CN105126931A - Catalyst supporting method for methanol-steam reforming hydrogen-producing system - Google Patents
Catalyst supporting method for methanol-steam reforming hydrogen-producing system Download PDFInfo
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- CN105126931A CN105126931A CN201510509943.1A CN201510509943A CN105126931A CN 105126931 A CN105126931 A CN 105126931A CN 201510509943 A CN201510509943 A CN 201510509943A CN 105126931 A CN105126931 A CN 105126931A
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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
- 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
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Abstract
The invention relates to a catalyst supporting method for a methanol-steam hydrogen-producing system, and concretely relates to a catalyst supporting method for improving performances of a methanol-steam minisize reformer. In order to solve the problems that reformer performances decreases because of falling off of a catalyst, the fell catalyst blocks air outlets, and the like, surface electrochemical corrosion is performed on a micro-channel aluminium plate, so that formed stepwise pores help to increase the surface roughness and the specific surface area. Then the aluminium plate subjected to electrochemical etching is oxidized in diluted nitric acid, so that a thin oxidation layer is formed on the surface and is used to provide a support for the catalyst and enable the catalyst to relatively easily attach to the carrier. Due to the fact that the catalyst is supported on the surface of the micro-channel aluminium plate processed according to the above process, the catalyst adhesion amount is increased, the adhesiveness of the catalyst on the carrier is improved, and thus the methanol conversion rate is improved and the performances of the methanol-vapor minisize reformer are improved.
Description
Technical field
The present invention relates to a kind of loading method that can improve the catalyst of methanol steam micro-reformer performance.
Background technology
Fuel cell is pollution-free, the generation technology that energy conversion efficiency is high of 21 century first-selection, has purposes widely in fields such as space flight, military affairs, communication and traffic.Fuel cell fuel used serviceability hydrogen be desirable selection, hydrogen fuel cell substantially can realize " zero-emission " on electric automobile.But hydrogen belongs to flammable explosive gas, in transport, storage etc., there is larger potential safety hazard, therefore can utilize and the micro-reformer of instant hydrogen energy source can be provided to address this problem.Miniature methanol reformer has good heat and mass transfer characteristics, and it has larger inside multiphase system response area.Indirect methanol fuel cell is that methyl alcohol is changed into through reformer the TRT that hydrogen resupplies fuel cell, and it is integrated with, and pure hydrogen fuel battery starts soon at low temperature, superiority in power, energy conversion rate etc.
In miniature methanol reformer, supporting of catalyst is a pith, support in process and how to ensure that catalyst activity uniform component distribution and catalyst and reactant have larger contact area, raising catalyst utilization, methyl alcohol conversion ratio and battery life tool are of great significance.In addition, having comparatively atmospheric pressure existence by passing into after methanol gasifying in reformer, easily the catalyst granules that carrier adheres to being blown off and causing the blocking of gas vent, so the tack of catalyst is also the major issue needing in catalyst loading process to consider.
Summary of the invention
To come off the problem such as the reformer hydraulic performance decline caused and the catalyst blockage venthole come off to solve catalyst, the invention provides a kind of loading method of methanol recapitalization steam hydrogen manufacturing system, by finished commercial prod's copper-based methanol catalyst loading on fluid channel aluminium sheet carrier.
Described object is achieved through the following technical solutions:
A kind of loading method of preparing hydrogen from methanol steam System Catalyst, the surface treatment carrying out electrochemical etching and oxidation to fluid channel surface of aluminum plate increases the roughness on its surface, with surface through the fluid channel aluminium sheet of electrochemical etching for carrier, become nano particle to make stable suspension finished commercial prod's copper-based catalysts ball milling, then utilize infusion method by catalyst loading on carrier.Concrete steps are as follows:
One, the preparation process of fluid channel carrier:
Get the aluminium sheet of one piece of suitable size, make the runner of the required size of experiment at the side engraving machine on its surface.By putting into the sodium chloride electrolysis matter solution of 0.05-0.15mol/l after its surperficial wash clean, using aluminium sheet as anode, graphite cake is as negative electrode, and passing into current density under room temperature is 10-30ms/cm
2, voltage is the constant current electrochemical etching 1-3h of 2-10V.By aluminium flake ethanol and deionized water ultrasonic cleaning successively after having etched, then put into drying box and dried.Next put it in the dust technology of 1-2mol/l and be oxidized 1-2 days, make its surface form layer oxide film.
Two, the preparation of catalyst suspension:
Finished commercial prod's copper-based methanol reforming catalyst is put into mortar, and hand-ground becomes comparatively small catalyst particle, then put it in agate tank add appropriate deionized water utilize high energy ball mill wet-milling until formed nanoparticle catalyst.The rotating speed of high energy ball mill is 200-300r/min, and Ball-milling Time is 12-24h.The catalyst that wet-milling is good is added appropriate deionized water, supersonic oscillations, then add a little dust technology, supersonic oscillations, then magnetic agitation forms uniform and stable suspension.Wherein the content of catalyst is 5-10wt.%, and the content of dust technology is 0.5-1.0mol/l, and the dust technology amount that every gram of catalyst is corresponding is 0.2-0.5ml.Adding a little dust technology is to prevent catalyst granules from condensing, and ensures the stability of suspension.
Three, the deposition process of catalyst on fluid channel carrier:
First fluid channel carrier is slowly immersed in the suspension prepared, with peristaltic pump, it is slowly at the uniform velocity taken out after a while, now unnecessary slurry will along runner landing, then put it in 60 DEG C of insulating boxs and dry 30-40min, finally put it in the reformer chamber that lucite makes, in reformer chamber, blast a large amount of gas to increase chamber internal gas pressure with high pressure air rifle, unstable for attachment catalyst is blown off from carrier.
Four, repeat step 3, fluid channel carrier just can adhere to the good catalyst of a certain amount of tack.Wherein the loading of catalyst is 10-40mg.cm
-2.
In the present invention, the channel size of fluid channel aluminium sheet: width of flow path is 0.1-0.5mm, the degree of depth of runner is 0.1-0.5mm, and the width of ridge is 0.1-0.5mm.
The present invention is the fastidious performance of methanol reforming catalyst and the tack on carrier thereof mainly, because methyl alcohol is higher with the conversion ratio of the larger methyl alcohol of contact area of catalyst, so the specific area of increase catalyst can improve its catalytic performance.Compared to prior art, tool of the present invention has the following advantages:
1, fluid channel aluminium sheet is carried out to the electrochemical corrosion on surface, make its surface occur the irregular step-like hole of several microns, increase the roughness on its surface, specific area and adsorptivity.
2, be oxidized in dust technology by the aluminium sheet that electrochemical etching is good, make its surface form the oxide layer of thin layer, oxide layer can provide support to make it more easily be attached to carrier for catalyst.
3, by catalyst loading to surface on the fluid channel aluminium sheet of said process process, the adhesion amount of catalyst can be increased, improve the tack of catalyst on carrier, fluid channel can allow unnecessary catalyst flow down along runner direction when catalyst deposit, the time of contact of methyl alcohol and catalyst can be increased when chemical reaction, thus improve the conversion ratio of methyl alcohol, improve the performance of methanol steam micro-reformer.
4, become nano particle to make it have small-size effect finished commercial prod's methanol reforming catalyst ball milling, not only increase its specific area, the deposit that suspension facilitates it on carrier can also be made into, make methyl alcohol and catalyst have larger contact area.
5, with high pressure air rifle, catalyst poor for the tack be at every turn deposited on carrier is blown off to improve the tack of catalyst on carrier, catalyst can be solved and to come off the problem such as the reformer hydraulic performance decline caused and the catalyst blockage venthole come off.
Accompanying drawing explanation
Fig. 1 is the fluid channel surface of aluminum plate after electrochemical etching;
Fig. 2 is uniform and stable catalyst suspension.
Detailed description of the invention
Below in conjunction with accompanying drawing, technical scheme of the present invention is further described; but be not limited thereto; everyly technical solution of the present invention modified or equivalent to replace, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
The invention provides a kind of loading method of preparing hydrogen from methanol steam System Catalyst, its concrete steps are as follows:
One, the preparation process of fluid channel carrier:
1, first carve the aluminium sheet of 30mm × 50mm × 20mm with engraving machine, then go out wide 0.5mm with the graduating with cutter of 0.5mm, the runner of dark 0.5mm, and ridge wide be 0.5mm.
2, the aluminium sheet carved is cleaned up rear alcohol, deionized water supersonic oscillations 5min successively, then the sodium chloride solution 200ml of 0.1mol/l is configured as electrolyte solution, with graphite as negative electrode, aluminium sheet is as anode, pass into the constant current of 0.3A, voltage is 4V, electrochemical etching 2h.
3, alcohol, deionized water supersonic oscillations 5min is successively used again by after the aluminium sheet wash clean etched, then the dust technology putting into 1mol/l is oxidized 24h, so just obtain surface roughness very high, and have the fluid channel aluminium sheet (Fig. 1) of skim oxide-film.
Two, the preparation of catalyst suspension:
1, take out 4g finished commercial prod copper-based methanol reforming catalyst and put into mortar, manually be ground into comparatively granule, then to put it in agate tank and to add 10ml deionized water, 18h is ground again with high energy ball mill, wherein the rotating speed of ball mill is 200r/mim, can obtain nanoparticle catalyst.
2, good for wet-milling catalyst is taken out, add 100ml deionized water, put it into the insulating box evaporating liquid of 60 DEG C to 40ml, supersonic oscillations 30min, then adding 1ml molal weight mark is the dust technology of 1mol/l, then supersonic oscillations 30min, then magnetic agitation 24h can obtain uniform and stable suspension (Fig. 2).
Three, the deposition process of catalyst on fluid channel carrier:
Fluid channel aluminium sheet is put into suspension gently, aluminium sheet is at the uniform velocity pulled out with the speed of 2cm/min with peristaltic pump, turbid night unnecessary in this process can flow back to beaker along runner, stay and aluminium sheet is the good catalyst of tack, then dry 30min in the insulating box of 60 DEG C is put it into, put it in the reformer chamber mould that lucite makes again, in mould, blast a large amount of gas with high pressure air rifle, make to be full of in chamber the larger air-flow of pressure with the poor catalyst of tack on the fluid channel aluminium sheet that blows off.Said process, just can obtain 15mg.cm on fluid channel aluminium sheet so repeatedly
-2the good catalyst of tack.Wherein in suspension, the mass fraction of catalyst and each catalyst support gauging substantial connection on carrier, and thickness got over by catalyst, and the amount at every turn supporting supported catalyst is larger, but its tack can be poor.In unit are, the loading of catalyst per and the porosity of its maximum loading and fluid channel surface of aluminum plate have much relations in addition, the more each loading of porosity is larger, the maximum of loading is larger, thus the larger aluminium sheet of surface roughness its to support effect better.
Four, hydrogen production from methanol-steam reforming process:
First verify the air-tightness of reformer chamber, sealed by the reformer screw assembled, put into water after passing into argon gas, each contact surface bubble-free of reformer chamber occurs then illustrating that air-tightness is good.Then the fluid channel aluminium sheet having supported catalyst is put into reformer chamber, assemble rear screw to be sealed, then start reformer chamber heating until 240 DEG C, pass into water alcohol than the methanol aqueous solution for 1.1:1 with peristaltic pump with certain flow rate simultaneously, methanol aqueous solution first gasifies in the chamber that then enters and be placed with catalyst and carries out catalytic reaction in reformer chamber, wherein catalyst needs the reduction through methyl alcohol 20min just can carry out the chemical reaction of preparing hydrogen by reforming methanol, namely after the temperature of reformer chamber reaches 240 DEG C, 20min just has hydrogen generation, then by the speed of drainage Self-adaptive gas and then the conversion ratio of reckoning methyl alcohol, utilize gas phase to survey spectrometer analysis and generate CO in gas, H
2percentage, then minimum by the content of the temperature studies CO under how many degree changing heating, the conversion ratio of methyl alcohol is maximum.
Claims (7)
1. a loading method for hydrogen production from methanol-steam reforming System Catalyst, is characterized in that described method step is as follows:
One, the preparation process of fluid channel carrier:
Make the required runner of experiment at surface of aluminum plate engraving machine, carry out electrochemical etching by after its surperficial wash clean; By aluminium flake ethanol and deionized water ultrasonic cleaning successively after having etched, then put into drying box and dried; Finally put into dust technology to be oxidized, make its surface form layer oxide film;
Two, the preparation of catalyst suspension:
Copper-based methanol reforming catalyst is put into mortar, grind to form catalyst granules, then put it in agate tank and utilize high energy ball mill wet-milling to form nanoparticle catalyst, the catalyst that wet-milling is good adds deionized water, and then supersonic oscillations add dust technology, supersonic oscillations, then magnetic agitation forms uniform and stable suspension, and wherein the content of catalyst is 5-10wt.%, and the content of dust technology is 0.5-1.0mol/l;
Three, the deposition process of catalyst on fluid channel carrier:
First fluid channel carrier is slowly immersed in the suspension prepared, with peristaltic pump, it is slowly at the uniform velocity taken out after a while, then put it in insulating box and dry, finally put it in the reformer chamber that lucite makes, in reformer chamber, blast gas with high pressure air rifle and unstable for attachment catalyst is blown off from carrier;
Four, step 3 is repeated, until the deposit amount of fluid channel supported catalyst is 10-40mg.cm
-2.
2. the loading method of hydrogen production from methanol-steam reforming System Catalyst according to claim 1, is characterized in that described width of flow path is 0.1-0.5mm, and the degree of depth of runner is 0.1-0.5mm, and the width of ridge is 0.1-0.5mm.
3. the loading method of hydrogen production from methanol-steam reforming System Catalyst according to claim 1, it is characterized in that described electrochemical etching method is as follows: using sodium chloride solution as electrolyte, aluminium sheet is as anode, and graphite cake is as negative electrode, and passing into current density under room temperature is 10-30ms/cm
2, voltage is the constant current of 2-10V, electrochemical etching 1-3h.
4. the loading method of hydrogen production from methanol-steam reforming System Catalyst according to claim 3, is characterized in that the concentration of described sodium chloride solution is 0.05-0.15mol/l.
5. the loading method of hydrogen production from methanol-steam reforming System Catalyst according to claim 1, is characterized in that the concentration of the dust technology that described surface oxidation is used is 1-2mol/l, and the time of oxidation is 1-2 days.
6. the loading method of hydrogen production from methanol-steam reforming System Catalyst according to claim 1, it is characterized in that the rotating speed of described high energy ball mill is 200-300r/min, Ball-milling Time is 12-24h.
7. the loading method of hydrogen production from methanol-steam reforming System Catalyst according to claim 1, is characterized in that the nitric acid that every gram of catalyst is corresponding is 0.2-0.5ml.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112829486A (en) * | 2021-01-22 | 2021-05-25 | 中汽创智科技有限公司 | Printing slurry, bipolar plate flow field using same and processing method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1697227A (en) * | 2004-05-13 | 2005-11-16 | 三星Sdi株式会社 | Reformer for fuel cell system, fabrication method thereof, and fuel cell system comprising the same |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1697227A (en) * | 2004-05-13 | 2005-11-16 | 三星Sdi株式会社 | Reformer for fuel cell system, fabrication method thereof, and fuel cell system comprising the same |
Non-Patent Citations (1)
| Title |
|---|
| ARUNABHA KUNDU, ET AL.: "Process intensification by micro-channel reactor for steam reforming of methanol", 《CHEMICAL ENGINEERING JOURNAL》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112829486A (en) * | 2021-01-22 | 2021-05-25 | 中汽创智科技有限公司 | Printing slurry, bipolar plate flow field using same and processing method thereof |
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Inventor after: Deng Huichao Inventor after: Zhang Yufeng Inventor after: Degaudy scenery Inventor after: Liu Xiaowei Inventor after: Zhang Xuelin Inventor before: Zhang Yufeng Inventor before: Degaudy scenery Inventor before: Liu Xiaowei Inventor before: Zhang Xuelin |
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