CN102908909B - Nickel-copper-rare earth-aluminum oxide catalysis separation composite film and preparation method and application thereof - Google Patents
Nickel-copper-rare earth-aluminum oxide catalysis separation composite film and preparation method and application thereof Download PDFInfo
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- CN102908909B CN102908909B CN201210453240.8A CN201210453240A CN102908909B CN 102908909 B CN102908909 B CN 102908909B CN 201210453240 A CN201210453240 A CN 201210453240A CN 102908909 B CN102908909 B CN 102908909B
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Abstract
The invention discloses a nickel-copper-rare earth-aluminum oxide catalysis separation composite film and a preparation method and the application thereof. The method includes adopting an electroplating method to plate a nickel-copper-rare earth film on the surface of a porous through hole anode alumina film. In the preparation process, the nickel-copper-rare earth film bonded to a cathode and plated on the face is compact in structure, and the thickness of the nickel-copper-rare earth film is 0.1-0.5mum. Finally, the nickel-copper-rare earth-aluminum oxide catalysis separation composite film with multiple nanometer holes on one face and the nickel-copper-rare earth film on the other face is formed. The nickel-copper-rare earth-aluminum oxide catalysis separation composite film is applied to reproduction of hydrogen by catalyzing methane and water vapor and separation of hydrogen in mixed gas. Finally, the methane catalysis and conversion rate is 100%, the hydrogen transmission rate is 7.52-8.02*10-6mol*m-2*s-1Pa-1, the separation coefficient of the hydrogen obtained in reproduction of hydrogen by catalyzing methane and water vapor is 996-1002, and the separation coefficient of the hydrogen in the mixed gas is 1000-1008.
Description
Technical field
The present invention relates to a kind of at nonmetallic surface formation nickel alloy film, on the surface of porous through hole anodic alumina films, form nickel-copper-rare earth alloys in particular to a kind of, namely a kind of nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane and preparation method thereof with its catalytic methane vapor reforming hydrogen production with to gaseous mixture in application in being separated of hydrogen.
Background technology
Anodic alumina films has the features such as the high-sequential in hole, specific area be large, has a wide range of applications in the field such as catalysis material, separation.Anodic alumina films can prepare catalytic membrane by infusion process and sol-gel process.
Such as: porous anodic alumina films is immersed in RuCl by Ganley JC etc.
3with Ni (NO
3)
2in mixed liquor, prepare Ru-Ni-Al
2o
3film catalyst be used for the decomposition of catalytic amine, experiment shows that the conversion ratio of amine significantly increases along with the increase of the load capacity of Ru.
Plateaus etc. adopt anodizing to prepare porous alumina membrane, then in fenestra, fill TiO by sol-gel process
2, the TiO with photocatalytic activity prepared
2nano wire film is used for the degraded of acridine orange than the TiO prepared under the same terms
2the catalytic activity of/glass-film is good.
At present, to metal film be formed at nonmetallic surface, usually adopt the method for chemical plating.The complex operation of electroless plating method, and, due to more activation step, sensitising step, before in the end must carrying out chemical plating, have a large amount of preprocessing process, inevitably can expend the more time.Metal Palladium and alloy film thereof study the inoranic membrane for Hydrogen Separation the earliest, also may be at present for the unique business-like inoranic membrane of Hydrogen Separation, but precious metal palladium is expensive.
In the catalyst of current catalytic methane vapor reforming hydrogen production, the catalyst simultaneously carrying out catalysis and centrifugation only has palladium and palldium alloy, because palladium is noble metal, expensive, limits the commercial Application of its reality.
Summary of the invention
An object of the present invention is in the catalyst in order to solve above-mentioned current catalytic methane vapor reforming hydrogen production, the catalyst simultaneously carrying out catalysis and centrifugation only has palladium and palldium alloy, because palladium is noble metal, expensive, limit the commercial Application problem of its reality and a kind of nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane is provided.
Two of object of the present invention is to provide the preparation method of above-mentioned a kind of nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane.
Three of object of the present invention above-mentioned a kind of nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane is used for being separated of catalytic methane vapor reforming hydrogen production and hydrogen in gaseous mixture.
technical scheme of the present invention
A kind of nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane, namely adopt galvanoplastic at the plated surface last layer nickel-copper-rare earth film of porous through hole anodic alumina films, and be attached to the compact structure of nickel-copper-rare earth film that this one side on negative electrode plates in preparation process, thickness is 0.1 ~ 0.5 μm, final formation one surface is Donna metre hole, and another surface is fine and close nickel-copper-rare-earth aluminum oxide catalytic separation composite membrane;
In described nickel-copper-rare earth film, calculated example in mass ratio, i.e. nickel: copper: rare earth is 1:0.2 ~ 1.3:0.001 ~ 0.4.
Described rare earth is one or more the mixture in lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, scandium.
The preparation method of above-mentioned a kind of nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane, specifically comprises the steps:
(1), by porous through hole anodic alumina films pure water is put into, with Ultrasonic Cleaning, dry, calcination;
Wherein ultrasonic treatment time is 5 ~ 30min; Baking temperature is 50 ~ 100 DEG C, drying time 0.5 ~ 5h; Calcination temperature is 800 ~ 1100 DEG C, calcination time 0.5 ~ 5h;
(2), with adhesive tape, the porous through hole anodic alumina films to be plated after above-mentioned process is pasted onto on negative electrode, pastes adhesive tape at the reverse side of negative electrode;
Described adhesive tape is adhesive tape or two-sided tape;
Described negative electrode is nickel plate, copper coin or steel plate;
(3), by rare earth oxide be dissolved in acid, be mixed with rare earths salt;
Its middle rare earth is the mixture of one or more the rare earth oxide in lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, scandium rare earth oxide;
Described acid is nitric acid or hydrochloric acid;
Described rare-earth salts is the mixture of rare earth nitrades, rare earth-iron-boron or rare earth nitrades and rare earth-iron-boron, and the concentration of rare earths salt rare earth elements is 10 ~ 50g/L;
(4), with water-soluble solution nickel salt, mantoquita, complexing agent, chloride, adding above-mentioned rare earths salt, is 2 ~ 4 by sodium hydroxide solution adjust ph, makes mantoquita-nickel salt-complexing agent-chloride-rare-earth salts electroplate liquid;
In described mantoquita-nickel salt-complexing agent-chloride-rare-earth salts electroplate liquid, the concentration of nickel salt, mantoquita, complexing agent, chloride, rare-earth salts is respectively 10 ~ 400g/L, 10 ~ 250g/L, 5 ~ 100g/L, 10 ~ 300g/L, 0.04 ~ 10g/L;
Described nickel salt is the mixture of one or more compositions in nickel nitrate, nickel chloride, nickelous sulfate;
Described mantoquita is the mixture of one or more compositions in copper sulphate, copper chloride, copper nitrate;
Described complexing agent is the mixture of one or more compositions in formic acid, acetic acid, citric acid, tartaric acid, lactic acid, amion acetic acid, glycolic acid;
Described chloride is the mixture of one or more compositions in sodium chloride, potassium chloride, ammonium chloride;
(5), plating piece to be plated is put into electroplate liquid to electroplate;
Electroplating technique condition is current density is 1 ~ 15A/dm
2, bath pH values is 2 ~ 4, and temperature is 5 ~ 50 DEG C, and speed of agitator is 100 ~ 600rpm, and plating time is 14 ~ 30min, and anode is copper coin;
(6), take out plating piece, rinse with water clean, air-dry, peel off adhesive tape, nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane is separated with negative electrode, obtain nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane.
Nickel-copper-rare earth-alundum (Al2O3) catalytic separation the composite membrane of above-mentioned gained is used for the separation of the hydrogen of gained after catalytic methane vapor reforming hydrogen production and catalytic methane vapor reforming hydrogen production
H in methane vapor
2o:CH
4: N
2for 3:1:2.8(volume ratio), flow (every gram of nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane volume flowing through unstripped gas per hour) is 13.820Lg
-1h
-1temperature is under 550 ~ 1000 DEG C of conditions, the methyl hydride catalyzed conversion ratio of final nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane is 100%, and nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane is to the separation (H of the hydrogen of gained after catalytic methane vapor reforming hydrogen production
2/ CH
4) be 996 ~ 1002, the saturating hydrogen rate of nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane is 7.52 ~ 8.02 × 10
-6molm
-2s
-1pa
-1.
Nickel-copper-rare earth-alundum (Al2O3) catalytic separation the composite membrane of above-mentioned gained is used for the separation of hydrogen in gaseous mixture
H in gaseous mixture
2: CH
4: N
2for 4:1:2.8(volume ratio), flow is 13.820Lg
-1h
-1, temperature is under 25 ~ 550 DEG C of conditions, and final nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane is to the separation (H of hydrogen in gaseous mixture
2/ CH
4) be 1000 ~ 1008.
Beneficial effect of the present invention
A kind of nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane of the present invention, because the hole of porous through hole anodic alumina films is straight hole, have employed galvanoplastic, form nickel-copper-rare earth film that a surface is Donna metre hole, another surface is densification on the surface of porous through hole anodic alumina films.Cu has the ability of certain absorption-desorption hydrogen, and there is the ability of anti-hydrogen embrittlement, Ni can catalytic methane vapor reforming hydrogen production, surface area due to this nickel-copper-rare earth film is large and have a lot of straight hole nano-pore, this nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane is used for catalytic methane vapor reforming hydrogen production, product hydrogen is separated by the nickel-copper-rare earth film of densification, straight hole is less than the resistance of curved hole, nano-pore has the nano effect improving catalytic performance, the present inventor finds that rare earth element has coordinating effect to nickel-copper catalysis and improves methyl hydride catalyzed conversion ratio, and rare earth doped be conducive in the nickel-copper film of densification hydrogen through, therefore a kind of nickel-copper-rare earth-di-aluminium trioxide film of the present invention is in catalytic methane vapor reforming hydrogen production, methyl hydride catalyzed conversion ratio reaches 100%, and there is the function being separated hydrogen simultaneously.
A kind of nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane of the present invention is for the separation of the hydrogen of gained after catalytic methane vapor reforming hydrogen production and catalytic methane vapor reforming hydrogen production, the methyl hydride catalyzed conversion ratio of final nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane is 100%, and nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane is to the separation (H of the hydrogen of gained after catalytic methane vapor reforming hydrogen production
2/ CH
4) be 996 ~ 1002, the saturating hydrogen rate of nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane is 7.52 ~ 8.02 × 10
-6molm
-2s
-1pa
-1.
A kind of nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane of the present invention is used for the separation of hydrogen in gaseous mixture, and final nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane is to the separation (H of hydrogen in gaseous mixture
2/ CH
4) be 1000 ~ 1008.
Accompanying drawing explanation
Fig. 1, porous through hole anodic alumina films are pasted onto the schematic diagram on negative electrode.
Detailed description of the invention
Also by reference to the accompanying drawings the present invention is set forth further below by specific embodiment, but do not limit the present invention.
embodiment 1
A preparation method for nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane, specifically comprises the steps:
(1), 90mm × 60mm × 250 μm porous through hole anodic alumina films is put into the beaker of 500mL, add in 420mL pure water, use Ultrasonic Cleaning 30min, take out porous through hole anodic alumina films, dry 0.5h in 100 DEG C of baking ovens, calcination 5h in 800 DEG C of high temperature furnaces, takes out porous through hole anodic alumina films and is chilled to room temperature;
(2), with adhesive tape, the porous through hole anodic alumina films to be plated after above-mentioned process is pasted onto on the sheet nickel of 150mm × 60mm × 2mm, adhesive tape is pasted at the reverse side of this sheet nickel, specifically as shown in Figure 1, namely first porous through hole anodic alumina films to be plated for above-mentioned process is placed on the sheet nickel of 150mm × 60mm × 2mm and one end of negative electrode, then with adhesive tape, porous through hole anodic alumina films to be plated for above-mentioned process is fixed on this sheet nickel, pastes adhesive tape at the reverse side of this sheet nickel;
(3), take 0.5864g lanthana in 50mL small beaker, under agitation add the hydrochloric acid that 5mL mass concentration is 37%, heating, makes it dissolve, and after its cooling, move in the volumetric flask of 25mL, be diluted with water to scale, in this solution, la concn is 20g/L;
(4), in the beaker of 2L, 10g nickel nitrate, 10g copper sulphate, 5g formic acid, 10g sodium chloride is added, add the water-soluble solution of 975mL, add the solution 2.0mL that above-mentioned la concn is 20g/L, form nickel nitrate-copper sulphate-formic acid-sodium chloride-lanthanum chloride mixed liquor, be 2 by sodium hydroxide solution adjust ph, move in 1L volumetric flask, be diluted with water to scale, obtained electroplate liquid;
(5), above-mentioned electroplate liquid is proceeded in the beaker of 2L, the above-mentioned sheet nickel being pasted with the 150mm × 60mm × 2mm of porous through hole anodic alumina films being put into electroplate liquid is also negative electrode, anode is the electrolytic copper plate of 150mm × 100mm × 2mm, magnetic agitation, speed of agitator is 100rpm, and current density is 1.5A/dm
2, bath pH values is 2, and temperature is 5 DEG C, and plating time is 14min;
(6), take out plating piece, rinse with water clean, air-dry, peel off adhesive tape, nickel-copper-lanthanum-alundum (Al2O3) catalytic separation composite membrane is separated with negative electrode, obtain nickel-copper-lanthanum-alundum (Al2O3) catalytic separation composite membrane.
Nickel-copper-lanthanum the film thickness recording compact structure with German Fisher XMDVM-T7.1-W calibrator is 0.1 μm.
Measure with the nickel-copper-lanthanum-alundum (Al2O3) catalytic separation composite membrane of German Brooker AXS Co., Ltd APEX2 model electron spectrometer to above-mentioned gained, result shows, nickel, copper and lanthanum ratio in mass ratio in nickel-copper-lanthanum-alundum (Al2O3) catalysis composite membrane, i.e. nickel: copper: lanthanum is 1:0.9:0.001.
Nickel-copper-lanthanum-alundum (Al2O3) catalytic separation the composite membrane of above-mentioned gained is used for the separation of gained hydrogen after catalytic methane vapor reforming hydrogen production and catalytic methane vapor reforming hydrogen production
H in methane vapor
2o:CH
4: N
2for 3:1:2.8(volume ratio), flow is 13.820Lg
-1h
-1temperature is under 550 DEG C of conditions, the methyl hydride catalyzed conversion ratio of final nickel-copper-lanthanum-alundum (Al2O3) catalytic separation composite membrane is 100%, and nickel-copper-lanthanum-alundum (Al2O3) catalytic separation composite membrane is to the separation (H of the hydrogen of gained after catalytic methane vapor reforming hydrogen production
2/ CH
4) be 1002, the saturating hydrogen rate of nickel-copper-lanthanum-alundum (Al2O3) catalytic separation composite membrane is 7.52 × 10
-6molm
-2s
-1pa
-1.
Nickel-copper-lanthanum-alundum (Al2O3) catalytic separation the composite membrane of above-mentioned gained is used for the separation of hydrogen in methane mixed gas
H in methane mixed gas
2: CH
4: N
2for 4:1:2.8(volume ratio), flow is 13.820Lg
-1h
-1, temperature is under 25 DEG C of conditions, and final nickel-copper-lanthanum-alundum (Al2O3) catalytic separation composite membrane is to the separation (H of hydrogen in gaseous mixture
2/ CH
4) be 1000.
embodiment 2
A preparation method for nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane, specifically comprises the steps:
(1), 90mm × 60mm × 250 μm porous through hole anodic alumina films is put into the beaker of 500mL, add in 420mL pure water, use Ultrasonic Cleaning 5min, take out porous through hole anodic alumina films, dry 5h in 50 DEG C of baking ovens, calcination 0.5h in 1100 DEG C of high temperature furnaces, takes out porous through hole anodic alumina films and is chilled to room temperature;
(2), with two-sided tape, the porous through hole anodic alumina films to be plated after above-mentioned process is pasted onto in the electrolytic copper plate of 150mm × 60mm × 2mm, pastes adhesive tape, specifically with embodiment 1 at the reverse side of this electrolytic copper plate;
(3), take 5.7631g gadolinium oxide in 100mL small beaker, under agitation add 30mL red fuming nitric acid (RFNA), heating, makes it dissolve, and after its cooling, move in the volumetric flask of 100mL, be diluted with water to scale, in this solution, gadolinium concentration is 50g/L;
Take 5.8320g neodymia in 100mL small beaker, under agitation add 30mL red fuming nitric acid (RFNA), heating, makes it dissolve, and after its cooling, move in the volumetric flask of 100mL, be diluted with water to scale, in this solution, neodymium concentration is 50g/L;
(4), in the beaker of 2L, 400g nickel chloride, 250g copper chloride, 50g acetic acid, 50g citric acid, 300g potassium chloride is added, add the water-soluble solution of 785mL, add the solution 100mL that solution 100mL that above-mentioned gadolinium concentration is 50g/L and above-mentioned neodymium concentration are 50g/L, form nickel chloride-copper chloride-acetic acid-citric acid-potassium chloride-gadolinium nitrate-neodymium nitrate mixed liquor, be 4 by sodium hydroxide solution adjust ph, move in 1L volumetric flask, be diluted with water to scale, obtained electroplate liquid;
(5), above-mentioned electroplate liquid is proceeded in the beaker of 2L, the above-mentioned electrolytic copper plate being pasted with the 150mm × 60mm × 2mm of porous through hole anodic alumina films being put into electroplate liquid is also negative electrode, anode is the electrolytic copper plate of 150mm × 100mm × 2mm, magnetic agitation, speed of agitator is 600rpm, and current density is 15A/dm
2, bath pH values is 4, and temperature is 50 DEG C, and plating time is 30min;
(6), take out plating piece, rinse with water clean, air-dry, peel off adhesive tape, nickel-copper-gadolinium-neodymium-alundum (Al2O3) catalytic separation composite membrane is separated with negative electrode, obtain nickel-copper-gadolinium-neodymium-alundum (Al2O3) catalytic separation composite membrane.
Nickel-copper-gadolinium-neodymium the film thickness recording compact structure with German Fisher XMDVM-T7.1-W calibrator is 0.5 μm.
Measure with the nickel-copper-gadolinium-neodymium-alundum (Al2O3) catalytic separation composite membrane of German Brooker AXS Co., Ltd APEX2 model electron spectrometer to above-mentioned gained, result shows, nickel, copper, gadolinium and neodymium ratio in mass ratio in nickel-copper-gadolinium-neodymium-alundum (Al2O3) catalysis composite membrane, i.e. nickel: copper: gadolinium: neodymium is 1:0.6:0.22:0.18.
Nickel-copper-gadolinium-neodymium-alundum (Al2O3) catalytic separation the composite membrane of above-mentioned gained is used for the separation of the hydrogen of gained after catalytic methane vapor reforming hydrogen production and catalytic methane vapor reforming hydrogen production
H in methane vapor
2o:CH
4: N
2for 3:1:2.8(volume ratio), flow is 13.820Lg
-1h
-1temperature is under 1000 DEG C of conditions, the methyl hydride catalyzed conversion ratio of nickel-copper-gadolinium-neodymium-alundum (Al2O3) catalytic separation composite membrane is 100%, and nickel-copper-gadolinium-neodymium-alundum (Al2O3) catalytic separation composite membrane is to the separation (H of the hydrogen of gained after catalytic methane vapor reforming hydrogen production
2/ CH
4) be 996, the saturating hydrogen rate of nickel-copper-gadolinium-neodymium-alundum (Al2O3) catalytic separation composite membrane is 8.02 × 10
-6molm
-2s
-1pa
-1.
Nickel-copper-gadolinium-neodymium-alundum (Al2O3) catalytic separation the composite membrane of above-mentioned gained is used for the separation of hydrogen in methane mixed gas
H in methane mixed gas
2: CH
4: N
2for 4:1:2.8(volume ratio), flow is 13.820Lg
-1h
-1, temperature is under 400 DEG C of conditions, and final nickel-copper-gadolinium-neodymium-alundum (Al2O3) catalytic separation composite membrane is to the separation (H of hydrogen in gaseous mixture
2/ CH
4) be 1005.
embodiment 3
A preparation method for nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane, specifically comprises the steps:
(1), 90mm × 60mm × 250 μm porous through hole anodic alumina films is put into the beaker of 500mL, add in 420mL pure water, use Ultrasonic Cleaning 17min, take out porous through hole anodic alumina films, dry 2h in 85 DEG C of baking ovens, calcination 3h in 900 DEG C of high temperature furnaces, takes out porous through hole anodic alumina films and is chilled to room temperature;
(2), with adhesive tape, the porous through hole anodic alumina films to be plated after above-mentioned process is pasted onto on the steel plate of 150mm × 60mm × 2mm, pastes adhesive tape, specifically with embodiment 1 at the reverse side of this steel plate;
(3), take 0.5852g praseodymium oxide in 100mL small beaker, under agitation add 15mL red fuming nitric acid (RFNA), heating, makes it dissolve, and after its cooling, move in the volumetric flask of 50mL, be diluted with water to scale, in this solution, praseodymium concentration is 10g/L;
(4), in the beaker of 2L, 100g nickelous sulfate, 100g nickel nitrate, 40g copper nitrate, 25g tartaric acid, 25g glycolic acid, 80g ammonium chloride, 70g sodium chloride is added, add the water-soluble solution of 965mL, add the solution 4mL that above-mentioned praseodymium concentration is 10g/L, form nickelous sulfate-nickel nitrate-copper nitrate-tartaric acid-glycolic acid-ammonium chloride-sodium chloride-praseodymium nitrate mixed liquor, be 3 by sodium hydroxide solution adjust ph, move in 1L volumetric flask, be diluted with water to scale, obtained electroplate liquid;
(5), above-mentioned electroplate liquid is proceeded in the beaker of 2L, the above-mentioned steel plate being pasted with the 150mm × 60mm × 2mm of porous through hole anodic alumina films being put into electroplate liquid is also negative electrode, anode is the electrolytic copper plate of 150mm × 100mm × 2mm, magnetic agitation, speed of agitator is 300rpm, and current density is 10A/dm
2, bath pH values is 3, and temperature is 25 DEG C, and plating time is 20min;
(6), take out plating piece, rinse with water clean, air-dry, peel off adhesive tape, nickel-copper-praseodymium-alundum (Al2O3) catalytic separation composite membrane is separated with negative electrode, obtain nickel-copper-praseodymium-alundum (Al2O3) catalytic separation composite membrane.
Nickel-copper-praseodymium the film thickness recording compact structure with German Fisher XMDVM-T7.1-W calibrator is 0.35 μm.
Measure with the nickel-copper-praseodymium-alundum (Al2O3) catalytic separation composite membrane of German Brooker AXS Co., Ltd APEX2 model electron spectrometer to above-mentioned gained, result shows, nickel, copper and praseodymium ratio in mass ratio in nickel-copper-praseodymium-alundum (Al2O3) catalysis composite membrane, i.e. nickel: copper: praseodymium is 1:0.2:0.001.
Nickel-copper-praseodymium-alundum (Al2O3) catalytic separation the composite membrane of above-mentioned gained is used for the separation of the hydrogen of gained after catalytic methane vapor reforming hydrogen production and catalytic methane vapor reforming hydrogen production
H in methane vapor
2o:CH
4: N
2for 3:1:2.8(volume ratio), flow is 13.820Lg
-1h
-1temperature is under 600 DEG C of conditions, the methyl hydride catalyzed conversion ratio of final nickel-copper-praseodymium-alundum (Al2O3) catalytic separation composite membrane is 100%, and nickel-copper-praseodymium-alundum (Al2O3) catalytic separation composite membrane is to the separation (H of the hydrogen of gained after catalytic methane vapor reforming hydrogen production
2/ CH
4) be 996, the saturating hydrogen rate of nickel-copper-praseodymium-alundum (Al2O3) catalytic separation composite membrane is 7.52 × 10
-6molm
-2s
-1pa
-1.
Nickel-copper-praseodymium-alundum (Al2O3) catalytic separation the composite membrane of above-mentioned gained is used for the separation of hydrogen in methane mixed gas
H in methane mixed gas
2: CH
4: N
2for 4:1:2.8(volume ratio), flow is 13.820Lg
-1h
-1, temperature is under 200 DEG C of conditions, and final nickel-copper-praseodymium-alundum (Al2O3) catalytic separation composite membrane is to the separation (H of hydrogen in gaseous mixture
2/ CH
4) be 1000.
embodiment 4
A preparation method for nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane, specifically comprises the steps:
(1), 90mm × 60mm × 250 μm porous through hole anodic alumina films is put into the beaker of 500mL, add in 420mL pure water, use Ultrasonic Cleaning 15min, take out porous through hole anodic alumina films, dry 1.5h in 90 DEG C of baking ovens, calcination 4h in 880 DEG C of high temperature furnaces, takes out porous through hole anodic alumina films and is chilled to room temperature;
(2), with adhesive tape, the porous through hole anodic alumina films to be plated after above-mentioned process is pasted onto on the sheet nickel of 150mm × 60mm × 2mm, pastes adhesive tape, specifically with embodiment 1 at the reverse side of this sheet nickel;
(3), get 11.4351g erbium oxide in 200mL small beaker, under agitation add the hydrochloric acid that 60mL mass concentration is 37%, heating, makes it dissolve, and after its cooling, move in the volumetric flask of 250mL, be diluted with water to scale, in this solution, erbium concentration is 40g/L;
(4), in the beaker of 2L, 150g nickel nitrate, 200g copper sulphate, 40g formic acid, 30g ammonium chloride is added, add the water-soluble solution of 725mL, add the solution 250mL that above-mentioned erbium concentration is 40g/L, form nickel nitrate-copper sulphate-formic acid-ammonium chloride-erbium chloride mixed liquor, be 2 by sodium hydroxide solution adjust ph, move in 1L volumetric flask, be diluted with water to scale, obtained electroplate liquid;
(5), above-mentioned electroplate liquid is proceeded in the beaker of 2L, the above-mentioned sheet nickel being pasted with the 150mm × 60mm × 2mm of porous through hole anodic alumina films being put into electroplate liquid is also negative electrode, anode is the electrolytic copper plate of 150mm × 100mm × 2mm, magnetic agitation, speed of agitator is 200rpm, and current density is 11A/dm
2, bath pH values is 3.5, and temperature is 32 DEG C, and plating time is 15min;
(6), take out plating piece, rinse with water clean, air-dry, peel off adhesive tape, nickel-copper-erbium-alundum (Al2O3) catalytic separation composite membrane is separated with negative electrode, obtain nickel-copper-erbium-alundum (Al2O3) catalytic separation composite membrane.
Nickel-copper-erbium the film thickness recording compact structure with German Fisher XMDVM-T7.1-W calibrator is 0.15 μm.
Measure with the nickel-copper-erbium-alundum (Al2O3) catalytic separation composite membrane of German Brooker AXS Co., Ltd APEX2 model electron spectrometer to above-mentioned gained, result shows, nickel, copper and erbium ratio in mass ratio in nickel-copper-erbium-alundum (Al2O3) catalysis composite membrane, i.e. nickel: copper: erbium is 1:1.3:0.4.
Nickel-copper-erbium-alundum (Al2O3) catalytic separation the composite membrane of above-mentioned gained is used for the separation of the hydrogen of gained after catalytic methane vapor reforming hydrogen production and catalytic methane vapor reforming hydrogen production
H in methane vapor
2o:CH
4: N
2for 3:1:2.8(volume ratio), flow is 13.820Lg
-1h
-1temperature is under 900 DEG C of conditions, the methyl hydride catalyzed conversion ratio of final nickel-copper-erbium-alundum (Al2O3) catalytic separation composite membrane is 100%, and nickel-copper-erbium-alundum (Al2O3) catalytic separation composite membrane is to the separation (H of the hydrogen of gained after catalytic methane vapor reforming hydrogen production
2/ CH
4) be 996, the saturating hydrogen rate of nickel-copper-erbium-alundum (Al2O3) catalytic separation composite membrane is 7.53 × 10
-6molm
-2s
-1pa
-1.
Nickel-copper-erbium-alundum (Al2O3) catalytic separation the composite membrane of above-mentioned gained is used for the separation of hydrogen in methane mixed gas
H in methane mixed gas
2: CH
4: N
2for 4:1:2.8(volume ratio), flow is 13.820Lg
-1h
-1, temperature is under 500 DEG C of conditions, and final nickel-copper-erbium-alundum (Al2O3) catalytic separation composite membrane is to the separation (H of hydrogen in gaseous mixture
2/ CH
4) be 1001.
embodiment 5
A preparation method for nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane, specifically comprises the steps:
(1), 90mm × 60mm × 250 μm porous through hole anodic alumina films is put into the beaker of 500mL, add in 420mL pure water, use Ultrasonic Cleaning 20min, take out porous through hole anodic alumina films, dry 2h in 95 DEG C of baking ovens, calcination 3.5h in 980 DEG C of high temperature furnaces, takes out porous through hole anodic alumina films and is chilled to room temperature;
(2), with adhesive tape, the porous through hole anodic alumina films to be plated after above-mentioned process is pasted onto on the steel plate of 150mm × 60mm × 2mm, pastes adhesive tape, specifically with embodiment 1 at the reverse side of this steel plate;
(3), take 2.8991g samarium oxide in 100mL small beaker, under agitation add the hydrochloric acid that 35mL mass concentration is 37%, heating, makes it dissolve, and after its cooling, move in the volumetric flask of 100mL, be diluted with water to scale, in this solution, samarium concentration is 25g/L;
(4), in the beaker of 2L, 100g nickelous sulfate, 90g copper sulphate, 35g citric acid, 100g potassium chloride is added, add the water-soluble solution of 865mL, add the solution 100mL that above-mentioned samarium concentration is 25g/L, form nickelous sulfate-copper sulphate-citric acid-potassium chloride-samarium trichloride mixed liquor, be 2.5 by sodium hydroxide solution adjust ph, move in 1L volumetric flask, be diluted with water to scale, obtained electroplate liquid;
(5), above-mentioned electroplate liquid is proceeded in the beaker of 2L, the above-mentioned steel plate being pasted with the 150mm × 60mm × 2mm of porous through hole anodic alumina films being put into electroplate liquid is also negative electrode, anode is the electrolytic copper plate of 150mm × 100mm × 2mm, magnetic agitation, speed of agitator is 350rpm, and current density is 9A/dm
2, bath pH values is 2.5, and temperature is 48 DEG C, and plating time is 22min;
(6), take out plating piece, rinse with water clean, air-dry, peel off adhesive tape, nickel-copper-samarium-alundum (Al2O3) catalytic separation composite membrane is separated with negative electrode, obtain nickel-copper-samarium-alundum (Al2O3) catalytic separation composite membrane.
Nickel-copper-samarium the film thickness recording compact structure with German Fisher XMDVM-T7.1-W calibrator is 0.39 μm.
Measure with the nickel-copper-samarium-alundum (Al2O3) catalytic separation composite membrane of German Brooker AXS Co., Ltd APEX2 model electron spectrometer to above-mentioned gained, result shows, nickel, copper and samarium ratio in mass ratio in nickel-copper-samarium-alundum (Al2O3) catalysis composite membrane, i.e. nickel: copper: samarium is 1:0.8:0.1.
Nickel-copper-samarium-alundum (Al2O3) catalytic separation the composite membrane of above-mentioned gained is used for the separation of the hydrogen of gained after catalytic methane vapor reforming hydrogen production and catalytic methane vapor reforming hydrogen production
H in methane vapor
2o:CH
4: N
2for 3:1:2.8(volume ratio), flow is 13.820Lg
-1h
-1temperature is under 800 DEG C of conditions, the methyl hydride catalyzed conversion ratio of final nickel-copper-samarium-alundum (Al2O3) catalytic separation composite membrane is 100%, and nickel-copper-samarium-alundum (Al2O3) catalytic separation composite membrane is to the separation (H of the hydrogen of gained after catalytic methane vapor reforming hydrogen production
2/ CH
4) be 997, the saturating hydrogen rate of nickel-copper-samarium-alundum (Al2O3) catalytic separation composite membrane is 7.81 × 10
-6molm
-2s
-1pa
-1.
Nickel-copper-samarium-alundum (Al2O3) catalytic separation the composite membrane of above-mentioned gained is used for the separation of hydrogen in methane mixed gas
H in methane mixed gas
2: CH
4: N
2for 4:1:2.8(volume ratio), flow is 13.820Lg
-1h
-1, temperature is under 300 DEG C of conditions, and final nickel-copper-samarium-alundum (Al2O3) catalytic separation composite membrane is to the separation (H of hydrogen in gaseous mixture
2/ CH
4) be 1007.
embodiment 6
A preparation method for nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane, specifically comprises the steps:
(1), 90mm × 60mm × 250 μm porous through hole anodic alumina films is put into the beaker of 500mL, add in 420mL pure water, use Ultrasonic Cleaning 25min, take out porous through hole anodic alumina films, dry 4h in 65 DEG C of baking ovens, calcination 2h in 1050 DEG C of high temperature furnaces, takes out porous through hole anodic alumina films and is chilled to room temperature;
(2), with two-sided tape, the porous through hole anodic alumina films to be plated after above-mentioned process is pasted onto in the electrolytic copper plate of 150mm × 60mm × 2mm, pastes adhesive tape, specifically with embodiment 1 at the reverse side of this electrolytic copper plate;
(3), take 0.8529g luteium oxide in 50mL small beaker, under agitation add 5mL red fuming nitric acid (RFNA), heating, makes it dissolve, and after its cooling, move in the volumetric flask of 50mL, be diluted with water to scale, in this solution, lutetium concentration is 15g/L;
(4), in the beaker of 2L, 50g nickel chloride, 15g copper chloride, 15g copper nitrate, 30g amion acetic acid, 150g sodium chloride is added, add the water-soluble solution of 935mL, add the solution 50mL that above-mentioned lutetium concentration is 15g/L, form nickel chloride-copper chloride-copper nitrate-amion acetic acid-sodium chloride-lutecium nitrate mixed liquor, be 2.8 by sodium hydroxide solution adjust ph, move in 1L volumetric flask, be diluted with water to scale, obtained electroplate liquid;
(5), above-mentioned electroplate liquid is proceeded in the beaker of 2L, the above-mentioned electrolytic copper plate being pasted with the 150mm × 60mm × 2mm of porous through hole anodic alumina films being put into electroplate liquid is also negative electrode, anode is the electrolytic copper plate of 150mm × 100mm × 2mm, magnetic agitation, speed of agitator is 450rpm, and current density is 8A/dm
2, bath pH values is 2.8, and temperature is 38 DEG C, and plating time is 26min;
(6), take out plating piece, rinse with water clean, air-dry, peel off adhesive tape, nickel-copper-lutetium-alundum (Al2O3) catalytic separation composite membrane is separated with negative electrode, obtain nickel-copper-lutetium-alundum (Al2O3) catalytic separation composite membrane.
Nickel-copper-lutetium the film thickness recording compact structure with German Fisher XMDVM-T7.1-W calibrator is 0.46 μm.
Measure with the nickel-copper-lutetium-alundum (Al2O3) catalytic separation composite membrane of German Brooker AXS Co., Ltd APEX2 model electron spectrometer to above-mentioned gained, result shows, nickel, copper and lutetium ratio in mass ratio in nickel-copper-lutetium-alundum (Al2O3) catalysis composite membrane, i.e. nickel: copper: lutetium is 1:0.6:0.03.
Nickel-copper-lutetium-alundum (Al2O3) catalytic separation the composite membrane of above-mentioned gained is used for the separation of the hydrogen of gained after catalytic methane vapor reforming hydrogen production and catalytic methane vapor reforming hydrogen production
H in methane vapor
2o:CH
4: N
2for 3:1:2.8(volume ratio), flow is 13.820Lg
-1h
-1temperature is under 950 DEG C of conditions, the methyl hydride catalyzed conversion ratio of final nickel-copper-lutetium-alundum (Al2O3) catalytic separation composite membrane is 100%, and nickel-copper-lutetium-alundum (Al2O3) catalytic separation composite membrane is to the separation (H of the hydrogen of gained after catalytic methane vapor reforming hydrogen production
2/ CH
4) be 996, the saturating hydrogen rate of nickel-copper-lutetium-alundum (Al2O3) catalytic separation composite membrane is 7.98 × 10
-6molm
-2s
-1pa
-1.
Nickel-copper-lutetium-alundum (Al2O3) catalytic separation the composite membrane of above-mentioned gained is used for the separation of hydrogen in methane mixed gas
H in methane mixed gas
2: CH
4: N
2for 4:1:2.8(volume ratio), flow is 13.820Lg
-1h
-1, temperature is under 450 DEG C of conditions, and final nickel-copper-lutetium-alundum (Al2O3) catalytic separation composite membrane is to the separation (H of hydrogen in gaseous mixture
2/ CH
4) be 1003.
embodiment 7
A preparation method for nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane, specifically comprises the steps:
(1), 90mm × 60mm × 250 μm porous through hole anodic alumina films is put into the beaker of 500mL, add in 420mL pure water, use Ultrasonic Cleaning 9min, take out porous through hole anodic alumina films, dry 3.5h in 70 DEG C of baking ovens, calcination 2.5h in 1000 DEG C of high temperature furnaces, takes out porous through hole anodic alumina films and is chilled to room temperature;
(2), with adhesive tape, the porous through hole anodic alumina films to be plated after above-mentioned process is pasted onto on the sheet nickel of 150mm × 60mm × 2mm, pastes adhesive tape, specifically with embodiment 1 at the reverse side of this sheet nickel;
(3), take 9.5250g yittrium oxide in 200mL small beaker, under agitation add the hydrochloric acid that 60mL mass concentration is 37%, heating, makes it dissolve, and after its cooling, move in the volumetric flask of 250mL, be diluted with water to scale, in this solution, yttrium concentration is 30g/L;
(4), in the beaker of 2L, 150g nickel nitrate, 100g nickel chloride, 60g copper nitrate, 25g glycolic acid, 200g ammonium chloride is added, add the water-soluble solution of 730mL, add the solution 250mL that above-mentioned yttrium concentration is 30g/L, form nickel nitrate-nickel chloride-copper nitrate-glycolic acid-ammonium chloride-yttrium chloride mixed liquor, be 2.2 by sodium hydroxide solution adjust ph, move in 1L volumetric flask, be diluted with water to scale, obtained electroplate liquid;
(5), above-mentioned electroplate liquid is proceeded in the beaker of 2L, the above-mentioned sheet nickel being pasted with the 150mm × 60mm × 2mm of porous through hole anodic alumina films being put into electroplate liquid is also negative electrode, anode is the electrolytic copper plate of 150mm × 100mm × 2mm, magnetic agitation, speed of agitator is 550rpm, and current density is 12A/dm
2, bath pH values is 2.2, and temperature is 48 DEG C, and plating time is 23min;
(6), take out plating piece, rinse with water clean, air-dry, peel off adhesive tape, nickel-copper-yttrium-alundum (Al2O3) catalytic separation composite membrane is separated with negative electrode, obtain nickel-copper-yttrium-alundum (Al2O3) catalytic separation composite membrane.
Nickel-copper-yttrium the film thickness recording compact structure with German Fisher XMDVM-T7.1-W calibrator is 0.41 μm.
Measure with the nickel-copper-yttrium-alundum (Al2O3) catalytic separation composite membrane of German Brooker AXS Co., Ltd APEX2 model electron spectrometer to above-mentioned gained, result shows, nickel, copper and yttrium ratio in mass ratio in nickel-copper-yttrium-alundum (Al2O3) catalysis composite membrane, i.e. nickel: copper: yttrium is 1:0.21:0.28.
Nickel-copper-yttrium-alundum (Al2O3) catalytic separation the composite membrane of above-mentioned gained is used for the separation of the hydrogen of gained after catalytic methane vapor reforming hydrogen production and catalytic methane vapor reforming hydrogen production
H in methane vapor
2o:CH
4: N is 3:1:2.8(volume ratio), flow is 13.820Lg
-1h
-1temperature is under 650 DEG C of conditions, the methyl hydride catalyzed conversion ratio of final nickel-copper-yttrium-alundum (Al2O3) catalytic separation composite membrane is 100%, and nickel-copper-yttrium-alundum (Al2O3) catalytic separation composite membrane is to the separation (H of the hydrogen of gained after catalytic methane vapor reforming hydrogen production
2/ CH
4) be 998, the saturating hydrogen rate of nickel-copper-yttrium-alundum (Al2O3) catalytic separation composite membrane is 7.71 × 10
-6molm
-2s
-1pa
-1.
Nickel-copper-yttrium-alundum (Al2O3) catalytic separation the composite membrane of above-mentioned gained is used for the separation of hydrogen in methane mixed gas
H in methane mixed gas
2: CH
4: N
2for 4:1:2.8(volume ratio), flow is 13.820Lg
-1h
-1, temperature is under 350 DEG C of conditions, and final nickel-copper-yttrium-alundum (Al2O3) catalytic separation composite membrane is to the separation (H of hydrogen in gaseous mixture
2/ CH
4) be 1007.
embodiment 8
A preparation method for nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane, specifically comprises the steps:
(1), 90mm × 60mm × 250 μm porous through hole anodic alumina films is put into the beaker of 500mL, add in 420mL pure water, use Ultrasonic Cleaning 10min, take out porous through hole anodic alumina films, dry 4.5h in 60 DEG C of baking ovens, calcination 4.5h in 850 DEG C of high temperature furnaces, takes out porous through hole anodic alumina films and is chilled to room temperature;
(2), with two-sided tape, the porous through hole anodic alumina films to be plated after above-mentioned process is pasted onto in the electrolytic copper plate of 150mm × 60mm × 2mm, pastes adhesive tape, specifically with embodiment 1 at the reverse side of this electrolytic copper plate;
(3), get 2.0842g europium oxide in 50mL small beaker, under agitation add 15mL red fuming nitric acid (RFNA), heating, makes it dissolve, and after its cooling, move in the volumetric flask of 100mL, be diluted with water to scale, in this solution, europium concentration is 18g/L;
(4), in the beaker of 2L, 270g nickel nitrate, 80g copper chloride, 30g formic acid, 28g lactic acid, 180g sodium chloride is added, add the water-soluble solution of 885mL, add the solution 100mL that above-mentioned europium concentration is 18g/L, form nickel nitrate-copper chloride-formic acid-lactic acid-sodium chloride-europium nitrate mixed liquor, be 3.6 by sodium hydroxide solution adjust ph, move in 1L volumetric flask, be diluted with water to scale, obtained electroplate liquid;
(5), above-mentioned electroplate liquid is proceeded in the beaker of 2L, the above-mentioned electrolytic copper plate being pasted with the 150mm × 60mm × 2mm of porous through hole anodic alumina films being put into electroplate liquid is also negative electrode, anode is the electrolytic copper plate of 150mm × 100mm × 2mm, magnetic agitation, speed of agitator is 450rpm, and current density is 3A/dm
2, bath pH values is 3.6, and temperature is 23 DEG C, and plating time is 21min;
(6), take out plating piece, rinse with water clean, air-dry, peel off adhesive tape, nickel-copper-europium-alundum (Al2O3) catalytic separation composite membrane is separated with negative electrode, obtain nickel-copper-europium-alundum (Al2O3) catalytic separation composite membrane.
Nickel-copper-europium the film thickness recording compact structure with German Fisher XMDVM-T7.1-W calibrator is 0.37 μm.
Measure with the nickel-copper-europium-alundum (Al2O3) catalytic separation composite membrane of German Brooker AXS Co., Ltd APEX2 model electron spectrometer to above-mentioned gained, result shows, nickel, copper and europium ratio in mass ratio in nickel-copper-europium-alundum (Al2O3) catalysis composite membrane, i.e. nickel: copper: europium is 1:0.25:0.08.
Nickel-copper-europium-alundum (Al2O3) catalytic separation the composite membrane of above-mentioned gained is used for the separation of the hydrogen of gained after catalytic methane vapor reforming hydrogen production and catalytic methane vapor reforming hydrogen production
H in methane vapor
2o:CH
4: N
2for 3:1:2.8(volume ratio), flow is 13.820Lg
-1h
-1temperature is the methyl hydride catalyzed conversion ratio of final nickel-copper-europium-alundum (Al2O3) catalytic separation composite membrane under 750 DEG C of conditions is 100%, and nickel-copper-europium-alundum (Al2O3) catalytic separation composite membrane is to the separation (H of the hydrogen of gained after catalytic methane vapor reforming hydrogen production
2/ CH
4) be 997, the saturating hydrogen rate of nickel-copper-europium-alundum (Al2O3) catalytic separation composite membrane is 7.86 × 10
-6molm
-2s
-1pa
-1.
Nickel-copper-europium-alundum (Al2O3) catalytic separation the composite membrane of above-mentioned gained is used for the separation of hydrogen in methane mixed gas
H in methane mixed gas
2: CH
4: N
2for 4:1:2.8(volume ratio), flow is 13.820Lg
-1h
-1, temperature is under 250 DEG C of conditions, and final nickel-copper-europium-alundum (Al2O3) catalytic separation composite membrane is to the separation (H of hydrogen in gaseous mixture
2/ CH
4) be 1008.
embodiment 9
A preparation method for nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane, specifically comprises the steps:
(1), 90mm × 60mm × 250 μm porous through hole anodic alumina films is put into the beaker of 500mL, add in 420mL pure water, use Ultrasonic Cleaning 7min, take out porous through hole anodic alumina films, dry 3h in 75 DEG C of baking ovens, calcination 1.5h in 950 DEG C of high temperature furnaces, takes out porous through hole anodic alumina films and is chilled to room temperature;
(2), with adhesive tape, the porous through hole anodic alumina films to be plated after above-mentioned process is pasted onto on the sheet nickel of 150mm × 60mm × 2mm, pastes adhesive tape, specifically with embodiment 1 at the reverse side of this sheet nickel;
(3), take 4.5907g dysprosia in 100mL small beaker, under agitation add 24mL red fuming nitric acid (RFNA), heating, makes it dissolve, and after its cooling, move in the volumetric flask of 100mL, be diluted with water to scale, in this solution, dysprosium concentration is 40g/L;
(4), in the beaker of 2L, 200g nickel nitrate, 100g copper sulphate, 40g tartaric acid, 100g sodium chloride is added, add the water-soluble solution of 915mL, add the solution 75mL that above-mentioned dysprosium concentration is 40g/L, form nickel nitrate-copper sulphate-tartaric acid-sodium chloride-dysprosium nitrate mixed liquor, be 2.5 by sodium hydroxide solution adjust ph, move in 1L volumetric flask, be diluted with water to scale, obtained electroplate liquid;
(5), above-mentioned electroplate liquid is proceeded in the beaker of 2L, the above-mentioned sheet nickel being pasted with the 150mm × 60mm × 2mm of porous through hole anodic alumina films being put into electroplate liquid is also negative electrode, anode is the sheet nickel of 150mm × 100mm × 2mm, magnetic agitation, speed of agitator is 400rpm, and current density is 5.5A/dm
2, bath pH values is 4, and temperature is 30 DEG C, and plating time is 19min;
(6), take out plating piece, rinse with water clean, air-dry, peel off adhesive tape, nickel-copper-dysprosium-alundum (Al2O3) catalytic separation composite membrane is separated with negative electrode, obtain nickel-copper-dysprosium-alundum (Al2O3) catalytic separation composite membrane.
Nickel-copper-dysprosium the film thickness recording compact structure with German Fisher XMDVM-T7.1-W calibrator is 0.32 μm.
Measure with the nickel-copper-dysprosium-alundum (Al2O3) catalytic separation composite membrane of German Brooker AXS Co., Ltd APEX2 model electron spectrometer to above-mentioned gained, result shows, nickel, copper and dysprosium ratio in mass ratio in nickel-copper-dysprosium-alundum (Al2O3) catalysis composite membrane, i.e. nickel: copper: dysprosium is 1:0.5:0.19.
Nickel-copper-dysprosium-alundum (Al2O3) catalytic separation the composite membrane of above-mentioned gained is used for the separation of the hydrogen of gained after catalytic methane vapor reforming hydrogen production and catalytic methane vapor reforming hydrogen production
H in methane vapor
2o:CH
4: N
2for 3:1:2.8(volume ratio), flow is 13.820Lg
-1h
-1temperature is under 700 DEG C of conditions, the methyl hydride catalyzed conversion ratio of final nickel-copper-dysprosium-alundum (Al2O3) catalytic separation composite membrane is 100%, and nickel-copper-dysprosium-alundum (Al2O3) catalytic separation composite membrane is to the separation (H of the hydrogen of gained after catalytic methane vapor reforming hydrogen production
2/ CH
4) be 997, the saturating hydrogen rate of nickel-copper-dysprosium-alundum (Al2O3) catalytic separation composite membrane is 7.82 × 10
-6molm
-2s
-1pa
-1.
Nickel-copper-dysprosium-alundum (Al2O3) catalytic separation the composite membrane of above-mentioned gained is used for the separation of hydrogen in methane mixed gas
H in methane mixed gas
2: CH
4: N
2for 4:1:2.8(volume ratio), flow is 13.820Lg
-1h
-1, temperature is under 100 DEG C of conditions, and final nickel-copper-dysprosium-alundum (Al2O3) catalytic separation composite membrane is to the separation (H of hydrogen in gaseous mixture
2/ CH
4) be 1006.
embodiment 10 (comparative example of embodiment 9)
A preparation method for nickel-copper-alundum (Al2O3) catalytic separation composite membrane, specifically comprises the steps:
(1), 90mm × 60mm × 250 μm porous through hole anodic alumina films is put into the beaker of 500mL, add in 420mL pure water, use Ultrasonic Cleaning 7min, take out porous through hole anodic alumina films, dry 3h in 75 DEG C of baking ovens, calcination 1.5h in 950 DEG C of high temperature furnaces, takes out porous through hole anodic alumina films and is chilled to room temperature;
(2), with adhesive tape, the porous through hole anodic alumina films to be plated after above-mentioned process is pasted onto on the sheet nickel of 150mm × 60mm × 2mm, pastes adhesive tape, specifically with embodiment 1 at the reverse side of this sheet nickel;
(3), in the beaker of 2L, 200g nickel nitrate, 100g copper sulphate, 40g tartaric acid, 100g sodium chloride is added, add the water-soluble solution of 985mL, form copper sulphate-nickel nitrate-tartaric acid-sodium chloride mixed liquor, be 2.5 by sodium hydroxide solution adjust ph, move in 1L volumetric flask, be diluted with water to scale, obtained electroplate liquid;
(4), above-mentioned electroplate liquid is proceeded in the beaker of 2L, the above-mentioned sheet nickel being pasted with the 150mm × 60mm × 2mm of porous through hole anodic alumina films being put into electroplate liquid is also negative electrode, anode is the sheet nickel of 150mm × 100mm × 2mm, magnetic agitation, speed of agitator is 400rpm, and current density is 5.5A/dm
2, bath pH values is 4, and temperature is 30 DEG C, and plating time is 19min;
(5), take out plating piece, rinse with water clean, air-dry, peel off adhesive tape, nickel-copper-alundum (Al2O3) catalytic separation composite membrane is separated with negative electrode, obtain nickel-copper-alundum (Al2O3) catalytic separation composite membrane.
It is 0.31 μm with nickel-copper film thickness that German Fisher XMDVM-T7.1-W calibrator records compact structure.
Measure with the nickel-copper-dysprosium-alundum (Al2O3) catalytic separation composite membrane of German Brooker AXS Co., Ltd APEX2 model electron spectrometer to above-mentioned gained, result shows, nickel and copper ratio in mass ratio in nickel-copper-alundum (Al2O3) catalysis composite membrane, i.e. nickel: copper is 1:0.48.
Nickel-the copper of above-mentioned gained-alundum (Al2O3) catalytic separation composite membrane is used for the separation of the hydrogen of gained after catalytic methane vapor reforming hydrogen production and catalytic methane vapor reforming hydrogen production
H in methane vapor
2o:CH
4: N
2for 3:1:2.8(volume ratio), flow is 13.820Lg
-1h
-1, temperature is under 700 DEG C of conditions, and the methyl hydride catalyzed conversion ratio of final nickel-copper-alundum (Al2O3) catalytic separation composite membrane is 100%, and nickel-copper-alundum (Al2O3) catalytic separation composite membrane is to the separation (H of the hydrogen of gained after catalytic methane vapor reforming hydrogen production
2/ CH
4) be 889, the saturating hydrogen rate of nickel-copper-alundum (Al2O3) catalytic separation composite membrane is 5.62 × 10
-6molm
-2s
-1pa
-1.
Nickel-the copper of above-mentioned gained-alundum (Al2O3) catalytic separation composite membrane is used for the separation of hydrogen in methane mixed gas
H in methane mixed gas
2: CH
4: N
2for 4:1:2.8(volume ratio), flow is 13.820Lg
-1h
-1, temperature is under 100 DEG C of conditions, and final nickel-copper-dysprosium-alundum (Al2O3) catalytic separation composite membrane is to the separation (H of hydrogen in gaseous mixture
2/ CH
4) be 895.
By the contrast of embodiment 10 with embodiment 9, can find out that nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane prepared by the present invention is all significantly improved for separation, thoroughly the hydrogen rate of Hydrogen Separation in the hydrogen of gained after catalytic methane vapor reforming hydrogen production and gaseous mixture, wherein after catalytic methane vapor reforming hydrogen production, the separation of the hydrogen of gained improves 12.15%, in gaseous mixture, the separation of the separation of hydrogen improves 12.4%, and saturating hydrogen rate improves 39.14%.
The above is only the citing of embodiments of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvement and modification, these improve and modification also should be considered as protection scope of the present invention.
Claims (2)
1. the preparation method of nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane, adopt galvanoplastic at the plated surface last layer nickel-copper-rare earth film of porous through hole anodic alumina films, and be attached to the compact structure of nickel-copper-rare earth film that this one side on negative electrode plates in preparation process, thickness is 0.1 ~ 0.5 μm, final formation one surface is Donna metre hole, and another surface is fine and close nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane; In described nickel-copper-rare earth film, calculate in mass ratio, i.e. nickel: copper: rare earth is 1:0.2 ~ 1.3:0.001 ~ 0.4, it is characterized in that specifically comprising the steps:
(1), by porous through hole anodic alumina films pure water is put into, with Ultrasonic Cleaning, dry, calcination;
(2), with adhesive tape, the porous through hole anodic alumina films to be plated after above-mentioned process is pasted onto on negative electrode, pastes adhesive tape at the reverse side of negative electrode;
Described adhesive tape is adhesive tape or two-sided tape;
Described negative electrode is nickel plate, copper coin or steel plate;
(3), by rare earth oxide be dissolved in acid, be mixed with rare earths salt;
Its middle rare earth is the mixture of one or more the rare earth oxide in lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, scandium rare earth oxide;
Described acid is nitric acid or hydrochloric acid;
Described rare-earth salts is the mixture of rare earth nitrades, rare earth-iron-boron or rare earth nitrades and rare earth-iron-boron, and the concentration of rare earths salt rare earth elements is 10 ~ 50g/L;
(4), with water-soluble solution nickel salt, mantoquita, complexing agent, chloride, adding above-mentioned rare earths salt, is 2 ~ 4 by sodium hydroxide solution adjust ph, makes mantoquita-nickel salt-complexing agent-chloride-rare-earth salts electroplate liquid;
In described mantoquita-nickel salt-complexing agent-chloride-rare-earth salts electroplate liquid, the concentration of nickel salt, mantoquita, complexing agent, chloride, rare-earth salts is respectively 10 ~ 400g/L, 10 ~ 250g/L, 5 ~ 100g/L, 10 ~ 300g/L, 0.04 ~ 10g/L;
Described nickel salt is the mixture of one or more compositions in nickel nitrate, nickel chloride, nickelous sulfate;
Described mantoquita is the mixture of one or more compositions in copper sulphate, copper chloride, copper nitrate;
Described complexing agent is the mixture of one or more compositions in formic acid, acetic acid, citric acid, tartaric acid, lactic acid, amion acetic acid, glycolic acid;
Described chloride is the mixture of one or more compositions in sodium chloride, potassium chloride, ammonium chloride;
(5), plating piece to be plated is put into electroplate liquid to electroplate;
Electroplating technique condition is current density is 1 ~ 15A/dm
2, bath pH values is 2 ~ 4, and temperature is 5 ~ 50 DEG C, and speed of agitator is 100 ~ 600rpm, and plating time is 14 ~ 30min, and anode is copper coin;
(6), take out plating piece, rinse with water clean, air-dry, peel off adhesive tape, nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane is separated with negative electrode, obtain nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane.
2. the preparation method of a kind of nickel-copper-rare earth-alundum (Al2O3) catalytic separation composite membrane as claimed in claim 1, is characterized in that the ultrasonic treatment time described in step (1) is 5 ~ 30min; Baking temperature is 50 ~ 100 DEG C, drying time 0.5 ~ 5h; Calcination temperature is 800 ~ 1100 DEG C, calcination time 0.5 ~ 5h.
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| US20070256562A1 (en) * | 2006-05-07 | 2007-11-08 | Synkera Technologies, Inc. | Composite membranes and methods for making same |
| CN102247849A (en) * | 2011-05-24 | 2011-11-23 | 上海应用技术学院 | Alumina-nickel catalytic composite membrane and preparation method and application thereof |
| CN102247858A (en) * | 2011-05-24 | 2011-11-23 | 上海应用技术学院 | Aluminium oxide-nickel-rare earth catalytic composite membrane as well as preparation method and application thereof |
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| US20070256562A1 (en) * | 2006-05-07 | 2007-11-08 | Synkera Technologies, Inc. | Composite membranes and methods for making same |
| CN102247849A (en) * | 2011-05-24 | 2011-11-23 | 上海应用技术学院 | Alumina-nickel catalytic composite membrane and preparation method and application thereof |
| CN102247858A (en) * | 2011-05-24 | 2011-11-23 | 上海应用技术学院 | Aluminium oxide-nickel-rare earth catalytic composite membrane as well as preparation method and application thereof |
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