CN102658159B - Catalyst coating for preparing ammonia through hydration of solid urea and preparation method of same - Google Patents
Catalyst coating for preparing ammonia through hydration of solid urea and preparation method of same Download PDFInfo
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- CN102658159B CN102658159B CN2012101207310A CN201210120731A CN102658159B CN 102658159 B CN102658159 B CN 102658159B CN 2012101207310 A CN2012101207310 A CN 2012101207310A CN 201210120731 A CN201210120731 A CN 201210120731A CN 102658159 B CN102658159 B CN 102658159B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention belongs to the field of tail gas purification of a diesel vehicle, and particular relates to a catalyst coating used for preparing ammonia through hydration of solid urea and coated on an alloying metal carrier as well as a preparation method of the catalyst coating. The catalyst coating is made of mixed oxides comprising TiO2 and Al2O3; and the mixed oxides account for 5 to 10 percent of the mass of a FeCrAl alloy carrier, wherein, the molar ratio of Ti to Al is 4:1 to 1:3. The catalyst coating is prepared by adopting a collosol-gelling method, and the preparation method comprises the steps as follows: firstly, the FeCrAl alloy carrier is pre-processed; then a TiO2-Al2O3 coating is prepared through the collosol-gelling method; and finally, TiO2-Al2O3 coating solution is applied on the FeCrAl alloy carrier. The prepared catalyst coating has the advantages of low initiation temperature and high catalytic efficiency. By adopting the optimized TiO2-Al2O3 coating, the conversion rate of isocyanic acid can reach more than 95 percent when the temperature of the carrier reaches 150 DEG C, and the conversion rate approximates to 100 percent after the temperature of the carrier reaches 200 DEG C.
Description
Technical field
The invention belongs to the diesel car tail gas refining field, be specifically related to a kind of catalyst coat and preparation method of being used for solid urea hydrolysis ammonia processed who is coated on the alloying metal carrier.
Background technology
Along with developing rapidly of automobile industry, China's automobile pollution continues to increase, and still, enjoys the while easily that automobile brings people, and the pollution problem that exhaust emissions brings also is on the rise.Because a large amount of motor vehicles that use, pollutes very seriously in the big city, China's motor vehicle NOx discharge capacity reached 599.4 ten thousand tons in 2010, and growth trend is arranged, and NOx is the one of the main reasons of generation acid rain, photochemical fog and ozone hole.
Because characteristics such as SCR technology denitration efficiency height, anti-sulphur are strong adapt to China's national situation, at present the medium and heavy diesel engine for automobile of China for reach state IV, state V emission request is mainly selected the SCR technology path.SCR (SCR) technology is used ammonia (NH usually
3) as reducing agent, with the NO in the diesel engine exhaust
xSelect to be catalysed and reduced into N
2Consider that the liquefied ammonia storage is difficult, toxicity is big, the general urea ammonia processed that adopts, but the mass fraction that has come into operation at present is that 32.5% aqueous solution of urea takes up space greatly, should not use at cold district, if available solid urea directly makes ammonia, will overcome the weak point of above urea liquid ammonia processed.So the present invention is intended to develop the catalyst coat for solid urea hydrolysis ammonia processed.
Solid urea hydrolysis ammonia key processed is the hydrolysis of isocyanic acid, solid urea can thermal decomposition be ammonia and isocyanic acid (HNCO) at 160 ℃, isocyanic acid generates ammonia and carbon dioxide with the water reaction again, so hydrolysis of urea namely refers to the hydrolysis of isocyanic acid, but gaseous state isocyanic acid hydrolysis efficiency is low and generate polymer easily when temperature is lower than 300 ℃.Compare with ceramic monolith, metal alloy carrier has good heat conductivity and lower thermal capacitance, and be beneficial to catalyst and play a role fast, and, metal alloy carrier has better shock resistance, higher mechanical strength, is fit to very much do isocyanic acid hydrolyzation catalysis carrier.But alloy material is combined difficulty with catalyst coat, has the little and coating of catalyst loadings problem such as easily come off.
TiO
2, Al
2O
3Hydrolysis has good catalytic action to isocyanic acid (HNCO).TiO
2, Al
2O
3For reaction provides the active acid position, HNCO is adsorbed on oxide surface, meets the carbamic acid class material (NH that water forms ADSORPTION STATE
2COOH), carbamic acid class material becomes carbamate (NH (CO) O-) subsequently, and carbamate takes off CO
2Generate amine groups (NH
2), the amino group of this class ADSORPTION STATE is from being adsorbed on the H of adjacent active position then
2Obtain H among the O, generate NH
3And CO
2
Patent CN 101708473A discloses a kind of washcoat suspension for the manufacture of urea hydrolysis catalyst, and the catalytic activity composition is made up of titanium dioxide, silica and Containing Sulfur compound, does not mention Al
2O
3Use.This patent need be added with organic silicon compound and strengthen the coating bond properties, and SiO
2Not obvious and specific area is less, part Si O to the isocyanic acid catalytic effect
2The affiliation that adds reduce the TiO with catalytic activity
2The load ratio.
German patent DE 19734627 C1 and European patent EP 0487886 B1, EP0555746 B1,1153648 B1 disclose the hydrolysis of urea catalyst coatings separately, but the shortcoming of above catalyst coatings is, does not take into account the high catalysis of coating, anticorrosive and adhesion firmness comprehensively.
Summary of the invention
At the problems referred to above, the purpose of this invention is to provide a kind of catalyst coat and preparation method of being used for solid urea hydrolysis ammonia processed who is coated on the alloying metal carrier.This catalyst coat and metal alloy carrier adhere to firmly, and catalyst loadings is big, and catalytic effect is good, can resist the isocyanic acid corrosion.
The selection of carrier and coating ingredients: choose the FeCrAl alloy as carrier, FeCrAl alloy carrier is by relevant (CN1414892A) patent disclosure, fast, the mechanical strength advantages of higher of the heat transfer that the FeCrAl alloy has been taken into account metal, and the FeCrAl carrier surface generates Al behind the high-temperature oxydation
2O
3Whisker has increased the specific area of carrier, contains Al
2O
3The easier and Al of coating
2O
3The whisker combination, therefore, the present invention selects for use the coating of being made up of titanium dioxide, alundum (Al to apply FeCrAl alloy carrier, thereby catalyst loadings is increased.
The catalyst coat that is used for solid urea hydrolysis ammonia processed that is coated on the metal alloy carrier of the present invention is TiO
2With Al
2O
3The mixed oxide of forming, the quality that mixed oxide accounts for the FeCrAl carrier is 5～10%, wherein Ti and Al mol ratio are 4: 1～1: 3 (preferred ratio is 3: 1～1: 3).Coating performance the best when Ti and Al mol ratio are 3: 1, catalytic effect and to adhere to firmness all better; Ti and Al mol ratio are that 4: 1 o'clock coating catalytic effects are fine, but the adhesion firmness is poor slightly.
The present invention provides a kind of method of utilizing this catalyst coat of Prepared by Sol Gel Method simultaneously, and concrete steps are as follows:
1, FeCrAl alloy carrier is carried out preliminary treatment:
It is in 1: 1: 5 the mixed solution of ammoniacal liquor, hydrogen peroxide and water that FeCrAl alloy carrier is immersed in volume ratio fully, ultrasonic cleaning 20～50min; The alloy carrier is taken out, be immersed in the deionized water ultrasonic cleaning 20～50min; Again the alloy carrier is taken out, be immersed in the absolute ethyl alcohol ultrasonic cleaning 20～50min; At last the alloy carrier is taken out, under 80～150 ℃, in baking oven, dry and be placed in the Muffle furnace, standby behind 850～950 ℃ of roasting 4～6h under air ambient;
2, utilize sol-gel process to prepare TiO
2-Al
2O
3Coating:
Get ethanol 7.8ml, acetic acid 5.8ml, butyl titanate 5.67ml, together put into the beaker that capacity is 100ml, after agitator stirs, obtain mixed solution; Nine water aluminum nitrates are soluble in water, be made into mass fraction and be 37.5% aluminum nitrate solution, get 2.37～28.43g aluminum nitrate solution then, dropwise splash in the above-mentioned mixed solution with glue head dropper, after continuing to stir 20～50min, namely get TiO
2-Al
2O
3Coating solution; With TiO
2-Al
2O
3Coating solution is standby after still aging 4～6 hours;
3, with TiO
2-Al
2O
3Coating solution is coated on the FeCrAl alloy carrier:
Use TiO
2-Al
2O
3Coating solution applies pretreated FeCrAl alloy carrier, after drying in the shade, places baking oven in 80～150 ℃ of oven dry down in the FeCrAl alloy carrier that applies, and take out the cooling back; Again the FeCrAl alloy carrier that applies is placed Muffle furnace, in 450～650 ℃ of following roasting 1～3h; Repeating above-mentioned coating, oven dry and calcination steps 3～5 times, is 5～10% until the load capacity of coating on FeCrAl alloy carrier.
Compare with existing isocyanic acid hydrolyzation catalysis coating, the present invention has following characteristics:
(1) to be used for preparing the cost of material of catalyst coatings cheap in the present invention, and the preparation method is simple, is suitable for the scale industry and produces;
(2) catalyst coatings and the FeCrAl alloys adhesion of the present invention preparation are firm, the coating difficult drop-off, and catalyst loadings is big, and coating ingredients is all the catalyst activity composition, and catalytic activity is good;
(3) the anti-isocyanic acid corrosion of coating of the present invention, Al
2O
3Adding help to improve anti-isocyanic acid corrosive nature;
(4) catalyst coatings of the present invention has the advantage that initiation temperature is low, catalytic efficiency is high.Preferred TiO
2-Al
2O
3When coating reached 150 ℃ when temperature, the isocyanic acid conversion ratio reached more than 95%, and 200 ℃ of later conversion ratios are all near 100%.
Description of drawings
Fig. 1: the TiO of different proportionings
2-Al
2O
3The conversion rate curve of coating catalysis HNCO hydrolysis;
Fig. 2: through preliminary treatment FeCrAl carrier S EM (ESEM) photo of uncoated coating solution also;
Fig. 3: the SEM photo that applies FeCrAl carrier after the coating that Ti and Al mol ratio are 4: 1 (proportioning A);
Fig. 4: the SEM photo that applies FeCrAl carrier after the coating that Ti and Al mol ratio are 3: 1 (proportioning B);
Fig. 5: the SEM photo that applies FeCrAl carrier after the coating that Ti and Al mol ratio are 1: 1 (proportioning C);
Fig. 6: the SEM photo that applies FeCrAl carrier after the coating that Ti and Al mol ratio are 1: 3 (proportioning D).
As shown in Figure 1, A, B coating good catalytic activity, when temperature reached 150 ℃, the isocyanic acid conversion ratio reached more than 95%, and 200 ℃ of later conversion ratios are all near 100%;
As shown in Figure 2, pretreated FeCrAl carrier surface area increases;
Shown in Fig. 3,4,5,6, the coating that applies among Fig. 4 is smooth, evenly; An amount of Al
2O
3Adding the coating surface performance is improved, rough surface, specific area increases, and is conducive to the carrying out of catalytic reaction.
The specific embodiment
Embodiment 1: the preparation of carrier preliminary treatment and coating
At first, need to carry out preliminary treatment to FeCrAl alloy carrier: it is in 1: 1: 5 the mixed solution that FeCrAl alloy carrier is immersed ammoniacal liquor, hydrogen peroxide, water volume ratio fully, ultrasonic cleaning 30min; Carrier is taken out, immerse in the deionized water ultrasonic cleaning 30min; Again carrier is taken out, immerse in the absolute ethyl alcohol ultrasonic cleaning 30min; Then the alloy carrier is taken out, in 100 ℃ of baking ovens, dry and be placed in the Muffle furnace, standby behind 900 ℃ of roasting 5h under air ambient.
Secondly, utilize sol-gel process to prepare the TiO of different Ti, Al mol ratio
2-Al
2O
3Coating: get ethanol 7.8ml, acetic acid 5.8ml, butyl titanate 5.67ml, the capacity of putting into are that the beaker of 100ml mixes, and stir at agitator.Nine water aluminum nitrates are soluble in water, be made into mass fraction and be 37.5% aluminum nitrate solution, dropwise splash in the above-mentioned mixed solution with glue head dropper then, after continuing to stir 20min, namely get TiO
2-Al
2O
3Coating solution.Again with TiO
2-Al
2O
3Still aging 5 hours of coating solution, standby.Medicine proportioning consumption is as shown in table 1:
Table 1: amount of samples proportioning table
At last, with TiO
2-Al
2O
3Coating is coated on the pretreated FeCrAl alloy carrier: apply the FeCrAl carrier with the coating solution for preparing previously, after drying in the shade, the FeCrAl alloy carrier that applies is placed 100 ℃ of oven dry of baking oven, take out the cooling back.Again the FeCrAl alloy carrier that applies is placed Muffle furnace, 500 ℃ of roasting 1h.So repetitive coatings, oven dry and calcination steps are 3～5 times, reach 6% of metallic carrier quality until the coating load capacity.
With Ti: the Al mol ratio=coating was designated as the A coating, Ti in 4: 1: the Al mol ratio=coating was designated as the B coating, Ti in 3: 1: the Al mol ratio=coating was designated as the C coating, Ti in 1: 1: the Al mol ratio=coating was designated as the D coating in 1: 3.
Embodiment 2: ultrasonic test
Be 50Hz with the metal alloy carrier of applying coating in frequency, power is to finish the sonic oscillation test in the ultrasonic cleaner of 1000W: will apply cated metal alloy carrier and put into deionized water for ultrasonic cleaning 30min, by measuring ultrasonic preceding dry vehicle weight and the carrier quality of ultrasonic back oven dry, investigate the adhesion firmness of coating.Ultrasonic back weighing result is as shown in table 2, and the result shows TiO in the coating
2Too many (the A coating Ti: Al mol ratio=4: 1) cause the result of coating adhesiveness difference easily, reduce TiO in right amount of content
2Content, namely increase Al
2O
3Content in coating is of value to increases the adhesion of coating firmness.
The ultrasonic expulsion rate of the different proportioning coatings of table 2
| The coating label | A | B | C | D |
| Coating shedding rate (%) | 35.1 | 6.2 | 4.9 | 5.0 |
Embodiment 3: isocyanic acid hydrolyzation catalysis active testing
Isocyanic acid is obtained by the cyanuric acid depolymerization, and cyanuric acid can get isocyanic acid 300～330 ℃ of following depolymerization.Be carrier gas with nitrogen, the 12g cyanuric acid is added in the quartz ampoule, put into the temperature programming stove again and heat, change heating-up temperature and can change the concentration of isocyanic acid (HNCO) in carrier gas.
Test condition: HNCO is 1000ppm (volume fraction), H
2O is 6% (volume fraction), and all the other are N
2, air speed 100000h
-1
Test by experiment, the isocyanic acid hydrolyst coating of above-mentioned different proportionings all has the advantage that initiation temperature is low, catalytic efficiency is high.Wherein A, B coating good catalytic activity, when the alloying metal bed temperature reached 150 ℃, the isocyanic acid conversion ratio reached more than 95%; When the alloying metal bed temperature reached more than 200 ℃, the isocyanic acid conversion ratio was all near 100%.The low-temperature catalyzed effect of coating C, D is a bit weaker, but 200 ℃ of later isocyanic acid conversion ratios are all near 100%.
Comprehensive embodiment 2 and embodiment 3 experimental results, the present invention chooses B coating (Ti: Al=3: 1) be the isocyanic acid hydrolyzation catalysis coating of performance the best.
Claims (2)
1. catalyst coat that is used for solid urea hydrolysis ammonia processed, it is characterized in that: catalyst coat is coated on the FeCrAl alloy carrier, and coating is TiO
2With Al
2O
3The mixed oxide of forming, the quality that mixed oxide accounts for FeCrAl alloy carrier is 5～10%, wherein Ti and Al mol ratio are 4:1～1:3; And this catalyst coat is prepared by following steps,
(1) FeCrAl alloy carrier is carried out preliminary treatment:
FeCrAl alloy carrier is immersed in fully in the mixed solution of ammoniacal liquor, hydrogen peroxide and water that volume ratio is 1:1:5 ultrasonic cleaning 20～50min; The alloy carrier is taken out, be immersed in the deionized water ultrasonic cleaning 20～50min; Again the alloy carrier is taken out, be immersed in the absolute ethyl alcohol ultrasonic cleaning 20～50min; At last the alloy carrier is taken out, under 80～150 ℃, in baking oven, dry and be placed in the Muffle furnace, standby behind 850～950 ℃ of roasting 4～6h under air ambient;
(2) utilize sol-gel process to prepare TiO
2-Al
2O
3Coating:
Get ethanol 7.8ml, acetic acid 5.8ml, butyl titanate 5.67ml, together put into the beaker that capacity is 100ml, after agitator stirs, obtain mixed solution; Nine water aluminum nitrates are soluble in water, be made into mass fraction and be 37.5% aluminum nitrate solution, get 2.37～28.43g aluminum nitrate solution then, dropwise splash in the above-mentioned mixed solution with glue head dropper, after continuing to stir 20～50min, namely get TiO
2-Al
2O
3Coating solution; With TiO
2-Al
2O
3Coating solution is standby after still aging 4～6 hours;
(3) with TiO
2-Al
2O
3Coating solution is coated on the FeCrAl alloy carrier:
Use TiO
2-Al
2O
3Coating solution applies pretreated FeCrAl alloy carrier, after drying in the shade, places baking oven in 80～150 ℃ of oven dry down in the FeCrAl alloy carrier that applies, and take out the cooling back; Again the FeCrAl alloy carrier that applies is placed Muffle furnace, in 450～650 ℃ of following roasting 1～3h; Repeating above-mentioned coating, oven dry and calcination steps 3～5 times, is 5～10% until the load capacity of coating on FeCrAl alloy carrier, thereby prepares catalyst coat for solid urea hydrolysis ammonia processed at FeCrAl alloy carrier.
2. a kind of catalyst coat for solid urea hydrolysis ammonia processed as claimed in claim 1, it is characterized in that: Ti and Al mol ratio are 3:1～1:3 in the catalyst coat.
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|---|---|---|---|
| CN2012101207310A CN102658159B (en) | 2012-04-23 | 2012-04-23 | Catalyst coating for preparing ammonia through hydration of solid urea and preparation method of same |
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|---|---|---|---|
| CN2012101207310A CN102658159B (en) | 2012-04-23 | 2012-04-23 | Catalyst coating for preparing ammonia through hydration of solid urea and preparation method of same |
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|---|---|
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| CN102658159B true CN102658159B (en) | 2013-09-25 |
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| CN104785289B (en) * | 2015-03-14 | 2017-04-12 | 桂林理工大学 | Preparation method of molecular sieve coating layer on metal carrier |
| CN113070054B (en) * | 2021-03-02 | 2023-07-14 | 中国华电科工集团有限公司 | Preparation method, product and application of non-supported catalyst |
| CN113750948B (en) * | 2021-09-09 | 2023-04-28 | 西安热工研究院有限公司 | Urea catalytic hydrolysis reactor and method for flue gas denitration |
| CN114433056A (en) * | 2022-01-26 | 2022-05-06 | 浙江科卓环保科技有限公司 | Preparation method of wide-temperature-zone honeycomb type SCR denitration catalyst |
| CN114768886B (en) * | 2022-03-17 | 2023-09-29 | 西安热工研究院有限公司 | Coating method of composite metal oxide catalyst |
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| DE10022842A1 (en) * | 2000-05-10 | 2001-11-22 | Dmc2 Degussa Metals Catalysts | Structured catalyst for the selective reduction of nitrogen oxides using ammonia using a compound that can be hydrolyzed to ammonia |
| DE102008046994B4 (en) * | 2008-09-12 | 2015-02-12 | Süd-Chemie Ip Gmbh & Co. Kg | Urea hydrolysis catalyst |
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