxalic acid replace citric acid and polyacrylic acid (ammonium vanadate itself is water insoluble, and oxalic acid in conjunction with after be water soluble), remaining reaction condition all, with above-described embodiment 1, obtains.
The vanadium base SCR catalyst that the present embodiment 1 and comparative example 1 are made carries out the investigation of NOx removal efficiency on fixed bed reactors.The catalyst size of using 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 ℃; Gas component is all used infrared detection.
The vanadium base SCR catalyst of embodiment 1 and comparative example 1 preparation is to NO
xconversion ratio as shown in table 1.The letter of bracket the inside represents state, and wherein f represents freshly, and a represents aging sample; Aging condition is: 600 ℃ of temperature, moisture content 5%, air speed 40000h
-1.
The vanadium base SCR catalyst of table 1 embodiment 1 and comparative example 1 preparation is to NO
xconversion ratio
As can be seen from Table 1, fresh, the aging sample of vanadium base SCR catalyst of embodiment 1 preparation all has good activity, full temperature section balancing performance, and fresh ageing properties is balanced; And do not add vanadium base SCR catalyst prepared by anchoring dispersant only in fresh sample low temperature active better, high temperature section is poor, aging rear full temperature section is all obviously deteriorated.Show, after interpolation anchoring dispersant, not only improved the activity of vanadium base SCR catalyst, improved 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; Under stirring, add 15kg metatitanic acid, at 90 ℃, ageing 0.5h, obtains suspension; Add 3kg zirconium colloidal sol (in zirconium colloidal sol, zirconium dioxide content is 10%), stir, obtain catalyst pulp.
The catalyst pulp making is coated on carrier cordierite ceramic to dry 1h at 80 ℃ by coating machine; Finally roasting 0.5h at 650 ℃, obtains.
Comparative example 2: adopt oxalic acid to replace tartaric acid, remaining reaction condition all, with above-described embodiment 2, obtains.
The vanadium base SCR catalyst that embodiment 2 and comparative example 2 are made respectively carries out NO on fixed bed reactors
xremoval efficiency is investigated, and investigation condition is with embodiment 1.Result is as shown in table 2.
The vanadium base SCR catalyst of table 2 embodiment 2 and comparative example 2 preparations is to NO
xconversion ratio
As can be seen from Table 2, the fresh sample performance of catalyst and the comparative example 2 of embodiment 2 preparations are basically identical, but aging rear activity is obviously better than comparative example 2.
Embodiment 3
By 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; Under stirring, add 28kg metatitanic acid, at 70 ℃, ageing 3h, obtains suspension; Add 6kg aluminium colloidal sol, stir, obtain catalyst pulp.
The catalyst pulp making is coated on carrier cordierite ceramic to dry 0.5h at 150 ℃ by coating machine; Finally roasting 5h at 250 ℃, obtains.
Comparative example 3: adopt oxalic acid to replace OP-10 and hydrogen peroxide, remaining reaction condition all, with above-described embodiment 3, obtains.
The vanadium base SCR catalyst that embodiment 3 and comparative example 3 are made respectively carries out NO on fixed bed reactors
xremoval efficiency is investigated, and investigation condition is with embodiment 1.Result is as shown in table 3.
The vanadium base SCR catalyst of table 3 embodiment 3 and comparative example 3 preparations is to NO
xconversion ratio
As can be seen from Table 3, the fresh sample cryogenic property of catalyst that embodiment 3 makes is slightly worse than comparative example 3, but its high-temperature behavior has more significantly advantage.And after the catalyst ageing that comparative example 3 makes, degradation is 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; Under stirring, add 7kg metatitanic acid, 6kg titanium dioxide, at 60 ℃, ageing 4h, obtains suspension; Add 2kg acetic acid zirconium, stir, obtain catalyst pulp.
The catalyst pulp making is coated on carrier cordierite ceramic to dry 0.8h at 100 ℃ by coating machine; Finally roasting 2h at 500 ℃, obtains.
Comparative example 4: adopt oxalic acid to replace hydrogen peroxide and polyacrylic acid, remaining reaction condition all, with above-described embodiment 4, obtains.
The vanadium base SCR catalyst that embodiment 4 and comparative example 4 are made respectively carries out NO on fixed bed reactors
xremoval efficiency is investigated, and investigation condition is with embodiment 1.Result is as shown in table 4.
The vanadium base SCR catalyst of table 4 embodiment 4 and comparative example 4 preparations is to NO
xconversion ratio
As can be seen from Table 4, embodiment 4 makes the fresh sample of catalyst 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; Under stirring, add 18kg titanium dioxide, at 80 ℃, ageing 2.5h, obtains suspension; Add 5kg boehmite, stir, obtain catalyst pulp.
The catalyst pulp making is coated on carrier cordierite ceramic to dry 1h at 80 ℃ by coating machine; Finally roasting 2.5h at 400 ℃, obtains.
Comparative example 5: adopt oxalic acid to replace hydrogen peroxide, tartaric acid and OP-10, remaining reaction condition all, with above-described embodiment 5, obtains.
The vanadium base SCR catalyst that embodiment 5 and comparative example 5 are made respectively carries out NO on fixed bed reactors
xremoval efficiency is investigated, and investigation condition is with embodiment 1.Result is as shown in table 5.
The vanadium base SCR catalyst of table 5 embodiment 5 and comparative example 5 preparations is to NO
xconversion ratio
The fresh sample of the catalyst that as can be seen from Table 5, embodiment 5 makes and aging sample performance are all better than comparative example 5.
Known according to the data in table 1～5, in the preparation process of vanadium base SCR catalyst, add anchoring dispersant, can realize " treating different things alike ", shorten production procedure, the vanadium base SCR catalyst simultaneously making is compared with the catalyst that adopts oxalic acid to replace anchoring dispersant to make, and it is active and durability is better.The vanadium base SCR catalyst effect of wherein being prepared by method described in embodiment 1 is best, and fresh, aging sample is all had to good activity, full temperature section balancing performance, and fresh ageing properties is balanced.
Embodiment 6
On the basis of embodiment 1, change composition and the consumption of anchoring dispersant, remaining reaction condition, all with embodiment 1, is investigated composition and the impact of consumption on vanadium base SCR catalyst performance of anchoring dispersant, and wherein the preparation method of vanadium base SCR catalyst 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.
Vanadium base SCR catalyst A～F that embodiment 1 and the present embodiment 6 are prepared respectively carries out NO on fixed bed reactors
xremoval efficiency is investigated, and investigation condition is with embodiment 1.Result is as shown in table 6.
The vanadium base SCR catalyst of table 6 embodiment 1 and embodiment 6 preparations is to NO
xconversion ratio
As can be seen from Table 6, the vanadium base SCR catalyst of the vanadium base SCR catalyst of embodiment 1 preparation and embodiment 6 preparations all has good activity and durability.But the vanadium base SCR catalyst of embodiment 1 preparation 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; E is complete, and temperature section is balanced, but conversion ratio is not high.Hence one can see that, and the vanadium base SCR catalyst performance of being prepared by the method described in embodiment 1 is best, also that is to say, described anchoring dispersant by citric acid and polyacrylic acid by weight consisting of best preferred version of the present invention for 2:1.
Test example 1
The vanadium base SCR catalyst of embodiment 1 preparation is carried out to stand NO
xremoval efficiency test, 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; Use infrared-gas pond quantitatively to detect tail gas.Vanadium base SCR catalyst is carried out to Operation mode cycle aging, the time is 500h; After aging completing, carry out ETC circulation, the test of ESC state of cyclic operation, its NO
xremoval efficiency is as shown in table 7.
Fresh, the aging nitrogen oxide emission contrast of vanadium base SCR catalyst stand of table 7 embodiment 1 preparation
Fresh, the aging sample ETC of the vanadium base SCR catalyst that as shown in Table 7, prepared by the present invention, ESC cycle bleeder amount are lower than state's IV emission limit.
Comparative example 1
By method described in embodiment 1, prepare 10, full-page proof, be of a size of 267*152cm/400cpsi, volume is 1～No. 10.
Get 10 of commercial catalysts 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 referring to the comparative example of patent of invention CN103263912A: 1.303kg oxalic acid is dissolved in 8kg deionized water, after oxalic acid dissolves completely, adds 0.771kg ammonium metavanadate, 50 ℃ of heating water baths stir 1 hour, obtain blue solution.Add water and adjust liquor capacity to 17.46L, then, by joining in this solution in 19.4kg titanium silicon tungsten powder, stir 1～3 hour, obtain blue powder.Put into baking oven, in 70 ℃, dry 2h, 120 ℃ of baking 24h; Then at 550 ℃ of roasting 3h, obtain catalyst powder; This powder, again through slurrying, applies, and dry, 600 ℃ of roasting 2h, obtain catalyst I.
Method described in employing patent of invention CN102698736A embodiment 4 is prepared sample: take 6g oxalic acid soluble in water, at 80 ℃, be heated to dissolve completely, be mixed with 6% oxalic acid aqueous solution.In oxalic acid solution, add 0.257g ammonium metavanadate, at 80 ℃ of constant temperature, down to dissolving completely, stir 0.5h.In above-mentioned solution, add 12.614g cerous nitrate again, at 80 ℃ of constant temperature down to dissolving completely.In above-mentioned solution, add terbium nitrate 12.383g again, at 80 ℃ of constant temperature down to dissolving completely.In above-mentioned solution, add erbium nitrate 11.589g again, at 80 ℃ of constant temperature down to dissolving completely.In above-mentioned solution, add zirconyl nitrate 10.845g again, at 80 ℃ of constant temperature, down to dissolving completely, stir 0.5h.In system, add 200ml water, then add tungsten titanium valve 83g, at 80 ℃ of constant temperature, stir 0.5h.Add wherein again the aluminium colloidal sol of mixed liquor volume 10% as binding agent, under room temperature, stir 2h, obtain slurry.Blank cordierite honeycomb ceramic carrier is immersed in slurry, takes out the raffinate in after-blow clear opening road, at 120 ℃ of dry 1.5h, then at 450 ℃ 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.
Method described in employing application for a patent for invention 201010274007.4 embodiment 3 is prepared sample: take 4.67g oxalic acid soluble in water, at 60 ℃, be heated to dissolve completely, be mixed with 8% oxalic acid aqueous solution.In oxalic acid solution, add 6g vanadic anhydride, at 60 ℃ of constant temperature, down to dissolving completely, stir 0.5h.In above-mentioned solution, add acetic acid zirconium 11.7g again, at 60 ℃ of constant temperature, down to dissolving completely, stir 0.5h.In system, add 200ml water, continue to add tungsten titanium valve 100g, add the tungstic acid of 8-10g and the titanium dioxide of 90-92g, at 60 ℃ of constant temperature, be stirred to completely and dissolve.Add wherein again the methylcellulose of mixed solution quality 25%, as binding agent, under room temperature, stir 2h to dissolving completely, obtain slurry.Blank cordierite honeycomb ceramic carrier is immersed in slurry, takes out the raffinate in after-blow clear opening road, at 150 ℃ of dry 1h, then at 550 ℃ of roasting 3h, obtain catalyst, be labeled as catalyst I II.
Catalyst I～the III of the vanadium base SCR catalyst of embodiment 1 preparation and comparative example 1 preparation is carried out to NO on fixed bed reactors
xremoval efficiency is investigated, and investigation condition is with embodiment 1.Result is as shown in table 8.
The catalyst of table 8 embodiment 1 and comparative example 1 preparation is to NO
xconversion ratio
According to shown in table 8, catalyst activity and the endurance quality of embodiment 1 preparation are slightly better than catalyst I, are obviously better than catalyst I I and the III that prepared by method described in CN102698736A and 201010274007.4.
The catalyst I of the vanadium base SCR catalyst of embodiment 1 preparation and comparative example 1 preparation is carried out to NO on fixed bed reactors
xremoval efficiency is investigated, and investigation condition is with embodiment 1.Calculate at its 250 ℃, 500 ℃ NO
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 vanadium base SCR catalyst that prepared by the present invention is to NO
xthe variance of conversion ratio is significantly less than catalyst I, i.e. the stability of vanadium base SCR catalyst 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 vanadium base SCR catalyst, not only realized the preparation technology that vanadium base SCR catalyst " is treated different things alike ", shortened technological process, save production cost, vanadium base SCR catalyst activity, durability and the good stability of preparation, have a extensive future simultaneously.
Claims (10)
1. a preparation method for diesel car tail gas refining vanadium base SCR catalyst, is characterized in that, comprises the steps:
(1) anchoring dispersant is dissolved in deionized water, stirs, then add He Wu source, vanadium source, stirring and dissolving, obtains mixed liquor;
(2) under stirring, in step (1) gained mixed liquor, add titanium source, ageing, obtains suspension;
(3) in step (2) gained suspension, add binding agent, stir, obtain catalyst pulp;
(4) step (3) gained slurry is coated on carrier, dry, roasting, obtains diesel car tail gas refining vanadium base SCR catalyst.
Wherein, the middle anchoring dispersant of described step (1) 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) 0.5～3 part of anchoring dispersant is dissolved in 20～35 parts of deionized waters, stirs, 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) under stirring, in step (1) gained mixed liquor, add 13～30 parts of titanium sources, ageing, obtains suspension;
(3) in step (2) gained suspension, add 2～6 parts of binding agents, stir, obtain catalyst pulp;
(4) step (3) gained slurry is coated on carrier cordierite ceramic, dry, roasting, obtains diesel car tail gas refining vanadium base SCR catalyst.
Wherein, the middle anchoring dispersant of described step (1) 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 by citric acid and polyacrylic acid by weight forming for 2:1.
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, aluminium colloidal sol, 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 ℃, 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 ℃, and the time is 0.5～5h.
10. preparation method according to claim 2, is characterized in that: in described step (4), adopt automatic coating machine that slurry is coated on carrier cordierite ceramic, applying 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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| WO2015184911A1 (en) * | 2014-06-06 | 2015-12-10 | 四川中自尾气净化有限公司 | Process for preparing vanadium-base scr catalyst coating for purifying tail gas of diesel vehicle |
| WO2016188989A1 (en) | 2015-05-26 | 2016-12-01 | Treibacher Industrie Ag | Process for the preparation of titania/metal vanadate based catalyst compositions |
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| 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 |
| 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 |
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