CN105561974A - Diesel engine exhaust SCR denitration catalyst and preparation method thereof - Google Patents
Diesel engine exhaust SCR denitration catalyst and preparation method thereof Download PDFInfo
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- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- 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
- B01J23/28—Molybdenum
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- 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
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- B01D2258/012—Diesel engines and lean burn gasoline engines
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The present invention relates to a diesel engine exhaust SCR denitration catalyst and a preparation method thereof, a cerium molybdenum complex oxide is used as a catalytically active component, praseodymium, tungsten or lanthanum is used as a cocatalyst blend, and alumina is used as a carrier. The cerium molybdenum complex oxide, a co-catalysis ion precursor complex solution, pseudo-boehmite, pure gamma alumina, citric acid monohydrate and other organic additives are uniformly stirred, mixed, decayed, extruded and molded, then dried in the shade, dried, and roasted to obtain an integrated catalyst. The catalyst is environment-friendly, high in NOx removal efficiency, and wide in range of active temperature, NOx removal efficiency at 250 DEG C-425 DEG C is more than 95%, the highest denitration activity is up to 100%; and the diesel engine exhaust SCR denitration catalyst has excellent sulfur resistance, water poisoning resistance, high mechanical strength, good ammonia storage performance, high CO and HC catalytic oxidation activity and low catalyst cost, and is cost-effective, and especially suitable for diesel engine exhaust NOx removal.
Description
Technical field
The present invention relates to a kind of diesel engine vent gas denitration Catalysts and its preparation method, belong to environment protection catalytic material and air contaminant treatment field, be specially adapted to the tail gas denitration of marine diesel high sulfur content.
Background technology
International Maritime Organization (IMO) determine, according to international treaties by from 2016 to boats and ships discharge nitrogen oxide (NO
x) implement phase III limit value discharge.NOx reduces discharging Amplitude Ratio primary limits value in 2005 and significantly improves about 80%.NO
xbecome the emphasis that country " 12 " reduces discharging.China's inland navigation craft is numerous, stops intensive, boat diesel engine NO
xdischarge is in no-console condition, annual NO substantially
xtotal emission volumn up to 1,000,000 tons, and increases year after year, has a strong impact on the life and health of littoral people.At present, all use denitrating catalyst manufacturer without special purpose ship both at home and abroad, use maximum denitrating catalysts peculiar to vessel to be thermal power plant V
2o
5(WO
3)/TiO
2catalyst.But integral honeycombed catalyst crush strength is low, and active temperature windows is narrow, and active material has severe toxicity containing vanadium, limits it and further develops in field peculiar to vessel.Current, the research and development of domestic ships SCR denitration are still in the pre-test stage, how abroad to be monopolized and study mostly to concentrate on vanadium Ti-base catalyst.
At present, have both at home and abroad and patent discloses various types of denitrating catalyst and preparation technology thereof in a large number, but relatively less for marine diesel, the boat diesel engine vent gas treatment mode of main flow is generally treatment technology and off engine control technology technology in machine, according to research, in machine, treatment technology can only meet the Abgasgesetz in TierI, II stage, along with Abgasgesetz is more and more stricter, in machine, treatment technology can not meet the TierIII stage marine diesel exhaust emissions restriction being about to implement, in order to better process the NO in tail gas
x, marine diesel needs to be equipped with NO
xreduce device, can discharge standard be met.At present, popular, the most ripe in the world boat diesel engine exhaust aftertreatment technology is SCR technology (SCR).Patent (CN201310370851.0), (CN201510195861.4), (CN201410756640.5) are several sections of special patents for the catalyst preparing of marine diesel vent gas treatment.Pyrophillite joins in active powder as plasticizer and obtains extruding dry powder by its Patent (CN201310370851.0) employing, pug is prepared by shear action to extrude dry powder, aluminosilicate glass, aluminium glue, copper based molecular sieve, calcium lignosulfonate, stearic acid and appropriate deionized water, after drying, roasting, obtain finished product, this complicated process of preparation and cost is higher; (CN201510195861.4) catalyst is using high-specific surface area ZSM-5 molecular sieve as carrier, and using vanadium, tungsten, copper, manganese, ce metal element as active component, this catalyst, using vanadium as chief active element, easily causes environmental pollution, and runs into SO
2easy in inactivation.
Summary of the invention
The object of the invention is the current situation and existing problems for the research of existing ship denitrating catalyst, and propose a kind of diesel engine vent gas denitration catalyst of environmentally friendly low cost, another object of the present invention is to provide the preparation method of above-mentioned catalyst.
Technical scheme of the present invention is: a kind of diesel engine vent gas SCR denitration catalyst, it is characterized in that with cerium molybdenum composite oxides for catalytic active component, with praseodymium, tungsten or lanthanum (also can be one or more in group of the lanthanides) for co-catalyst, with dissimilar aluminium oxide batch mixing for carrier, with the aluminium oxide batch mixing carrier quality after burning till for benchmark, cerium molybdenum composite oxides mass percentage 12.5% ~ 33.3%, co-catalyst oxide mass percentage composition 1.25% ~ 6%; In described cerium molybdenum composite oxides active component, the elemental mole ratios of Ce and Mo is 1:(0.10 ~ 0.40); Dissimilar aluminium oxide batch mixing is gamma aluminium oxide and boehmite is 1:(1 ~ 1.33 in mass ratio) mixing.
Present invention also offers the method for above-mentioned diesel engine vent gas SCR denitration catalyst, its concrete steps are:
(1) preparation of cerium molybdenum composite oxides precursor solution
Take boehmite, add deionized water and stirring and drip that acid is obtained stablize aluminium glue uniformly simultaneously, be placed in 80 DEG C ~ 100 DEG C thermostat water baths stirring dispergation; Wherein the mass ratio of boehmite, deionized water and acid is 1:(7 ~ 14): (0.5 ~ 0.6), finally adds in cerium solution (dissolving cerium salt) and stirs, obtain solution A; The boehmite wherein preparing aluminium glue is (0.045 ~ 0.065) with cerium salt oxide mass ratio: 1;
Take molybdenum salt, monohydrate potassium add deionized water mixing; Wherein the mass ratio of molybdenum salt, monohydrate potassium and deionized water is 1:(1 ~ 1.25): (3 ~ 4.8), then stir until solution is clear shape, obtain solution B; Be 1:(0.10 ~ 0.40 by the elemental mole ratios of Ce and Mo), solution B is added drop-wise in solution A, needs in dropping process to stir;
(2) co-catalyst presoma solion configuration
Take and add deionized water mixing containing promoter metal salt; Mass ratio wherein containing promoter metal salt and deionized water is 1:(2 ~ 3.5), then stir until solution is clear shape, obtained co-catalyst presoma solion;
(3) preparation of carrier
Be 1:(1 ~ 1.33 according to gamma aluminium oxide and boehmite mass percent) take two kinds of raw materials, through ball mill mixing (general 1 ~ 3h), obtained mixed carrier;
(4) co-catalyst presoma solion mixing cerium molybdenum composite oxides precursor solution obtained for step (1) and step (2) obtained, stir (general about 20min ~ 30min), then add in the obtained mixed carrier of step (3) together with additive, stir pugging, after old drying in the shade, heat preservation and dryness;
(5) roasting of catalyst
Catalyst pug step (4) obtained in air atmosphere roasting obtains diesel engine vent gas SCR denitration catalyst.
The cerium salt of preferred steps (1) is cerous nitrate, cerium oxalate or cerium chloride; In step (1), molybdenum salt is ammonium molybdate or ammonium paramolybdate; Monohydrate potassium purposes is for regulating PH; Be the praseodymium nitrate or the hydrochloride that contain promoter metal containing promoter metal salt in step (2).
The mixing of above-mentioned steps (1) A, B solution is in the solution A that is added drop-wise in stirring of B solution, prevents molybdic acid from being formed.
The aluminium glue of preparation in preferred steps (1) needs 80 DEG C ~ 100 DEG C thermostat water baths to stir 20min ~ 30min dispergation.
Acid solution described in preferred steps (1) is the one in nitric acid, hydrochloric acid or sulfuric acid.
Additive in preferred steps (4) is one or more in carboxylic propyl methocel, carboxymethyl cellulose, glycerine or acetamide; Wherein the mass ratio of additive and cerium molybdenum composite oxides is (0.04 ~ 0.06): 1.
Drying in preferred steps (4) is temperature is 80 DEG C ~ 100 DEG C, heat preservation and dryness 1 ~ 4h in air dry oven.
Roasting in preferred steps (5) for inserting in Muffle furnace in air atmosphere, at 500 DEG C ~ 600 DEG C, insulation 1.5 ~ 3h.
Catalytic reaction condition of the present invention and result: get 10ml catalyst sample and load in catalyst performance evaluation reaction unit, pass into simulator and carry out activity rating.The W6L20C type marine diesel that analog gas is produced with reference to Wa Lanxi NSD, operate power is the on-the-spot test gained emission data of 25%, consisting of of the gas of simulation: NO (930ppm), NH
3(930ppm), O
2(10vol.%), H
2o (5vol.% adds during use), SO
2(475ppm adds during use), N
2for carrier gas, catalyst grain size is: diameter 3.5mm, long 3.5-5.5mm, GHSV are 7200h
-1, total gas flow rate is 1200ml/min.NO is deviate from 250 DEG C ~ 425 DEG C
xefficiency is all greater than 95%, and denitration activity is up to 100%.
Beneficial effect:
This catalyst removal NO
xefficiency is high, and active temperature interval is wide, has higher to remove NO in 250 DEG C ~ 500 DEG C
xefficiency, concerted catalysis oxidation CO and HC activity is high, and have excellent sulfur resistive water resistant poisoning capability, higher mechanical strength, good storage ammonia performance, and catalyst cost is lower, cost performance is high, environmental friendliness, is specially adapted to marine diesel oil tail gas NO simultaneously
xremove, compared with commercial vanadium titanium catalyst, this catalyst oxidation CO and HC activity is high, has significantly storage ammonia performance, better stablizes denitration efficiency, minimizing the escaping of ammonia in the uneven situation of spray ammonia.
Accompanying drawing explanation
The catalyst denitration activity change curve of Fig. 1 prepared by embodiment 1;
The catalyst sulfur resistive water resistant poisoning denitration activity change curve of Fig. 2 prepared by embodiment 1;
The catalyst of Fig. 3 prepared by embodiment 1 and the maximum storage ammonia amount of traditional vanadium titanium catalyst and storage ammonia time changing curve.
Detailed description of the invention
Example 1
(1) preparation of cerium molybdenum composite oxides presoma
Measure 0.35g boehmite, it is even to add 3.25g deionized water and stirring, then drips that 0.18g nitric acid is obtained stablize aluminium glue, is placed in 80 DEG C of thermostat water baths and stirs 20min dispergation, obtain Alumina gel.Then take 19.2g six nitric hydrate cerium dissolve in 80 DEG C of water-baths stir into settled solution after mix with Alumina gel, stir 20min;
Be 1:0.1 according to Ce/Mo elemental mole ratios, take 0.78g Ammonium Molybdate Tetrahydrate and 0.78g monohydrate potassium adds the mixing of 2.34g deionized water, then stir until solution be clear shape, after be added drop-wise in cerium solution, need stirring in dropping process;
(2) co-catalyst presoma solion configuration
Take 1.58g six nitric hydrate praseodymium and add the mixing of 3.16g deionized water, then stir until solution is clear shape, obtained co-catalyst presoma;
(3) preparation of catalyst carrier
Take 12.36g gamma aluminium oxide and 14.83g boehmite powder, through ball mill mixing 1h, obtained mixed carrier;
(4) the co-catalyst presoma that step (2) is obtained is added drop-wise in the obtained cerium molybdenum composite solution of step (1) (stirring of dropping limit, limit), stir 30min, then together add in the obtained support material of step (3) with 0.49g carboxylic propyl methocel, stir pugging, after old drying in the shade, be put in heat preservation and dryness 2h in 80 DEG C of air dry ovens;
(5) roasting, shaping of catalyst
The catalyst pug that step (4) is obtained is inserted 550 DEG C of roasting 2h in Muffle furnace in air atmosphere and obtains sample; In prepared catalyst, with the aluminium oxide batch mixing carrier quality after burning till for benchmark, cerium molybdenum composite oxides mass percentage 33.3%, co-catalyst oxide mass percentage composition 3.33%.
(6) denitration rate is tested: consisting of of the gas of simulation: NO (930ppm), NH
3(930ppm), O
2(10vol.%), H
2o (5vol.% adds during use), SO
2(475ppm adds during use), N
2for carrier gas, catalyst amount 10ml, catalyst grain size is: diameter 3.5mm, long 3.5-5.5mm, GHSV are 7200h
-1, total gas flow rate is 1200ml/min.Fig. 1 is the test of fresh sample, and in 210 DEG C ~ 480 DEG C, denitration rate is 88.31% ~ 99.76%.Fig. 2, Fig. 3 are respectively catalyst sulfur resistive water resistant poisoning denitration activity change curve and the maximum storage ammonia amount of catalyst and store up ammonia time changing curve, can find out that catalyst has the storage ammonia performance of good sulfur resistive, water resistant poisoning performance and excellence.
Example 2:
(1) preparation of cerium molybdenum composite oxides presoma
Measure 0.5g boehmite, it is even to add 7.0g deionized water and stirring, then drips that 0.3g nitric acid is obtained stablize aluminium glue, is placed in 80 DEG C of thermostat water baths and stirs 25min dispergation, obtain Alumina gel.Then take 19.2g six nitric hydrate cerium dissolve in 85 DEG C of water-baths stir into settled solution after mix with Alumina gel, stir 25min;
Be 1:0.15 according to Ce/Mo elemental mole ratios, take 1.17g ammonium molybdate and 1.46g monohydrate potassium adds the mixing of 5.62g deionized water, then stir until solution be clear shape, after be added drop-wise in cerium solution, need stirring in dropping process;
(2) co-catalyst presoma solion configuration
Take 2.95g six nitric hydrate praseodymium and add the mixing of 5.91g deionized water, then stir until solution is clear shape, obtained co-catalyst presoma;
(3) preparation of catalyst carrier
Take 24.94g gamma aluminium oxide and 24.94g boehmite powder, through ball mill mixing 1.5h, obtained mixed carrier;
(4) the co-catalyst presoma that step (2) is obtained is added drop-wise in the obtained cerium molybdenum composite solution of step (1) (stirring of dropping limit, limit), stir 30min, then together add in the obtained support material of step (3) with 0.33g carboxymethyl cellulose, stir pugging, after old drying in the shade, be put in heat preservation and dryness 2h in 90 DEG C of air dry ovens;
(5) roasting, shaping of catalyst
The catalyst pug that step (4) is obtained is inserted 500 DEG C of roasting 1.5h in Muffle furnace in air atmosphere and obtains sample; In prepared catalyst, with the aluminium oxide batch mixing carrier quality after burning till for benchmark, cerium molybdenum composite oxides mass percentage 20.0%, co-catalyst oxide mass percentage composition 3.6%.
(6) denitration rate is tested: obtained catalyst is 7200h at GHSV
-1, ammonia nitrogen than be 1 condition under, in 210 DEG C ~ 480 DEG C, denitration rate is 86.3% ~ 97.33%.
Example 3:
(1) preparation of cerium molybdenum composite oxides presoma
Measure 0.5g boehmite, it is even to add 7.0g deionized water and stirring, then drips that 0.3g hydrochloric acid is obtained stablize aluminium glue, is placed in 80 DEG C of thermostat water baths and stirs 30min dispergation, obtain Alumina gel.Then take 10.89g cerium chloride dissolve in 80 DEG C of water-baths stir into settled solution after mix with Alumina gel, stir 30min;
Be 1:0.4 according to Ce/Mo elemental mole ratios, take 2.94g ammonium paramolybdate and 2.94g monohydrate potassium adds the mixing of 10.92g deionized water, then stir until solution be clear shape, after be added drop-wise in cerium solution, need stirring in dropping process;
(2) co-catalyst presoma solion configuration
Take 2.37g praseodymium chloride and add the mixing of 9.30g deionized water, then stir until solution is clear shape, obtained co-catalyst presoma;
(3) preparation of catalyst carrier
Take 40.64g gamma aluminium oxide and 54.19g boehmite powder, through ball mill mixing 1.5h, obtained mixed carrier;
(4) the co-catalyst presoma that step (2) is obtained is added drop-wise in the obtained cerium molybdenum composite solution of step (1) (stirring of dropping limit, limit), stir 30min, then together add in the obtained support material of step (3) with 0.33g glycerine, stir pugging, after old drying in the shade, be put in heat preservation and dryness 2h in 80 DEG C of air dry ovens;
(5) roasting, shaping of catalyst
The catalyst pug that step (4) is obtained is inserted 550 DEG C of roasting 1.5h in Muffle furnace in air atmosphere and obtains sample; In prepared catalyst, with the aluminium oxide batch mixing carrier quality after burning till for benchmark, cerium molybdenum composite oxides mass percentage 12.5%, co-catalyst oxide mass percentage composition 1.8%.
(6) denitration rate is tested: obtained catalyst is 7200h at GHSV
-1, ammonia nitrogen than be 1 condition under, in 210 DEG C ~ 480 DEG C, denitration rate is 86.3% ~ 97.33%.
Example 4
(1) preparation of cerium molybdenum composite oxides presoma
Measure 0.35g boehmite, it is even to add 3.25g deionized water and stirring, then drips that 0.18g nitric acid is obtained stablize aluminium glue, is placed in 80 DEG C of thermostat water baths and stirs 20min dispergation, obtain Alumina gel.Then take 24.07g cerium oxalate dissolve in 100 DEG C of water-baths stir into settled solution after mix with Alumina gel, stir 20min;
Be 1:0.15 according to Ce/Mo elemental mole ratios, take 1.17g ammonium molybdate and 1.46g monohydrate potassium adds the mixing of 5.62g deionized water, then stir until solution be clear shape, after be added drop-wise in cerium solution, need stirring in dropping process;
(2) co-catalyst presoma solion configuration
Take 1.86g ammonium metatungstate and add the mixing of 3.8g deionized water, then stir until solution is clear shape, obtained co-catalyst presoma;
(3) preparation of catalyst carrier
Take 21.4g gamma aluminium oxide and 28.46g boehmite powder, through ball mill mixing 1.5h, obtained mixed carrier;
(4) the co-catalyst presoma that step (2) is obtained is added drop-wise in the obtained cerium molybdenum composite solution of step (1) (stirring of dropping limit, limit), stir 30min, then together add in the obtained support material of step (3) with 0.41g acetamide, stir pugging, after old drying in the shade, be put in heat preservation and dryness 2h in 90 DEG C of air dry ovens;
(5) roasting, shaping of catalyst
The catalyst pug that step (4) is obtained is inserted in Muffle furnace in air atmosphere, and 500 DEG C of roasting 2h obtain sample; In prepared catalyst, with the aluminium oxide batch mixing carrier quality after burning till for benchmark, cerium molybdenum composite oxides mass percentage 20%, co-catalyst oxide mass percentage composition 3%.
(6) denitration rate is tested: obtained catalyst is 7200h at GHSV
-1, ammonia nitrogen than be 1 condition under, in 210 DEG C ~ 480 DEG C, denitration rate is 75.83% ~ 98.54%.
Example 5
(1) preparation of cerium molybdenum composite oxides presoma
Measure 0.5g boehmite, it is even to add 7.0g deionized water and stirring, then drips that 0.25g nitric acid is obtained stablize aluminium glue, is placed in 90 DEG C of thermostat water baths and stirs 20min dispergation, obtain Alumina gel.Then take 19.2g six nitric hydrate cerium dissolve in 90 DEG C of water-baths stir into settled solution after mix with Alumina gel, stir 30min;
Be 1:0.1 according to Ce/Mo elemental mole ratios, take 0.78g ammonium molybdate and 0.78g monohydrate potassium adds the mixing of 2.34g deionized water, then stir until solution be clear shape, after be added drop-wise in cerium solution, need stirring in dropping process;
(2) co-catalyst presoma solion configuration
Take 2.19g lanthanum nitrate and add the mixing of 5.2g deionized water, then stir until solution is clear shape, obtained co-catalyst presoma;
(3) preparation of catalyst carrier
Take 24.72g gamma aluminium oxide and 32.88g boehmite powder, through ball mill mixing 2h, obtained mixed carrier;
(4) the co-catalyst presoma that step (2) is obtained is added drop-wise in the obtained cerium molybdenum composite solution of step (1) (stirring of dropping limit, limit), stir 30min, then together add in the obtained support material of step (3) with 0.33g carboxylic propyl methocel, stir pugging, after old drying in the shade, be put in heat preservation and dryness 2h in 80 DEG C of air dry ovens;
(5) roasting, shaping of catalyst
The catalyst pug that step (4) is obtained is inserted 600 DEG C of roasting 3h in Muffle furnace in air atmosphere and obtains sample; In prepared catalyst, with the aluminium oxide batch mixing carrier quality after burning till for benchmark, cerium molybdenum composite oxides mass percentage 16.7%, co-catalyst oxide mass percentage composition 1.67%.
(6) denitration rate is tested: obtained catalyst is 7200h at GHSV
-1, ammonia nitrogen than be 1 condition under, in 210 DEG C ~ 480 DEG C, denitration rate is 88.4% ~ 89.70%.
Example 6
(1) preparation of cerium molybdenum composite oxides presoma
Measure 0.5g boehmite, it is even to add 7.0g deionized water and stirring, then drips that 0.25g hydrochloric acid is obtained stablize aluminium glue, is placed in 100 DEG C of thermostat water baths and stirs 30min dispergation, obtain Alumina gel.Then take 19.2g six nitric hydrate cerium dissolve in 100 DEG C of water-baths stir into settled solution after mix with Alumina gel, stir 30min;
Be 1:0.4 according to Ce/Mo elemental mole ratios, take 2.93g ammonium paramolybdate and 2.93g monohydrate potassium adds the mixing of 14.01g deionized water, then stir until solution be clear shape, after be added drop-wise in cerium solution, need stirring in dropping process;
(2) co-catalyst presoma solion configuration
Take 0.65g praseodymium nitrate, 0.45g lanthanum nitrate and 0.41g ammonium metatungstate and add the mixing of 4.33g deionized water, then stir until solution is clear shape, obtained co-catalyst presoma;
(3) preparation of catalyst carrier
Take 40.64g gamma aluminium oxide and 54.18g boehmite powder, through ball mill mixing 3h, obtained mixed carrier;
(4) the co-catalyst presoma that step (2) is obtained is added drop-wise in the obtained cerium molybdenum composite solution of step (1) (stirring of dropping limit, limit), stir 30min, then together add in the obtained support material of step (3) with 0.50g carboxylic propyl methocel, stir pugging, after old drying in the shade, be put in heat preservation and dryness 2h in 90 DEG C of air dry ovens;
(5) roasting, shaping of catalyst
The catalyst pug that step (4) is obtained is inserted 550 DEG C of roasting 2h in Muffle furnace in air atmosphere and obtains sample; In prepared catalyst, with the aluminium oxide batch mixing carrier quality after burning till for benchmark, cerium molybdenum composite oxides mass percentage 12.5%, co-catalyst oxide mass percentage composition 1.25%.
(6) denitration rate is tested: obtained catalyst is 7200h at GHSV
-1, ammonia nitrogen than be 1 condition under, in 210 DEG C ~ 480 DEG C, denitration rate is 88.8% ~ 98.26%.
Claims (8)
1. a diesel engine vent gas SCR denitration catalyst, is characterized in that with cerium molybdenum composite oxides for catalytic active component, with praseodymium, tungsten or lanthanum for co-catalyst, with aluminium oxide batch mixing for carrier; With the aluminium oxide batch mixing carrier quality after burning till for benchmark, cerium molybdenum composite oxides mass percentage 12.5% ~ 33.3%, co-catalyst oxide mass percentage composition 1.25% ~ 6%; In described cerium molybdenum composite oxides active component, the elemental mole ratios of Ce and Mo is 1:(0.10 ~ 0.40); Aluminium oxide batch mixing is gamma aluminium oxide and boehmite is 1:(1 ~ 1.33 in mass ratio) mixing.
2. prepare a method for diesel engine vent gas SCR denitration catalyst as claimed in claim 1, its concrete steps are:
(1) preparation of cerium molybdenum composite oxides precursor solution
Take boehmite, add deionized water and stirring and drip that acid is obtained stablize aluminium glue uniformly simultaneously, be placed in 80 DEG C ~ 100 DEG C thermostat water baths stirring dispergation; Wherein the mass ratio of boehmite, deionized water and acid is 1:(7 ~ 14): (0.5 ~ 0.6), finally adds in cerium solution and stirs, obtain solution A; The boehmite wherein preparing aluminium glue is (0.045 ~ 0.065) with cerium salt oxide mass ratio: 1;
Take molybdenum salt, monohydrate potassium add deionized water mixing; Wherein the mass ratio of molybdenum salt, monohydrate potassium and deionized water is 1:(1 ~ 1.25): (3 ~ 4.8), then stir until solution is clear shape, obtain solution B; Be 1:(0.10 ~ 0.40 by the elemental mole ratios of Ce and Mo), solution B is added drop-wise in solution A, needs in dropping process to stir;
(2) co-catalyst presoma solion configuration
Take and add deionized water mixing containing promoter metal salt; Mass ratio wherein containing promoter metal salt and deionized water is 1:(2 ~ 3.5), then stir until solution is clear shape, obtained co-catalyst presoma solion;
(3) preparation of carrier
Be 1:(1 ~ 1.33 according to gamma aluminium oxide and boehmite mass percent) take two kinds of raw materials, through ball mill mixing, obtained mixed carrier;
(4) co-catalyst presoma solion mixing cerium molybdenum composite oxides precursor solution obtained for step (1) and step (2) obtained, stir, then add in the obtained mixed carrier of step (3) together with additive, stir pugging, after old drying in the shade, heat preservation and dryness;
(5) roasting of catalyst
Catalyst pug step (4) obtained in air atmosphere roasting obtains diesel engine vent gas SCR denitration catalyst.
3. method according to claim 2, is characterized in that the cerium salt of step (1) is cerous nitrate, cerium oxalate or cerium chloride; In step (1), molybdenum salt is ammonium molybdate or ammonium paramolybdate; Be the praseodymium nitrate or the hydrochloride that contain promoter metal containing promoter metal salt in step (2).
4. method according to claim 2, is characterized in that the aluminium glue of preparation in step (1) needs 80 DEG C ~ 100 DEG C thermostat water baths to stir 20min ~ 30min dispergation.
5. method according to claim 2, is characterized in that the acid solution described in step (1) is the one in nitric acid, hydrochloric acid or sulfuric acid.
6. method according to claim 2, the additive that it is characterized in that in step (4) is one or more in carboxylic propyl methocel, carboxymethyl cellulose, glycerine or acetamide; Wherein the mass ratio of additive and cerium molybdenum composite oxides is (0.04 ~ 0.06): 1.
7. method according to claim 2, the drying that it is characterized in that in step (4) is temperature is 80 DEG C ~ 100 DEG C, heat preservation and dryness 1 ~ 4h in air dry oven.
8. method according to claim 2, is characterized in that roasting in step (5) is for inserting in Muffle furnace in air atmosphere, at 500 DEG C ~ 600 DEG C, and insulation 1.5 ~ 3h.
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