CN101112684A - Methanol self-heating recapitalization perovskite honeycomb ceramic integral catalyzer and method for preparing the same - Google Patents
Methanol self-heating recapitalization perovskite honeycomb ceramic integral catalyzer and method for preparing the same Download PDFInfo
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- CN101112684A CN101112684A CNA2007102013044A CN200710201304A CN101112684A CN 101112684 A CN101112684 A CN 101112684A CN A2007102013044 A CNA2007102013044 A CN A2007102013044A CN 200710201304 A CN200710201304 A CN 200710201304A CN 101112684 A CN101112684 A CN 101112684A
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a carbinol spontaneous heating reforming perovskite honeycomb ceramic monolith catalyst and the preparation method thereof. The invention belongs to catalyst manufacture technical field. The general chemical formula of the catalyst is A1-xA'Xb1-yB'O3(x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1), wherein, the A and A' are the rare earth metals La, Ce, Pr and Gd; The B and B' are the transition metals Cr, Zr, Zn, Ni, Co and Mn. The catalyst is prepared by the sol-gel method; generally the nitrate is added into the citric acid ammonium solution or EDTA citric acid ammonium solution and is complex by adjusting the pH value; the gel is generated by dehydration in temperature-constant water bath and is then dried in the oven for 24 hours under the temperature of 120 DEG C, and the perovskite oxide powder is obtained after pre-roasting and roasting. The powder is grinded into material slurry by a ball mill and is then dipped and brushed on the honeycomb ceramic surface, and the carbinol spontaneous heating reforming perovskite honeycomb ceramic monolith catalyst is prepared after roasting. The invention has the advantages of high conversion of carbinol spontaneous heating reforming, long service life, simple preparation process, anti-vibration, small resistance and easy replacement of the structural catalyst, etc.
Description
Technical field
The present invention relates to a kind of catalyst for hydrogen production by self-heating reforming of methanol for fuel cell hydrogen-feeding fuel and preparation method thereof, belong to catalyst and preparing technical field thereof.
Background technology
Fuel cell, especially Proton Exchange Membrane Fuel Cells (PEMFC) are just entering accurate commercialization stage, and its ideal fuels is pure hydrogen, but up to the present, the fuel supply of fuel cell remains a bottleneck of its commercial applications of restriction.From fossil fuel,, supply with fuel cell through reformation hydrogen production and be considered to solve one of the most real approach of fuel cell hydrogen fuel supply as methyl alcohol, natural gas, dimethyl ether, gasoline and diesel oil etc.
The reforming system volume is little owing to having for the preparing hydrogen by reforming methanol technology, the reformation pneumatolytic divides less, the reforming reaction mild condition, the methyl alcohol cost is low and the filling convenient, the high extensive concern that has been subjected to of methyl alcohol energy density.The preparing hydrogen by reforming methanol technology comprises steam reforming, partial oxidation reformation and self-heating recapitalization, and the characteristics of steam reforming reaction are H
2The concentration height, reaction temperature is low, and CO content is low, but steam reforming is the endothermic reaction, needs the outside that heat is provided.
When the partial oxidation reforming reaction is oxidant with the pure oxygen, can provide 67%H
2, and reaction speed is fast, the reformer compactness, and volume is little, but because the partial oxidation reforming reaction is a strong exothermal reaction, causes beds temperature runaway phenomenon easily, makes catalysqt deactivation.When being oxidant with the air, H
2Concentration is reduced to 41%.
And autothermal reforming reaction combines the advantage of steam reforming reaction and partial oxidation reforming reaction, can produce the hydrogen of high concentration on the one hand, and reaction speed is fast on the other hand, can realize the heat self-sufficiency, does not form focus in the beds.
Perovskite composite oxides (ABO
3) A and B position metal ion all can part replace by other metal ions, Lattice Oxygen can change near stoichiometric number, thereby form certain oxygen vacancies, this has important reusing to catalytic activity, simultaneously perovskite composite oxides has excellent high-temperature stability, successfully has been used for the partial oxidation of purifying vehicle exhaust, hydro carbons or catalytic combustion, solid oxide fuel cell electrode Preparation of Catalyst, catalytic reduction removes processes such as SOx and NOx.
The disclosed application number of China is used to provide the solid solution rate of Pd high and have the manufacture method of stay-in-grade perovskite composite oxide and this perovskite composite oxide for 200580007637.2 patent of invention discloses, and then the carbon monoxide-olefin polymeric that comprises this perovskite composite oxide is provided.According to general formula AxB (1-y) PdyO
3+ δ(1) each atomic ratio of Biao Shi perovskite composite oxide is made the raw material prescription, makes perovskite composite oxide; In the formula, A represents by at least a element of selecting in rare earth element and the alkaline-earth metal, B represents at least a element selected from transition elements (remove rare earth element and Pd), Al and Si, x represents the atomic ratio of 1＜x, y represents the atomic ratio of 0＜y≤0.5, and δ represents the oxygen excess part.
China's application number is that 200510124033.8 patent of invention discloses a kind of novel RE perovskite type catalyst that is applied to oxidation of nitric oxide.Invention provides a kind of RE perovskite type catalyst that the catalytic oxidation nitric oxide is a nitrogen dioxide that is used for, and it is characterized in that described catalyst comprises the Ca-Ti ore type active component shown in the following general formula: A1-xA ' xB1-yB '
yO
3A represents rare-earth metals La in the formula, and A ' comprises Zr, Ce, Sr, Ca, Ba, Pr; B and B ' represent transition metal Fe, Co, Ni, Mn, Cu and Ti; 0≤x≤0.9; 0≤y≤1.0.Catalyst preparation process of the present invention is simple, and cost is low.Catalyst of the present invention can reach 80% at 300 ℃ the highest to nitric oxide production oxidation activity.Alternative noble metal catalyst is used for before the purifying nitrogen oxides of lean-burn tail gas process, is nitric oxide pre-oxidation nitrogen dioxide, improves the removal efficient of nitrogen oxide.
Up to the present, do not find that as yet perovskite composite oxides is applied to oxidization of methanol reformation hydrogen production process.
Summary of the invention
The purpose of this invention is to provide whole catalyst for preparing hydrogen of a kind of methanol self-heating recapitalization honeycomb and its production and application.
It is A that catalyst chemical is formed general formula
1-xA '
XB
1-yB '
yO
3(0≤x≤1,0≤y≤1), catalyst support are honeycomb ceramic carrier, perovskite oxide A
1-xA '
XB
1-yB '
yO
3The final coating amount of ball milling slurry accounts for 10%60% of honeycomb ceramic carrier weight.
A and A ' are rare-earth metal La, Ce, Pr, Gd, Sm, and B and B ' are transition metal Cr, Zr, Zn, Ni, Co, Mn.
0.2≤x among the present invention≤0.8,0.2≤y≤0.8.
Perovskite oxide A
1-xA '
XB
1-yB '
yO
3The final coating amount of ball milling slurry accounts for the 20%-50% of honeycomb ceramic carrier weight.
Catalyst among the present invention is a main active component with rare earth metal and transition metal, makes the perovskite oxide powder by sol-gal process.Its preparation method is a sol-gal process, and concrete method is the nitrate adding complexing agent with A, A ', B or B ' metal, heating for dissolving, add ammoniacal liquor, regulator solution pH=5-7, dehydration generated gel in 2-6 hour in 60 ℃ of-90 ℃ of waters bath with thermostatic control, and this stage needs constantly to stir.With gel 100-150 in baking oven ℃ dry 10-36 hour, 400 ℃ preroast 1-4 hour, last 600 ℃-900 ℃ roasting 2-6 hour, obtain the perovskite oxide powder.
Complexing agent is ammonium citrate or ethylenediamine tetra-acetic acid ammonium citrate solution.
Oxide powder mixed being applied on the honeycomb ceramic carrier after the back adds the ball milling form slurry with the aqueous solution of nitric acid of pH1-2, make behind the drying and roasting.
Perovskite oxide ball milling slurry preparation method provided by the invention is as follows:
Perovskite powder and ball milling bead add in the ball grinder, and the part by weight of powder and bead is 1: 2-10, preferentially select 1: 6-8, used little bulb diameter is 3-16mm, and preferential 3-10mm adds the aqueous solution of nitric acid of pH=1-2 simultaneously, pH is preferential 1.4, makes in ball milling 6-24 hour.
To prepare the step of catalyst as follows for the perovskite oxide slurry among the present invention:
Adopt infusion process that oxide slurry is coated to through on the pretreated honeycomb ceramic carrier among the present invention, the 10%-60% of the weight duty white pottery porcelain weight of slurry, preferential 30%-50%.Carry out drying behind the slurry dipping, drying process can be selected forced air drying, freeze drying, microwave drying or vacuum drying.After the drying,, carry out high-temperature roasting at 300 ℃-1000 ℃ again, preferred 500 ℃-700 ℃ of temperature range through 120 ℃ of preroasts; Roasting time is 1-4 hour.
Application of Catalyst method of the present invention: get the honeycomb ceramic integral catalyzer of 1.5ml preparation, the internal diameter of packing into is in the quartz tube reactor of 8mm, with the slit between silica wool obstruction catalyst outer wall and the reactor wall.Feed methanol aqueous solution, water/methyl alcohol (mol ratio)=1.25, oxygen/methyl alcohol (mol ratio)=0.25 is 8000h at volume space velocity
-1, reaction temperature is 460 ℃-540 ℃, during synthesis under normal pressure, methanol conversion is 95%-100%, hydrogen selectivity＞80%.
Catalyst provided by the invention has following advantage:
1. need not through overactivation before the catalyst reaction of the present invention, eliminated the characteristic of Cu-series catalyst commonly used easy sintering under the condition of high temperature and aerobic existence simultaneously, at high temperature have very high catalytic activity and stability.
2. catalyst of the present invention does not contain the noble metal composition, has utilized the abundant rare earth element of China's reserves, and is with low cost.
3. the supporter of catalyst of the present invention is the ceramic honey comb structure, has structural catalyst antidetonation, little, the easy replacing of resistance drop, can effectively control characteristics such as reacting focus.
4. the invention has the advantages that methanol self-heating recapitalization conversion ratio height, shelf life is long, and preparation technology is simple.
5. experimental result shows that the course of reaction methanol conversion reaches 100%, and after start-stop reaction repeatedly, conversion ratio and selectivity remain unchanged, so this catalyst is fit to mobile fuel cell hydrogen source and fuel cell cogeneration system hydrogen production process.
The specific embodiment:
The pretreating process of honeycomb ceramic carrier is as follows:
1 handles the size that experiment needs with the cordierite honeycomb ceramic of 400cpsi or 600cpsi specification, and the aqueous solution of nitric acid with 3% soaks 2h, spends deionised water, removes acidic materials, to cleaning solution be neutrality;
Ceramic monolith after 2 washings is at 100 ℃ of dry 12h of air dry oven, and 900 ℃ of roasting 2h in Muffle furnace naturally cool to room temperature again;
3 ceramic monoliths of handling well are put into drier and are preserved with standby.
Example 1: preparation La
0.2Ce
0.8CrO
3The perovskite powder
(1) according to target composite oxides proportioning weighing nitrate and complexing agent make La: Ce: Cr=0.2: 0.8: 1, and (La+Ce+Cr): EDTA: Citirc Acid=1: 1: 1 simultaneously;
(2) EDTA and Citric Acid mixed dissolution are in ammoniacal liquor, and acid group and ammoniacal liquor stoichiometric proportion are 1: 1, obtain complex solution;
(3) nitrate is added in the complex solution, after the heating for dissolving, stir, make it naturally cool to room temperature, add ammoniacal liquor after cooling in complex liquid, regulating pH is 6;
(4) the water-bath temperature control is 80 ℃, stirs, and concentrates complex liquid, generates to gel; Again 120 ℃ of desiccant gels 10 hours;
(5) the gel calcination procedure is as follows: heated up 1 hour to 400 ℃ from room temperature, kept 1 hour; From 400 ℃ of intensifications 2 hours to 900 ℃, kept 5 hours then; Naturally cool to room temperature.
Example 2 preparation La
0.2Sm
0.8CrO
3The perovskite powder
(1) according to target composite oxides proportioning weighing nitrate and complexing agent make La: Sm: Cr=0.2: 0.8: 1, and (La+Sm+Cr): EDTA: Citirc Acid=1: 1: 1 simultaneously;
(2) EDTA and Citric Acid mixed dissolution are in ammoniacal liquor, and acid group and ammoniacal liquor stoichiometric proportion are 1: 1, obtain complex solution;
(3) nitrate is added complex solution, after the heating for dissolving, stir, make it naturally cool to room temperature, add ammoniacal liquor after cooling in complex liquid, regulating pH is 6;
(4) the water-bath temperature control is 60 ℃, stirs, and concentrates complex liquid, generates to gel; Again 120 ℃ of desiccant gels 18 hours;
(5) the gel calcination procedure is as follows: heated up 1 hour to 400 ℃ from room temperature, kept 1 hour; From 400 ℃ of intensifications 2 hours to 900 ℃, kept 5 hours; Naturally cool to room temperature.
Example 3: preparation La
0.2Ce
0.8Zn
0.8Cr
0.2O
3The perovskite powder
(1) according to target composite oxides proportioning weighing nitrate and complexing agent make La: Ce: Zn: Cr=0.2: 0.8: 0.8: 0.2, and (La+Ce+Zn+Cr): EDTA: Citirc Acid=1: 1: 1 simultaneously;
(2) EDTA and Citric Acid mixed dissolution are in ammoniacal liquor, and acid group and ammoniacal liquor stoichiometric proportion are 1: 1, obtain complex solution;
(3) nitrate is added complex solution, after the heating for dissolving, stir, make it naturally cool to room temperature, add ammoniacal liquor after cooling in complex liquid, regulating pH is 6;
(4) the water-bath temperature control is 90 ℃, stirs, and concentrates complex liquid, generates to gel; Again 120 ℃ of desiccant gels 24 hours;
(5) the gel calcination procedure is as follows: heated up 1 hour to 400 ℃ from room temperature, kept 1 hour; From 400 ℃ of intensifications 2 hours to 900 ℃, kept 5 hours; Naturally cool to room temperature.
Example 4: preparation Zn/La
0.2Ce
0.8CrO
3The preparation of honeycomb ceramic carrier integer catalyzer
(1) preparation La
0.2Ce
0.8CrO
3Perovskite powder such as example 1
(2) take by weighing 32 gram La
0.2Ce
0.8CrO
3The perovskite powder, the aqueous solution of nitric acid 55ml of adding pH=1.4, ball milling made the LaCeCr slurry in 6 hours.One of the honeycomb ceramic carrier that the pretreated 1.5680 gram hole density of learning from else's experience are 400cpsi (square inch), putting into the slurry dipping took out after 8 minutes, use the air purge residual slurry, after 120 ℃ of forced air dryings 12 hours, 500 ℃ of roastings 2 hours, repeat twice, the catalyst intermediate weight that obtains is 2.0156g.
(3) configuration 3M zinc nitrate solution 100ml is immersed in the catalyst intermediate of process (2) preparation in the zinc nitrate solution after 6 minutes, with the residual liquid of air purge, after 120 ℃ of forced air dryings 12 hours, 500 ℃ of roastings 2 hours repeat four times, and the catalyst finished weight is 2.2567g.
Example 5: preparation La
0.2Ce
0.8Zn
0.8Cr
0.2O
3Honeycomb ceramic integral catalyzer
(1) preparation La
0.2Ce
0.8Zn
0.8Cr
0.2O
3Perovskite powder such as example 2
(2) take by weighing 32 gram La
0.2Ce
0.8Zn
0.8Cr
0.2O
3The perovskite powder, the aqueous solution of nitric acid 55ml of adding pH=1, ball milling made La in 18 hours
0.2Ce
0.8Zn
0.8Cr
0.2O
3Slurry.One of the honeycomb ceramic carrier that the pretreated 1.5000 gram hole density of learning from else's experience are 400cpsi, putting into the slurry dipping took out after 5 minutes, use the air purge residual slurry, after 120 ℃ of forced air dryings 12 hours, 700 ℃ of roastings 2 hours, repeat twice, the catalyst finished weight that obtains is 1.9811g.
Example 6: preparation La
0.2Ce
0.8Zn
0.8Cr
0.2O
3Honeycomb ceramic integral catalyzer
(1) take by weighing the nitrate of La, Ce, Zn, Cr, make La: Ce: Zn: Cr=0.2: 0.8: 0.8: 0.2, add the aqueous solution of nitric acid 55ml of pH=2, ball milling made La in 12 hours
0.2Ce
0.8Zn
0.8Cr
0.2Slurry.
(2) one of the honeycomb ceramic carrier that pretreated 1.4852 gram hole density are 400cpsi of learning from else's experience, putting into the slurry dipping took out after 10 minutes, use the air purge residual slurry, after 120 ℃ of forced air dryings 12 hours, 600 ℃ of roastings 3 hours, repeat twice, the catalyst finished weight that obtains is 1.9605g.
Example 7: preparation Pr
0.2Ce
0.8Cr perovskite powder
(1) according to target composite oxides proportioning weighing nitrate and complexing agent make Pr: Ce: Cr=0.2: 0.8: 1, and (Pr+Ce+Cr): EDTA: Citirc Acid=1: 1: 1 simultaneously;
(2) EDTA and Citric Acid mixed dissolution are in ammoniacal liquor, and acid group and ammoniacal liquor stoichiometric proportion are 1: 1, obtain complex solution;
(3) nitrate is added complex solution, after the heating for dissolving, stir, make it naturally cool to room temperature, add ammoniacal liquor after cooling in complex liquid, regulating pH is 6;
(4) the water-bath temperature control is 90 ℃, stirs, and concentrates complex liquid, generates to gel; Again 120 ℃ of desiccant gels 20 hours;
(5) the gel calcination procedure is as follows: heating up from room temperature was warming up to 400 ℃ in 1 hour, kept 1 hour; From 400 ℃ of intensifications 2 hours to 900 ℃, kept 5 hours; Naturally cool to room temperature.
Example 8: preparation Gd
0.2Sm
0.8Cr perovskite powder
(1) according to target composite oxides proportioning weighing nitrate and complexing agent make Gd: Sm: Cr=0.2: 0.8: 1, and (Gd+Sm+Cr): EDTA: Citirc Acid=1: 1: 1 simultaneously;
(2) EDTA and Citric Acid mixed dissolution are in ammoniacal liquor, and acid group and ammoniacal liquor stoichiometric proportion are 1: 1, obtain complex solution;
(3) nitrate is added complex solution, after the heating for dissolving, stir, make it naturally cool to room temperature, add ammoniacal liquor after cooling in complex liquid, regulating pH is 6;
(4) the water-bath temperature control is 80 ℃, stirs, and concentrates complex liquid, generates to gel; Again 120 ℃ of desiccant gels 16 hours;
(5) the gel calcination procedure is as follows: heated up 1 hour to 400 ℃ from room temperature, kept 1 hour; From 400 ℃ of intensifications 2 hours to 900 ℃, kept 5 hours; Naturally cool to room temperature.
Example 9: preparation Pr
0.2Sm
0.8Cr perovskite powder
(1) according to target composite oxides proportioning weighing nitrate and complexing agent make Pr: Sm: Cr=0.2: 0.8: 1, and (Pr+Sm+Cr): EDTA: Citirc Acid=1: 1: 1 simultaneously;
(2) EDTA and Citric Acid mixed dissolution are in ammoniacal liquor, and acid group and ammoniacal liquor stoichiometric proportion are 1: 1, obtain complex solution;
(3) nitrate is added complex solution, after the heating for dissolving, stir, make it naturally cool to room temperature, add ammoniacal liquor after cooling in complex liquid, regulating pH is 7;
(4) the water-bath temperature control is 90 ℃, stirs, and concentrates complex liquid, generates to gel; Again 120 ℃ of desiccant gels 24 hours;
(5) the gel calcination procedure is as follows: heated up 1 hour to 400 ℃ from room temperature, kept 1 hour; From 400 ℃ of intensifications 2 hours to 800 ℃, kept 5 hours; Naturally cool to room temperature.
Example 10: preparation Sm
0.2Ce
0.8Cr perovskite powder
(1) according to target composite oxides proportioning weighing nitrate and complexing agent make Sm: Ce: Cr=0.2: 0.8: 1, and (Sm+Ce+Cr): EDTA: Citric Acid=1: 1: 1 simultaneously;
(2) EDTA and Citric Acid mixed dissolution are in ammoniacal liquor, and acid group and ammoniacal liquor stoichiometric proportion are 1: 1, obtain complex solution;
(3) nitrate is added complex solution, after the heating for dissolving, stir, make it naturally cool to room temperature, add ammoniacal liquor after cooling in complex liquid, regulating pH is 5;
(4) the water-bath temperature control is 90 ℃, stirs, and concentrates complex liquid, generates to gel; Again 120 ℃ of desiccant gels 24 hours;
(5) the gel calcination procedure is as follows: heated up 1 hour to 400 ℃ from room temperature, kept 1 hour; From 400 ℃ of intensifications 2 hours to 700 ℃, kept 4 hours; Naturally cool to room temperature.
Example 11 preparation Pr
0.2Ce
0.8CrO
3Honeycomb ceramic integral catalyzer
With embodiment 6:
Example 12 preparation Gd
0.2Sm
0.8CrO
3Honeycomb ceramic integral catalyzer
With embodiment 6:
Example 13 preparation Pr
0.2Sm
0.8CrO
3Honeycomb ceramic integral catalyzer
With embodiment 6:
Example 14 preparation Sm
0.2Ce
0.8CrO
3Honeycomb ceramic integral catalyzer
With embodiment 6.
Claims (10)
1. methanol self-heating recapitalization perovskite honeycomb ceramic integral catalyzer, it is characterized in that it is A1-xA ' XB1-yB ' yO3 (0≤x≤1 that catalyst is formed general formula, 0≤y≤1), wherein A and A ' are rare-earth metal La, Ce, Pr, Gd and Sm, and B and B ' are transition metal Cr, Zr, Zn, Ni, Co or Mn.
2. methanol self-heating recapitalization perovskite honeycomb ceramic integral catalyzer according to claim 1 is characterized in that described 0.2≤x≤0.8,0.2≤y≤0.8.
3. methanol self-heating recapitalization perovskite honeycomb ceramic integral catalyzer according to claim 1 is characterized in that catalyst is Gd0.2Sm0.8CrO3 honeycomb ceramic integral catalyzer, Pr0.2Sm0.8CrO3 honeycomb ceramic integral catalyzer, Sm0.2Ce0.8CrO3 honeycomb ceramic integral catalyzer, Pr0.2Ce0.8CrO3 honeycomb ceramic integral catalyzer, La0.2Ce0.8Zn0.8Cr0.2O3 honeycomb ceramic integral catalyzer, La0.2Ce0.8Zn0.8Cr0.2O3 honeycomb ceramic integral catalyzer or Zn/La0.2Ce0.8CrO3 honeycomb ceramic carrier integer catalyzer.
4. according to claim 1 or 3 described methanol self-heating recapitalization perovskite honeycomb ceramic integral catalyzers, it is characterized in that catalyst support is a honeycomb ceramic carrier.
5. the preparation method of a methanol self-heating recapitalization perovskite honeycomb ceramic integral catalyzer as claimed in claim 1 comprises the steps: that A, A ', B, B ' metal nitrate add complexing agent, heating for dissolving; Add ammoniacal liquor regulator solution pH=5-7; Dehydration generated gel in 2-6 hour in 60 ℃ of-90 ℃ of waters bath with thermostatic control; Gel is at 100-150 ℃ of dry 10-36 hour, 400 ℃ preroast 1-4 hour, 600 ℃-900 ℃ roasting 2-6 hour; With being applied on the honeycomb ceramic carrier after oxide powder and the aqueous solution of nitric acid mixing and ball milling form slurry, make behind the drying and roasting.
6. according to the preparation method of the described methanol self-heating recapitalization perovskite honeycomb ceramic integral catalyzer of claim 5, it is as follows to it is characterized in that the perovskite oxide slurry prepares the step of catalyst: with infusion process oxide slurry is coated to through on the pretreated honeycomb ceramic carrier, dry behind the ceramic monolith dipping sizing agent, preroast, high-temperature roasting.
7. according to the preparation method of the described methanol self-heating recapitalization perovskite honeycomb ceramic integral catalyzer of claim 5, it is characterized in that the 10%-60% of the weight duty white pottery porcelain weight of described slurry.
8. according to the preparation method of the described methanol self-heating recapitalization perovskite honeycomb ceramic integral catalyzer of claim 5, the pH that it is characterized in that aqueous solution of nitric acid is 1-2.
9. according to the preparation method of the described methanol self-heating recapitalization perovskite honeycomb ceramic integral catalyzer of claim 5, described complexing agent is ammonium citrate or ethylenediamine tetra-acetic acid ammonium citrate solution.
10. the application of methanol self-heating recapitalization perovskite honeycomb ceramic integral catalyzer in methanol self-heating reforming hydrogen manufacturing.
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| CNA2007102013044A CN101112684A (en) | 2007-08-08 | 2007-08-08 | Methanol self-heating recapitalization perovskite honeycomb ceramic integral catalyzer and method for preparing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103182308A (en) * | 2011-12-29 | 2013-07-03 | 中国石油化工股份有限公司 | Perovskite/metal composite oxide catalyst and preparation method thereof |
| CN109546190A (en) * | 2018-11-15 | 2019-03-29 | 中国矿业大学(北京) | A kind of solid oxide cell energy storage and conversion system |
| CN114272933A (en) * | 2022-01-05 | 2022-04-05 | 成都理工大学 | Calcium modified cobalt praseodymium perovskite type catalyst for autothermal reforming of acetic acid to produce hydrogen |
| CN114308046A (en) * | 2022-01-07 | 2022-04-12 | 成都理工大学 | Praseodymium-promoted nickel-lanthanum layered perovskite type catalyst for autothermal reforming of acetic acid to produce hydrogen |
| CN115945197A (en) * | 2023-01-13 | 2023-04-11 | 成都理工大学 | Y for autothermal reforming of acetic acid to produce hydrogen x Pr 2-x O 3-δ Solid solution type cobalt-based catalyst |
-
2007
- 2007-08-08 CN CNA2007102013044A patent/CN101112684A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103182308A (en) * | 2011-12-29 | 2013-07-03 | 中国石油化工股份有限公司 | Perovskite/metal composite oxide catalyst and preparation method thereof |
| CN103182308B (en) * | 2011-12-29 | 2015-05-20 | 中国石油化工股份有限公司 | Perovskite/metal composite oxide catalyst and preparation method thereof |
| CN109546190A (en) * | 2018-11-15 | 2019-03-29 | 中国矿业大学(北京) | A kind of solid oxide cell energy storage and conversion system |
| CN109546190B (en) * | 2018-11-15 | 2021-06-22 | 中国矿业大学(北京) | Solid oxide battery energy storage and conversion system |
| CN114272933A (en) * | 2022-01-05 | 2022-04-05 | 成都理工大学 | Calcium modified cobalt praseodymium perovskite type catalyst for autothermal reforming of acetic acid to produce hydrogen |
| CN114308046A (en) * | 2022-01-07 | 2022-04-12 | 成都理工大学 | Praseodymium-promoted nickel-lanthanum layered perovskite type catalyst for autothermal reforming of acetic acid to produce hydrogen |
| CN115945197A (en) * | 2023-01-13 | 2023-04-11 | 成都理工大学 | Y for autothermal reforming of acetic acid to produce hydrogen x Pr 2-x O 3-δ Solid solution type cobalt-based catalyst |
| CN115945197B (en) * | 2023-01-13 | 2024-04-05 | 成都理工大学 | Y for autothermal reforming of acetic acid to produce hydrogen x Pr 2-x O 3-δ Solid solution cobalt-based catalyst |
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