CN1586718A - Nano carbon material modified copper base catalyst and its preparing method - Google Patents
Nano carbon material modified copper base catalyst and its preparing method Download PDFInfo
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- CN1586718A CN1586718A CNA2004100532531A CN200410053253A CN1586718A CN 1586718 A CN1586718 A CN 1586718A CN A2004100532531 A CNA2004100532531 A CN A2004100532531A CN 200410053253 A CN200410053253 A CN 200410053253A CN 1586718 A CN1586718 A CN 1586718A
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Abstract
The present invention belongs to the field of chemical technology, and especially one kind of copper base catalyst with nanometer carbon material as co-catalyst for vapor reformation of methanol to prepare hydrogen and its preparation process. The catalyst is prepared through the process including the steps of: compounding 0.1 M solution of Cu/Zn/Al nitrate; compounding 0.1 M solution of sodium carbonate, dropping the 0.1 M solution of Cu/Zn/Al nitrate and 0.1 M solution of sodium carbonate in the same rate into reactor with nanometer carbon material for co-precipitation under strong stirring and 60 deg.c to obtain carbonate coprecipitate containing nanometer carbon material; washing, drying, roasting, etc. The prepared catalyst has unique porous structure of great specific surface area, high low temperature activity and high hydrogen selectivity, and may be used in preparing reformed product with hydrogen content up to 75 % and CO content lower than 0.1 %.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of copper-based catalysts of nano-carbon material modification, this catalyzer is applied to hydrogen production from methanol-steam reforming.
Technical background
Methyl alcohol is as liquid fuel, because of having high-energy-density, low carbon content, and advantages such as transportation and storage become that most promising height takes can fuel, immediately produce hydrogen by catalyzed conversion, can effectively solve Hydrogen Energy utilize in existing various problems, become the ideal hydrogen carrier, be the focus of research at present with the hydrogen source of its battery that acts as a fuel.The act as a fuel hydrogen source of battery is to H in the hydrogen-producing speed of hydrogen production from methanol-steam reforming reaction and the reformed gas
2With CO content certain requirement is arranged all, especially more harsh to the CO content requirement, because of easily causing fuel battery anode catalyst, CO poisons.By copper-based catalysts catalysis methanol vapor reforming hydrogen production is the potential approach that effectively solves hydrogen manufacturing demands such as on-vehicle fuel.But the traditional copper radical synthesizing methanol catalyst is all undesirable to low temperature active, hydrogen manufacturing selectivity and the catalytic stability of this reaction, thereby the development novel carbinol vapor reforming hydrogen production catalyzer that has high reactivity, high hydrogen selectivity and stability concurrently has become the hydrogen manufacturing system and further moves towards the important subject that practicability faces.
At present, the research for application and development of novel copper-based catalyst for preparing hydrogen by reforming methanol and water vapour is very extensive and deep.It is reported that preparation method and condition play crucial influence [J.Mol.Catal.A:Chem., 1997,124 (1): 123 to the structure and the catalytic performance of copper-based catalysts; J.Power Sources, 1999,84 (2): 187; Appl.Catal.A, 1999,179 (1): 21.].The copper-based catalysts preparation method of bibliographical information has method [Catal.Today, 2002,77 (1): 89 such as pickling process, template and co-precipitation; Int.J.Hydrogen Energy[J], 2000,25 (2): 211; Appl.Catal.A[J], 2000,194 (1): 21.].It is generally acknowledged the CuO/ZnO/Al that adopts coprecipitation method to prepare
2O
3Catalyzer has hydrogen production from methanol-steam reforming activity and hydrogen selectivity preferably.But the CuO/ZnO/Al that adopts this method to prepare
2O
3Catalyzer will just can reach higher methanol conversion usually under ℃ condition of temperature＞280, obviously can not satisfy the actual hydrogen manufacturing demand of on-vehicle fuel etc.Recently, having report to adopt the oxide compound of transition metals such as Mn, Cr, Zr is cocatalyst, makes the CuO/ZnO/Al of oxide compound remodeling
2O
3Catalyzer can be implemented under the condition about 250 ℃, the methanol conversion more than 95%, but the content of carbon monoxide is still higher in the reformed gas that such catalyzer obtains.Thereby further seek stable performance, low temperature high activity, the higher catalyzer of hydrogen selectivity and become the focus [J.Mol.Catal.A, 2003,194 (1): 99.] that numerous investigators pay close attention to.Nano-carbon material such as activated carbon fiber, carbon nanotube etc. remove its high mechanical strength, outside the unreactiveness, the nanotube walls structure of the class graphite of the uniqueness that it possessed, and the absorption property of high-ratio surface and excellence has caused extensive concern in recent years as the potential new catalytic material.
Summary of the invention
The objective of the invention is to propose modification copper-based catalysts of a kind of low-temperature catalyzed high reactivity, stable performance, nano-carbon material that the hydrogen selectivity is high and preparation method thereof.
The catalyzer that is used for hydrogen production from methanol-steam reforming that the present invention proposes is by CuO/ZnO/Al
2O
3Active ingredient and nano-carbon material combine, wherein, and CuO/ZnO/Al
2O
3The weight percentage of active ingredient is 70-99wt%, and remaining is a nano-carbon material.The weight content of nano-carbon material component between 5-15wt% for better.
The promoted copper-based catalysts of above-mentioned nano-carbon material, CuO/ZnO/Al wherein
2O
3CuO content is in the 30-70% mol ratio in the component, and ZnO content is at 20-60% mol ratio, Al
2O
3Content is in the 0-15% mol ratio.
Above-mentioned active constituent content preferably is that CuO is the 45-60% mol ratio, and ZnO is the 30-45% mol ratio, Al
2O
3Be 8～10% mol ratios.
The promoted copper-based catalysts of above-mentioned nano-carbon material, nano-carbon material wherein are activated carbon (AC, carbon content 〉=99wt%, specific surface area 800-1500m
2/ g), carbon nano fiber (NCE, carbon content 〉=99wt%, graphite-like carbon content 〉=80wt%, specific surface area 80-120m
2/ g), graphite (GR, carbon content 〉=99wt%, specific surface area 5-10m
2/ g), carbon nanotube (CNTs, external diameter 10-50nm, internal diameter 2-4nm, carbon content 〉=99wt%, graphite-like carbon content 〉=80wt.%, specific surface area 100-160m
2/ g), activated carbon fiber (ACF, carbon content 〉=99wt%, graphite-like carbon content 〉=80wt%, specific surface area 1000-2000m
2/ g) wait one or more.
The promoted copper-based catalysts of nano-carbon material that the present invention proposes can adopt traditional carbonate and flow the coprecipitation method preparation.Its concrete steps are: according to above-mentioned usage ratio, in strong mixing, room temperature--under 60 ℃ of conditions, with the aqueous solution of yellow soda ash and contain in the aqueous solution of copper, zinc and aluminium chlorate or nitrate with and stream mode join in the pre-dispersed aqueous solution that a certain amount of nano-carbon material arranged, room temperature--60 ℃ are stirred aging down; Washing, dry and roasting under particular atmosphere, granulation promptly gets this catalyzer.
Among the above-mentioned preparation method, the aqueous solution of yellow soda ash and cupric, zinc and aluminium chlorate or nitrate can once add, and also can slowly drip by certain speed.The concentration of sodium carbonate solution, chlorate or nitrate solution is between the 0.05M-0.5M, in strong mixing, room temperature--under 60 ℃ of conditions, chlorate or nitrate solution and sodium carbonate solution constant speed and drip are gone into to preset in the reactor of metering nano-carbon material to carry out coprecipitation reaction, reaction finishes the back and continues to stir 3-5 hour.Precipitated liquid is through distilled water wash, and fully making beating, filtration are dried then.Dried catalyzer is roasting under given atmosphere again, granulation.The atmosphere of roasting is generally air, oxygen, nitrogen, argon gas or hydrogen.Maturing temperature is generally 250～600 ℃, roasting time 2-10 hour.It is 60～80 purpose samples that catalyzer after the roasting is made mean particle size.
Among the present invention, the concentration of sodium carbonate solution, chlorate or nitrate solution is 0.1-0.3M.
Among the present invention, calcination atmosphere is nitrogen or argon gas.
Among the present invention, maturing temperature is 300-400 ℃.
Among the present invention, catalyzer is as the application of catalyst for steam reformation of methanol to produce hydrogen.
Can test with the following method activity of such catalysts provided by the invention: the catalyst activity evaluation is carried out in atmospheric fixed bed flowing reactive system, stainless steel reactor (300mm * Φ 10mm), temperature of reaction is controlled between 180～250 ℃, and reaction bed temperature is controlled through the program temperature controller by chromel-alumel couple.With catalyzer with putting into the reactor flat-temperature zone after the mixing of volume quartz sand, elder generation is with 5%H during activity rating
2/ Ar gas mixture feeds reactor, and the accent flow is 80mL/min, temperature programming to 250 ℃ reduction activation catalyzer 8h, then the Reaktionsofen temperature is dropped to the setting temperature of reaction, switch argon gas, transfer flow 30mL/min, argon gas stream is introduced reaction system with the mixed solution of water and methyl alcohol and is begun reaction.Be reflected at the setting temperature of reaction and stablize the analysis of 2h post-sampling, aerogenesis is earlier through the condenser cooling, and tail gas enters the GC122 on-line analysis after the six-way valve sampling, and unreacted water and methyl alcohol injection are analyzed, thermal conductivity detector (TCD) detects, and handles with the workstation control sampling process line data of going forward side by side.(Poropak-Q and TDX-01 2m) are used for separation of C H respectively to the chromatographic column of two parallel connections
3OH, higher alcohols and CO, CO
2, H
2Deng product.The catalyst low-temperature activity height of the present invention's preparation, good stability, to the hydrogen selective height, catalyst preparation process is simple, good reproducibility.Hydrogen content 50-75vol% in the reformation aerogenesis, CO are 0.08-0.3vol%, easily purifying treatment.
Description of drawings
Fig. 1 is scanning electron microscope (SEM) figure of the activated carbon fiber catalyzer among the embodiment seven.
Fig. 2 is the promoted copper-based catalysts scanning electron microscope of the activated carbon fiber among the embodiment seven (SEM) figure.
As seen can see very clearly that from above-mentioned figure activated carbon fiber is about 5 microns of diameter, be about the filamentary structure of 400-500 micron, the copper-based catalysts that contains the 12wt% activated carbon fiber then presents the vesicular structure of hypertrophy.
Embodiment
The invention will be further described with embodiment below.
Embodiment 1, at first with 7.26g Cu (NO
3)
23H
2O, 8.91g Zn (NO
3)
26H
2O, 2.50g Al (NO
3)
39H
2O (AR level) mixes after being mixed with the solution of 0.1M respectively, again with the anhydrous Na of 7.42g AR level
2CO
3Be mixed with the solution of 0.1M.Then under the strong mixing condition, nitrate solution and sodium carbonate solution and drip to be gone into to preset in the 100mL aqueous solution of 0.45g activated carbon powder (400-600 order), solution temperature is controlled at 60 ℃, and pH is 7.0-7.2.Reaction finishes the back and continues to stir 4h; use deionized water wash then; fully making beating; filter, at last in 110 ℃ of dry 12h, under nitrogen protection at 360 ℃ of roasting 4h; preparation gained catalyst oxidation attitude presoma; in the sample, Cu/Zn/Al=45/45/10 (mol ratio), activated carbon is 8wt% in the catalyst oxidation attitude presoma.
Catalyzer carries out (300mm * Φ 10mm) to the hydrogen production from methanol-steam reforming activity rating in atmospheric fixed bed continuous flow reactor system, catalyst levels is 0.5g.Earlier with 5%H
2/ Ar gas mixture feeds reactor, and the accent flow is 80mL/min, temperature programming to 250 ℃ reduction activation catalyzer 8h, then the Reaktionsofen temperature is dropped to the setting temperature of reaction, switch argon gas, transfer flow 30mL/min, argon gas stream is introduced reaction system with the mixed solution of water and methyl alcohol and is begun reaction.Be reflected at and set temperature of reaction and stablize the analysis of 2h post-sampling, aerogenesis is earlier through the condenser cooling, and tail gas enters the GC122 on-line analysis after the six-way valve sampling, and thermal conductivity detector (TCD) detects, with the line data processing of going forward side by side of workstation control sampling process.Evaluation result shows: at normal pressure, and 230 ℃ of low temperature, n (H
2O)/n (CH
3OH)=and 1.1/1.0, WHSV=3.61h
-1Reaction conditions under, methanol conversion is 79.3%, the hydrogen productive rate is 0.2357, hydrogen selective is 99.4%, CO
2Selectivity is 99.4%, and CO content is 0.14% in the reformation aerogenesis.Compare with the experimental result among the comparative example 1, activated carbon modification rear catalyst low temperature active does not improve, but the content of CO significantly reduces in the reformation aerogenesis, easily purifying treatment.
The comparative example 1
What prepare under identical experiment condition has a same composition ratio, does not contain the Cu/ZnO/Al of carbon material
2O
3On the catalyzer, the catalyst activity evaluation is with embodiment 1, at normal pressure, and 230 ℃ of low temperature, n (H
2O)/n (CH
3OH)=and 1.1/1.0, WHSV=3.61h
-1Reaction conditions under, methanol conversion is 83.1%, the hydrogen productive rate is 0.2465, hydrogen selective is 99.2%, CO
2Selectivity is 99.0%, and CO content is 0.25% in the reformation aerogenesis.
Embodiment 2
At first with 7.26g Cu (NO
3)
23H
2O, 8.91g Zn (NO
3)
26H
2O, 2.50g Al (NO
3)
39H
2O (AR level) mixes after being mixed with the solution of 0.1M respectively, again with the anhydrous Na of 7.42g AR level
2CO
3Be mixed with the solution of 0.1M.Then under the strong mixing condition, nitrate solution and sodium carbonate solution and drip to be gone into to preset in the 100mL aqueous solution of 0.45g carbon nano fiber, solution temperature is controlled at 20 ℃, and pH is 7.0-7.2.Reaction finishes the back and continues to stir 4h; use deionized water wash then; fully making beating; filter, at last in 110 ℃ of dry 12h, under nitrogen protection at 360 ℃ of roasting 4h; preparation gained catalyst oxidation attitude presoma; in the sample, Cu/Zn/Al=45/45/10 (mol ratio), carbon nano fiber is 8wt% in the catalyst oxidation attitude presoma.Catalyst activity is estimated with embodiment 1, and the result shows: at normal pressure, and 230 ℃ of low temperature, n (H
2O)/n (CH
3OH)=and 1.1/1.0, WHSV=3.61h
-1Reaction conditions under, methanol conversion is 85.9%, the hydrogen productive rate is 0.2551, hydrogen selective is 99.3%, CO
2Selectivity is 99.4%, and CO content is 0.15% in the reformation aerogenesis.With reference to contrast experiment one, the low-temperature catalyzed performance of carbon nano fiber modification rear catalyst is improved, and the content of CO also is reduced in the reformation aerogenesis.
Embodiment 3
At first with 7.26g Cu (NO
3)
23H
2O, 8.91g Zn (NO
3)
26H
2O, 2.50g Al (NO
3)
39H
2O (AR level) mixes after being mixed with the solution of 0.1M respectively, again with the anhydrous Na of 7.42g AR level
2CO
3Be mixed with the solution of 0.1M.Then under the strong mixing condition, nitrate solution and sodium carbonate solution and drip to be gone into to preset in the 100mL aqueous solution of 0.45g carbon nanotube, solution temperature is controlled at 60 ℃, and pH is 7.0-7.2.Reaction finishes the back and continues to stir 4h; use deionized water wash then; fully making beating; filter, at last in 110 ℃ of dry 12h, under nitrogen protection at 360 ℃ of roasting 4h; preparation gained catalyst oxidation attitude presoma; in the sample, Cu/Zn/Al=45/45/10 (amount of substance ratio), carbon nanotube is 8wt% in the catalyst oxidation attitude presoma.Catalyst activity is estimated with embodiment 1, and the result shows: at normal pressure, and 230 ℃ of low temperature, n (H
2O)/n (CH
3OH)=and 1.1/1.0, WHSV=3.61h
-1Reaction conditions under, methanol conversion is 93.2%, the hydrogen productive rate is 0.2784, hydrogen selective is 99.9%, CO
2Selectivity is 99.6%, and CO content is 0.11% in the reformation aerogenesis.With reference to contrast experiment one, the low-temperature catalyzed performance of carbon nano-tube modification rear catalyst is further enhanced, and the content of CO is significantly reduced in the reformation aerogenesis.
Embodiment 4
At first with 7.26g Cu (NO
3)
23H
2O, 8.91g Zn (NO
3)
26H
2O, 2.50g Al (NO
3)
39H
2O (AR level) mixes after being mixed with the solution of 0.1M respectively, again with the anhydrous Na of 7.42g AR level
2CO
3Be mixed with the solution of 0.1M.Then under the strong mixing condition, nitrate solution and sodium carbonate solution and drip to be gone into to preset in the 100mL aqueous solution of 0.45g graphite, solution temperature is controlled at 60 ℃, and pH is 7.0-7.2.Reaction finishes the back and continues to stir 4h; use deionized water wash then; fully making beating; filter, at last in 110 ℃ of dry 12h, under nitrogen protection at 360 ℃ of roasting 4h; preparation gained catalyst oxidation attitude presoma; in the sample, Cu/Zn/Al=45/45/10 (mol ratio), graphite is 8wt% in the catalyst oxidation attitude presoma.Catalyst activity is estimated with embodiment 1, and the result shows: at normal pressure, and 230 ℃ of low temperature, n (H
2O)/n (CH
3OH)=and 1.1/1.0, WHSV=3.61h
-1Reaction conditions under, methanol conversion is 95.3%, the hydrogen productive rate is 0.2835, hydrogen selective is 99.5%, CO
2Selectivity is 99.3%, and CO content is 0.17% in the reformation aerogenesis.With reference to contrast experiment one, the low-temperature catalyzed performance of graphite modified rear catalyst is significantly improved equally, and the content of CO is reduced in the reformation aerogenesis.
Embodiment 5
At first with 7.26g Cu (NO
3)
23H
2O, 8.91g Zn (NO
3)
26H
2O, 2.50g Al (NO
3)
39H
2O (AR level) mixes after being mixed with the solution of 0.1M respectively, again with the anhydrous Na of 7.42g AR level
2CO
3Be mixed with the solution of 0.1M.Then under the strong mixing condition, nitrate solution and sodium carbonate solution and drip to be gone into to preset in the 100mL aqueous solution of 0.45g activated carbon fiber, solution temperature is controlled at 60 ℃, and pH is 7.0-7.2.Reaction finishes the back and continues to stir 4h; use deionized water wash then; fully making beating; filter, at last in 110 ℃ of dry 12h, under nitrogen protection at 360 ℃ of roasting 4h; preparation gained catalyst oxidation attitude presoma; in the sample, Cu/Zn/Al=45/45/10 (mol ratio), activated carbon fiber is 8wt% in the catalyst oxidation attitude presoma.Catalyst activity is estimated with embodiment 1, and the result shows: at normal pressure, and 230 ℃ of low temperature, n (H
2O)/n (CH
3OH)=and 1.1/1.0, WHSV=3.61h
-1Reaction conditions under, methanol conversion is 97.5%, the hydrogen productive rate is 0.2912, hydrogen selective is 99.9%, CO
2Selectivity is 99.5%, and CO content is 0.12% in the reformation aerogenesis.With reference to contrast experiment one, the low-temperature catalyzed performance of activated carbon fiber modification rear catalyst is significantly improved, and the content of CO is reduced significantly in the reformation aerogenesis.
Embodiment 6
At first with 7.26g Cu (NO
3)
23H
2O, 8.91g Zn (NO
3)
26H
2O, 2.50g Al (NO
3)
39H
2O (AR level) mixes after being mixed with the solution of 0.1M respectively, again with the anhydrous Na of 7.42g AR level
2CO
3Be mixed with the solution of 0.1M.Then under the strong mixing condition, nitrate solution and sodium carbonate solution and drip to be gone into to preset in the 100mL aqueous solution of 1.13g activated carbon fiber, solution temperature is controlled at 60 ℃, and pH is 7.0-7.2.Reaction finishes the back and continues to stir 4h, use deionized water wash then, fully making beating, filter, at last in 110 ℃ of dry 12h, under air atmosphere at 360 ℃ of roasting 4h, preparation gained catalyst oxidation attitude presoma, in the sample, Cu/Zn/Al=45/45/10 (mol ratio), activated carbon fiber is 20wt% in the catalyst oxidation attitude presoma.Catalyst activity is estimated with embodiment 1, and the result shows: at normal pressure, and 230 ℃ of low temperature, n (H
2O)/n (CH
3OH)=and 1.1/1.0, WHSV=3.61h
-1Reaction conditions under, methanol conversion is 93.5%, the hydrogen productive rate is 0.2982, hydrogen selective is 99.9%, CO
2Selectivity is 99.5%, and CO content is 0.08% in the reformation aerogenesis.With reference to contrast experiment one, the low-temperature catalyzed performance of activated carbon fiber modification rear catalyst is significantly improved, and the content of CO obtains the reduction of very big degree in the reformation aerogenesis.
Embodiment 7
At first with 7.26g Cu (NO
3)
23H
2O, 8.91g Zn (NO
3)
26H
2O, 2.50g Al (NO
3)
39H
2O (AR level) mixes after being mixed with the solution of 0.1M respectively, again with the anhydrous Na of 7.42g AR level
2CO
3Be mixed with the solution of 0.1M.Then under the strong mixing condition, nitrate solution and sodium carbonate solution and drip to be gone into to preset in the 100mL aqueous solution of 0.05g activated carbon fiber, solution temperature is controlled at 60 ℃, and pH is 7.0-7.2.Reaction finishes the back and continues to stir 4h; use deionized water wash then; fully making beating; filter, at last in 110 ℃ of dry 12h, under nitrogen protection at 360 ℃ of roasting 4h; preparation gained catalyst oxidation attitude presoma; in the sample, Cu/Zn/Al=45/45/10 (mol ratio), activated carbon fiber is 2wt% in the catalyst oxidation attitude presoma.Catalyst activity is estimated with embodiment 1, and the result shows: at normal pressure, and 230 ℃ of low temperature, n (H
2O)/n (CH
3OH)=and 1.1/1.0, WHSV=3.61h
-1Reaction conditions under, methanol conversion is 90.5%, the hydrogen productive rate is 0.2782, hydrogen selective is 99.9%, CO
2Selectivity is 99.5%, and CO content is 0.12% in the reformation aerogenesis.With reference to contrast experiment one, the low-temperature catalyzed performance of activated carbon fiber modification rear catalyst is significantly improved, and the content of CO obtains the reduction of certain degree in the reformation aerogenesis.
The low-temperature catalyzed performance of the copper base catalyst for preparing hydrogen by reforming methanol and water vapour of more various carbon material modifications as can be known, except that activated carbon, the copper base catalyst for preparing hydrogen by reforming methanol and water vapour activity of carbon material modification all is improved, the content of CO obtains reducing in the aerogenesis, and especially activated carbon fiber modification copper-based catalysts shows best catalytic performance.
Embodiment 8
At first with 7.26g Cu (NO
3)
23H
2O, 8.91g Zn (NO
3)
26H
2O, 2.50g Al (NO
3)
39H
2O (AR level) mixes after being mixed with the solution of 0.1M respectively, again with the anhydrous Na of 7.42g AR level
2CO
3Be mixed with the solution of 0.1M.Then under the strong mixing condition, nitrate solution and sodium carbonate solution and drip to be gone into to preset in the 100mL aqueous solution of 0.71g activated carbon fiber, solution temperature is controlled at 60 ℃, and pH is 7.0～7.2.Reaction finishes the back and continues to stir 4h; use deionized water wash then; fully making beating; filter, at last in 110 ℃ of dry 12h, under nitrogen protection at 360 ℃ of roasting 4h; preparation gained catalyst oxidation attitude presoma; in the sample, Cu/Zn/Al=45/45/10 (mol ratio), activated carbon fiber is 12wt% in the catalyst oxidation attitude presoma.Catalyst activity is estimated with embodiment 1, and the result shows: at normal pressure, and 230 ℃ of low temperature, n (H
2O)/n (CH
3OH)=and 1.1/1.0, WHSV=3.61h
-1, GHSV=3600h
-1Reaction conditions under, methanol conversion is 94.3%, the hydrogen productive rate is 0.2816, hydrogen selective is 99.9%, CO
2Selectivity is 99.5%, and CO content is 0.14% in the reformation aerogenesis.
Embodiment 9
At first with 7.26g Cu (NO
3)
23H
2O, 8.91g Zn (NO
3)
26H
2O, 2.50g Al (NO
3)
39H
2O (AR level) mixes after being mixed with the solution of 0.1M respectively, again with the anhydrous Na of 7.42g AR level
2CO
3Be mixed with the solution of 0.1M.Then under the strong mixing condition, nitrate solution and sodium carbonate solution and drip to be gone into to preset in the 100mL aqueous solution of 1.69g activated carbon fiber, solution temperature is controlled at 60 ℃, and pH is 7.0-7.2.Reaction finishes the back and continues to stir 4h; use deionized water wash then; fully making beating; filter, at last in 110 ℃ of dry 12h, under nitrogen protection at 500 ℃ of roasting 4h; preparation gained catalyst oxidation attitude presoma; in the sample, Cu/Zn/Al=45/45/10 (mol ratio), activated carbon fiber is 30wt% in the catalyst oxidation attitude presoma.Catalyst activity is estimated with embodiment 1, and the result shows: at normal pressure, and 230 ℃ of low temperature, n (H
2O)/n (CH
3OH)=and 1.1/1.0, WHSV=3.61h
-1, GHSV=3600h
-1Reaction conditions under, methanol conversion is 90.3%, the hydrogen productive rate is 0.2886, hydrogen selective is 99.9%, CO
2Selectivity is 99.5%, and CO content is 0.10% in the reformation aerogenesis.
Embodiment 10
At first with 7.26g Cu (NO
3)
23H
2O, 8.91g Zn (NO
3)
26H
2O, 2.50g Al (NO
3)
39H
2O (AR level) mixes after being mixed with the solution of 0.1M respectively, again with the anhydrous Na of 7.42g AR level
2CO
3Be mixed with the solution of 0.1M.Then under the strong mixing condition, nitrate solution and sodium carbonate solution and drip to be gone into to preset in the 100mL aqueous solution of 0.45g activated carbon fiber and 0.26g carbon nanotube, solution temperature is controlled at 60 ℃, and pH is 7.0-7.2.Reaction finishes the back and continues to stir 4h; use deionized water wash then; fully making beating; filter, at last in 110 ℃ of dry 12h, under nitrogen protection at 400 ℃ of roasting 4h; preparation gained catalyst oxidation attitude presoma; in the sample, Cu/Zn/Al=45/45/10 (mol ratio), activated carbon fiber and carbon nanotube total amount are 12wt% in the catalyst oxidation attitude presoma.Catalyst activity is estimated with embodiment 1, and the result shows: at normal pressure, and 230 ℃ of low temperature, n (H
2O)/n (CH
3OH)=and 1.1/1.0, WHSV=3.61h
-1, GHSV=3600h
-1Reaction conditions under, methanol conversion is 98.5%, the hydrogen productive rate is 0.2988, hydrogen selective is 99.9%, CO
2Selectivity is 99.5%, and CO content is 0.07% in the reformation aerogenesis.
Claims (10)
1, a kind of copper-based catalysts of nano-carbon material modification is characterized in that by CuO/ZnO/Al
2O
3Active ingredient and nano-carbon material are formed, and wherein the nano-carbon material weight percentage is 1-30wt%, and all the other components are CuO/ZnO/Al
2O
3
2,, it is characterized in that the nano-carbon material weight percentage is 5-15wt% according to the described catalyzer of claim 1.
3, according to the described catalyzer of claim 1, it is characterized in that CuO/ZnO/Al
2O
3CuO content is the 30-70% mol ratio in the active ingredient, and ZnO content is the 20-60% mol ratio, Al
2O
3Content is the 0-15% mol ratio.
4, according to the described catalyzer of claim 3, it is characterized in that CuO content is the 45-60% mol ratio, ZnO content is the 30-45% mol ratio, Al
2O
3Content is the 8-10% mol ratio.
5,, it is characterized in that nano-carbon material is one or more in activated carbon, carbon nano fiber, graphite, carbon nanotube, the activated carbon fiber according to the described catalyzer of claim 1.
6, a kind of preparation method of copper-based catalysts of nano-carbon material modification as claimed in claim 1, it is characterized in that using and flowing the method preparation of co-precipitation, specifically be by usage ratio, in strong mixing, room temperature--under 60 ℃ of conditions, with the aqueous solution of yellow soda ash and contain the chlorate of copper, zinc and aluminium or the aqueous solution of nitrate with and stream mode join in the pre-dispersed aqueous solution that a certain amount of nano-carbon material arranged, the concentration of sodium carbonate solution, chlorate or nitrate solution is 0.05-0.5M, stirs and wears out in 3-5 hour; Washing, dry and 250-600 ℃ roasting 2-10 hour, granulation promptly gets this catalyzer.
7, according to the described Preparation of catalysts method of claim 6, the concentration that it is characterized in that sodium carbonate solution, chlorate or nitrate solution is 0.1-0.3M.
8, Preparation of catalysts method according to claim 6 is characterized in that calcination atmosphere is nitrogen or argon gas.
9, Preparation of catalysts method according to claim 6 is characterized in that maturing temperature is 300-400 ℃.
10, according to the application of claim 1 or 6 described catalyzer as catalyst for steam reformation of methanol to produce hydrogen.
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