CN1698951A - Metal structured catalyst for light alkane combustion and its preparation method - Google Patents
Metal structured catalyst for light alkane combustion and its preparation method Download PDFInfo
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- CN1698951A CN1698951A CN 200510013286 CN200510013286A CN1698951A CN 1698951 A CN1698951 A CN 1698951A CN 200510013286 CN200510013286 CN 200510013286 CN 200510013286 A CN200510013286 A CN 200510013286A CN 1698951 A CN1698951 A CN 1698951A
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Abstract
This invention relates to a metal structured catalyst used for lightening alkane burning, in addition to a preparing method. The catalyst comprises the metal carrier and catalyst, wherein the first layer is the metal carrier; the second layer is the sixth aluminate or its carried noble metal or non noble metal catalyst. The invention provides the preparing method of the metal structured catalyst at the same time.
Description
Technical field
The invention belongs to catalyst field, relate to the metal structured catalyst and the preparation method that are used for light alkane combustion.
Background technology
The catalyst that is used for light alkane combustion at present mainly contains noble metal, simple composite oxide, perovskite, hexa-aluminate etc.Can only adopt structural catalyst for the reaction that big air speeds such as burning, high heat are imitated, it can realize targets such as low pressure drop, high heat transfer effect, little reactor volume.In the structural catalyst carrier, metallic carrier has the advantage that wall is thin, thermal conductivity is high, thermal capacity is low, mechanical strength is high, thermal-shock resistance is good than ceramic monolith.But owing to physics and chemical property between metallic carrier and the catalyst differ bigger, so catalyst is difficult to stably stick on the metallic carrier.Some present metal structured catalysts exist that catalytic effect is bad, catalyst is easily from problems such as metallic carrier come off.
Consider from aspects such as catalytic activity, heat endurance, mechanical strength and thermal-shock resistances, hexa-aluminate is the combustion catalyst that application prospect is arranged most, makes the catalytic combustion that metal structured catalyst is used for light paraffins on the metallic carrier and yet there are no report but hexa-aluminate is carried on.
Summary of the invention
The objective of the invention is to disclose a kind of is the metallic walls and the incorporate metal structured catalyst that is used for light alkane combustion of catalyst of carrier with the metal, and the method that adopts dip-coating (dip-coating) is carried on hexa-aluminate and makes the catalytic combustion that metal structured catalyst is used for light paraffins on the metallic carrier and obtained good effect.
Metal structured catalyst provided by the invention, by metallic carrier with catalyst is two-layer forms, metallic carrier is as ground floor, and the second layer is hexa-aluminate or is the noble metal or the non-precious metal catalyst of hexa-aluminate and load thereof.
Described metal is stainless steel or high-temperature alloy.
Described hexa-aluminate is AM
XAl
12-XO
19, wherein A is alkaline-earth metal or La, M is a transition metal, and X=1, or 2, or 3.
Metal structured catalyst preparation method of the present invention may further comprise the steps:
(1) metal is processed into various needed shapes;
(2) metallic carrier is 900-1100 ℃ of heating pre-oxidation, and oxidization time is 5-20h;
Or in the solution that acid, salt or hydrochlorate mix, handle 3-10min, temperature is 30-80 ℃;
(3) hexa-aluminate adopts the coprecipitation method preparation, after 900-1200 ℃ of roasting, makes suspension through being dispersed in the lower boiling organic solvent behind screening, the ball milling, and the mass content of control hexa-aluminate is 3～8wt%;
Dip-coating (dip-coating) method of (4) employing routine on pretreated metallic carrier, is controlled time of immersion 3-5min, 20-50 ℃ of dip-coating temperature with catalyst cupport; At least through 2 dip-coatings, final heating-up temperature is 900-1200 ℃.
In above-mentioned method, can also be on the hexa-aluminate catalyzer layer load base metal or noble metal, common preparation method is an infusion process, to have the metallic carrier of hexa-aluminate layer to be immersed in the solution of base metal or noble metal takes out behind the 1-4min, dry, 300-800 ℃ of roasting 3-5h, wherein the base metal solution concentration is 0.5-2mol/l, is 0.05-0.5mol/l for precious metal solution concentration.
Above-mentioned said acid can be one or more sour mixed liquors of sulfuric acid, hydrochloric acid, nitric acid or acetic acid etc.; Salt can be halide.
Above-mentioned lower boiling organic solvent can be ethanol, acetylacetone,2,4-pentanedione, the mixed liquor of one or more solvents of acetone or ether etc.
Metal structured catalyst provided by the present invention, primary raw material are stainless steel or high-temperature alloy.Catalyst is mainly the noble metal or the non-precious metal catalyst of hexa-aluminate and load thereof, and the kind of these base metals or noble metal and prescription have obtained open in many patent documentations, repeat no more herein.Adopt the dip-coating method that catalyst is carried on the metallic carrier as the second layer.
Structural catalyst is easy to be processed into the shape of various complexity, the mechanical strength height, and good heat conductivity can adapt to the needs of various different situations, is a kind of light alkane combustion catalyst with broad prospect of application.The light paraffins catalytic combustion except that can being used for natural gas power, automobile engine, also can be used for aspects such as the heat supply of chemical reaction original position, civilian and commercial heater and boiler as a kind of cleaning, the approach of heat energy supply efficiently.
The specific embodiment
Embodiment 1:
With cellular Aludirome in acetone and water with ultrasonic wave clean, dry back is at 1000 ℃ of oxidation 5h.LaMn with 900 ℃ of roastings
2Al
10O
19Powder is crossed and is dispersed in concentration ratio behind the 300-400 mesh sieve is in 1: 1 the ethanol and acetylacetone,2,4-pentanedione organic solvent, ball milling 10h, control LaMn
2Al
10O
19Mass content be 3wt%.Metallic carrier after will handling immerses in the suspension and takes out behind the 3min, 900 ℃ of roasting 1h, repeat 3 times after, make metal structured catalyst at 1000 ℃ of roasting 5h.
At unstripped gas is 1.5vol% methane and 98.5vol% Air mixing gas, air speed 60Lg
-1H
-1The test experiments condition under, when using structural catalyst 720 ℃ in methane with regard to complete reaction, 750 ℃ of methane unreacted also when not using structural catalyst.
Embodiment 2:
After commercially available refractory metal cleaned with ultrasonic wave, be immersed in the H of 100g/l in acetone and water
2SO
4And handle 3min at 60 ℃ in the NaCl mixed liquor of 100g/l.BaCuAl with 1000 ℃ of roastings
11O
19Catalyst is crossed and is dispersed in ethanol and acetylacetone,2,4-pentanedione concentration ratio behind the 400-600 mesh sieve is ball milling 15h in 1: 3 the mixed solvent, control BaCuAl
11O
19Mass content be 5wt%.Metallic carrier after handling is immersed in BaCuAl
11O
19Take out behind the 5min in the suspension, 1000 ℃ of roasting 1h, repeat 2 times after, make metal structured catalyst at 1200 ℃ of roasting 5h.
The metal structured catalyst 30min that in the supersonic oscillations instrument of 40KHz/100w, vibrates, the hexa-aluminate 12-15% that only comes off; Metal structured catalyst takes out in the cold water be placed on 25 ℃ immediately and quenches behind 800 ℃ of heating 20min, repeat 10 times after, the hexa-aluminate 4-6% that only comes off.
Embodiment 3:
After commercially available stainless steel alloy cleaned with ultrasonic wave in acetone and water, be immersed among the HCl of 50g/l and handle 5min at 30 ℃.LaCo with 1100 ℃ of roastings
3Al
9O
19Powder is dispersed in ball milling 18h in the ethanol after crossing the 400-600 mesh sieve, control LaCo
3Al
9O
19Mass content be 8wt%.Metallic carrier after handling is immersed in LaCo
3Al
9O
19Take out behind the 2min in the suspension, 900 ℃ of roasting 1h, repeat 2 times after, at 1100 ℃ of roasting 4h.LaCo will be arranged
3Al
9O
19The metallic carrier of layer is immersed in Pd, Pt noble metal or the non-noble metal solution such as Cu, Mn and takes out behind the 1-5min, and 600 ℃ of roasting 3h make metal structured catalyst.
The present invention is not limited to the technology described in the embodiment; its description is illustrative; and it is nonrestrictive; authority of the present invention is limited by claim; based on present technique field personnel according to the present invention can change, technology related to the present invention that method such as reorganization obtains, all within protection scope of the present invention.
Claims (9)
1. metal structured catalyst by metallic carrier with catalyst is two-layer forms, is characterized in that metallic carrier as ground floor, and the second layer is a hexa-aluminate catalyzer.
2. a kind of metal structured catalyst as claimed in claim 1 is characterized in that the described second layer is the noble metal or the non-noble metal catalyst of hexa-aluminate and load thereof.
3. a kind of metal structured catalyst as claimed in claim 1 is characterized in that described metal is stainless steel or high-temperature alloy.
4. a kind of metal structured catalyst as claimed in claim 1 or 2 is characterized in that described hexa-aluminate is AM
XAl
12-XO
19, wherein A is alkaline-earth metal or La, M is a transition metal, and X=1, or 2, or 3.
5. metal structured catalyst preparation method may further comprise the steps:
(1) metal is processed into various needed shapes;
(2) metallic carrier is 900-1100 ℃ of heating pre-oxidation, and oxidization time is 5-20h;
(3) hexa-aluminate is made suspension through disperseing behind screening, the ball milling in the lower boiling organic solvent after 900-1200 ℃ of roasting, and the mass content of control hexa-aluminate is 3～8wt%;
(4) method of the conventional dip-coating of employing on pretreated metallic carrier, is controlled time of immersion 3-5min, 20-50 ℃ of dip-coating temperature with catalyst cupport; At least through 2 dip-coatings, final heating-up temperature is 900-1200 ℃.
6. the preparation method of a kind of metal structured catalyst as claimed in claim 5 is characterized in that described step (2) is to handle 3-10min in the solution that acid, salt or hydrochlorate mix, and temperature is 30-80 ℃.
7. as the preparation method of claim 5 or 6 described a kind of metal structured catalysts, it is characterized in that load base metal or noble metal on the hexa-aluminate layer of metallic carrier, to have the metallic carrier of hexa-aluminate layer to be immersed in the solution of base metal or noble metal takes out behind the 1-4min, dry, 300-800 ℃ of roasting 3-5h, wherein the base metal solution concentration is 0.5-2mol/l; Precious metal solution concentration is 0.05-0.5mol/l.
8. a kind of metal structured catalyst preparation method as claimed in claim 6 is characterized in that described acid is one or more sour mixed liquors of sulfuric acid, hydrochloric acid, nitric acid or acetic acid; Salt is halide salt.
9. as claim 5 or 6 described a kind of metal structured catalyst preparation methods, it is characterized in that described lower boiling organic solvent is the mixed liquor of one or more solvents of ethanol, acetylacetone,2,4-pentanedione, acetone or ether.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510013286 CN1698951A (en) | 2005-04-07 | 2005-04-07 | Metal structured catalyst for light alkane combustion and its preparation method |
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|---|---|---|---|
| CN 200510013286 CN1698951A (en) | 2005-04-07 | 2005-04-07 | Metal structured catalyst for light alkane combustion and its preparation method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107702094A (en) * | 2016-08-08 | 2018-02-16 | 吉恩特恩斯有限公司 | Utilize the burner of Catalytic Combustion over Hexaaluminate |
-
2005
- 2005-04-07 CN CN 200510013286 patent/CN1698951A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107702094A (en) * | 2016-08-08 | 2018-02-16 | 吉恩特恩斯有限公司 | Utilize the burner of Catalytic Combustion over Hexaaluminate |
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