CN1301793C - 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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- CN1301793C CN1301793C CNB2004100532531A CN200410053253A CN1301793C CN 1301793 C CN1301793 C CN 1301793C CN B2004100532531 A CNB2004100532531 A CN B2004100532531A CN 200410053253 A CN200410053253 A CN 200410053253A CN 1301793 C CN1301793 C CN 1301793C
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Abstract
The present invention belongs to the technical field of chemical engineering, and relates to a novel copper base methanol steam reformation hydrogen producing catalyst which uses nanometer carbon materials as catalyst promoters and a preparing method thereof. In the prior art, the methanol steam reformation hydrogen production adopts the traditional synthesis methanol copper base catalyst with the defects of high reacting temperature (the temperature is higher than 280 DEG C), low hydrogen contents in reforming products, low selectivity, etc. The catalyst is prepared by adopting a carbonate parallel flow coprecipitation method, namely, Cu/Zn/Al nitrates with metering components are prepared into solutions of 0.1M, and anhydrous sodium carbonates with a certain quantity are prepared into solutions of 0.1M. Under the conditions of strong stir and 60 DEG of temperature, the nitrate solutions and the sodium carbonate solutions are dripped into a reactor which is preliminarily filled with metering nanometer carbon materials in a constant speed and parallel flow way to carry out the coprecipitation reaction, carbonate coprecipitation objects comprising the nanometer carbon materials are prepared, and the present invention is prepared through washing, dryness, roasting, etc. The catalyst has the advantages of unique and large surface, developed and porous structure, low temperature, high activity, good stability, high selectivity for hydrogen, high hydrogen content of 75% in the reforming products, and low CO content below 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 catalyst 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 desirable 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 reformation 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 catalyst that has high activity, 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 infusion 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 to prepare
2O
3Catalyst has hydrogen production from methanol-steam reforming activity and hydrogen selectivity preferably.But the CuO/ZnO/Al that adopts this method to prepare
2O
3Catalyst 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 of transition metals such as Mn, Cr, Zr is cocatalyst, makes the CuO/ZnO/Al of oxide remodeling
2O
3Catalyst 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 reformation gas that such catalyst obtains.Thereby further seek stable performance, low temperature high activity, the higher catalyst of hydrogen selectivity and become the focus [J.Mol.Catal.A, 2003,194 (1): 99.] that numerous researchers pay close attention to.Nano-carbon material such as activated carbon fiber, CNT etc. remove its high mechanical properties, outside the chemical inertness, 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 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 activity, stable performance, nano-carbon material that the hydrogen selectivity is high and preparation method thereof.
The catalyst that is used for hydrogen production from methanol-steam reforming that the present invention proposes is by CuO/ZnO/Al
2O
3Active component and nano-carbon material combine, and wherein, the nano-carbon material weight percentage is 1-30wt%, CuO/ZnO/Al
2O
3The weight percentage of active component is 70-99wt%, and remaining is a nano-carbon material.The weight content of nano-carbon material component between 5-15wt% for better.
The copper-based catalysts that above-mentioned nano-carbon material promotes, CuO/ZnO/Al
2O
3The mol ratio of Cu, Zn, Al is Cu/Zn/Al=45/45/10 in the active component.
The copper-based catalysts that above-mentioned nano-carbon material promotes, nano-carbon material wherein is activated carbon (AC, phosphorus content 〉=99wt%, specific area 800-1500m
2/ g), carbon nano-fiber (NCF, phosphorus content 〉=99wt%, graphite-like carbon content 〉=80wt%, specific area 80-120m
2/ g), graphite (GR, phosphorus content 〉=99wt%, specific area 5-10m
2/ g), CNT (CNTs, external diameter 10-50nm, internal diameter 2-4nm, phosphorus content 〉=99wt%, graphite-like carbon content 〉=80wt.%, specific area 100-160m
2/ g), activated carbon fiber (ACF, phosphorus content 〉=99wt%, graphite-like carbon content 〉=80wt%, specific area 1000-2000m
2/ g) wait one or more.
The copper-based catalysts that the nano-carbon material that the present invention proposes promotes can adopt traditional carbonate and flow the coprecipitation preparation.Its concrete steps are: according to above-mentioned usage ratio, under strong mixing, room temperature-60 ℃ condition, with the aqueous solution of sodium carbonate and contain in the aqueous solution of copper, zinc and aluminium chlorate or nitrate with and the stream mode join in the pre-dispersed aqueous solution that a certain amount of nano-carbon material arranged, it is aging that room temperature-60 ℃ stirs down; Washing, dry and roasting under particular atmosphere, granulation promptly gets this catalyst.
Among the above-mentioned preparation method, the aqueous solution of sodium carbonate and cupric, zinc and aluminium chlorate or nitrate can once add, and also can slowly drip by certain speed.The concentration of sodium carbonate liquor, chlorate or nitrate solution is between the 0.05M-0.5M, under strong mixing, room temperature-60 ℃ condition, chlorate or nitrate solution and sodium carbonate liquor 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 washed through distilled water, fully making beating, filtration, oven dry then.Dried catalyst is roasting under given atmosphere again, granulation.The atmosphere of roasting is generally air, oxygen, nitrogen, argon gas or hydrogen.Sintering temperature is generally 250～600 ℃, roasting time 2-10 hour.It is 60～80 purpose samples that catalyst after the roasting is made particle mean size.
Among the present invention, the concentration of sodium carbonate liquor, chlorate or nitrate solution is 0.1-0.3M.
Among the present invention, calcination atmosphere is nitrogen or argon gas.
Among the present invention, sintering temperature is 300-400 ℃.
Among the present invention, catalyst 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), reaction temperature is controlled between 180～250 ℃, and reaction bed temperature is controlled through the program temperature controller by chromel-alumel couple.With catalyst 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 gaseous mixture feeds reactor, and the accent flow is 80mL/min, temperature programming to 250 ℃ reduction activation catalyst 8h, then the reacting furnace temperature is dropped to the setting reaction temperature, switch argon gas, transfer flow 30mL/min, argon gas stream is introduced reaction system with the mixed liquor of water and methyl alcohol and is begun reaction.Be reflected at the setting reaction temperature 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) (TCD) detects, and handles with the work station 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 alcohol 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 purified treatment.
Description of drawings
Fig. 1 is ESEM (SEM) figure of the activated carbon fiber catalyst among the embodiment seven.
Fig. 2 is copper-based catalysts ESEM (SEM) figure that the activated carbon fiber among the embodiment seven promotes.
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 loose structure of hypertrophy.
The specific 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 liquor 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; spend deionised water 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.
Catalyst carries out (300mm * Φ 10mm) to the hydrogen production from methanol-steam reforming activity rating in atmospheric fixed bed continuous flow reactor system, catalyst amount is 0.5g.Earlier with 5%H
2/ Ar gaseous mixture feeds reactor, and the accent flow is 80mL/min, temperature programming to 250 ℃ reduction activation catalyst 8h, then the reacting furnace temperature is dropped to the setting reaction temperature, switch argon gas, transfer flow 30mL/min, argon gas stream is introduced reaction system with the mixed liquor of water and methyl alcohol and is begun reaction.Be reflected at and set reaction temperature 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) (TCD) detects, with the line data processing of going forward side by side of work station 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 condition 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 purified treatment.
The comparative example 1
What prepare under identical experiment condition has a same composition ratio, does not contain the Cu/ZnO/Al of material with carbon element
2O
3On the catalyst, the catalyst activity evaluation is with embodiment 1, at normal pressure, and 230 ℃ of low temperature, n (H
2O)/n (CH
3OH)=1.1/10, WHSV=3.61h
-1Reaction condition 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 liquor and drip to be gone into to preset in the 100mL aqueous solution of rice carbon fiber in the 0.45g, solution temperature is controlled at 20 ℃, and pH is 7.0-7.2.Reaction finishes the back and continues to stir 4h; spend deionised water 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 condition 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 liquor and drip to be gone into to preset in the 100mL aqueous solution of 0.45g CNT, solution temperature is controlled at 60 ℃, and pH is 7.0-7.2.Reaction finishes the back and continues to stir 4h; spend deionised water 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), CNT 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 condition 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 7.42gAR level
2CO
3Be mixed with the solution of 0.1M.Then under the strong mixing condition, nitrate solution and sodium carbonate liquor 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; spend deionised water 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 condition 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 7.42gAR level
2CO
3Be mixed with the solution of 0.1M.Then under the strong mixing condition, nitrate solution and sodium carbonate liquor 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; spend deionised water 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 condition 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 liquor 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, spend deionised water 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 condition 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 liquor 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; spend deionised water 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 condition 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 material with carbon element modifications as can be known, except that activated carbon, the copper base catalyst for preparing hydrogen by reforming methanol and water vapour activity of material with carbon element 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 7.42gAR level
2CO
3Be mixed with the solution of 0.1M.Then under the strong mixing condition, nitrate solution and sodium carbonate liquor 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; spend deionised water 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 condition 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 7.42gAR level
2CO
3Be mixed with the solution of 0.1M.Then under the strong mixing condition, nitrate solution and sodium carbonate liquor 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; spend deionised water 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 condition 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 7.42gAR level
2CO
3Be mixed with the solution of 0.1M.Then under the strong mixing condition, nitrate solution and sodium carbonate liquor and drip to be gone into to preset in the 100mL aqueous solution of 0.45g activated carbon fiber and 0.26g CNT, solution temperature is controlled at 60 ℃, and pH is 7.0-7.2.Reaction finishes the back and continues to stir 4h; spend deionised water 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 CNT 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 condition 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 (9)
1, a kind of copper-based catalysts of nano-carbon material modification is characterized in that by CuO/ZnO/Al
2O
3Active component 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, the copper-based catalysts of nano-carbon material modification according to claim 1 is characterized in that the nano-carbon material weight percentage is 5-15wt%.
3, the copper-based catalysts of nano-carbon material modification according to claim 1 is characterized in that CuO/ZnO/Al
2O
3The mol ratio of Cu, Zn, Al is Cu/Zn/Al=45/45/10 in the active component.
4, the copper-based catalysts of nano-carbon material modification according to claim 1 is characterized in that nano-carbon material is one or more in activated carbon, carbon nano-fiber, graphite, CNT, the activated carbon fiber.
5, 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 sodium carbonate and contain the chlorate of copper, zinc and aluminium or the aqueous solution of nitrate with and the stream mode join in the pre-dispersed aqueous solution that a certain amount of nano-carbon material arranged, the concentration of sodium carbonate liquor, 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 catalyst.
6, the preparation method of the copper-based catalysts of nano-carbon material modification according to claim 5, the concentration that it is characterized in that sodium carbonate liquor, chlorate or nitrate solution is 0.1-0.3M.
7, the preparation method of the copper-based catalysts of nano-carbon material modification according to claim 5 is characterized in that calcination atmosphere is nitrogen or argon gas.
8, the preparation method of the copper-based catalysts of nano-carbon material modification according to claim 5 is characterized in that sintering temperature is 300-400 ℃.
9, according to claim 1 or 5 the copper-based catalysts of nano-carbon material modification as the application of catalyst for steam reformation of methanol to produce hydrogen.
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| AT501383B1 (en) * | 2005-02-10 | 2006-11-15 | Electrovac | Preparing gas mixture, used for producing e.g. nanofibers, comprises supplying feed gas in reformer and secondary reformer, contacting nano-structured catalyst with feed gas, and combining carbon monoxide and carbon dioxide free exhaust gas |
| DE502005002744D1 (en) | 2005-02-10 | 2008-03-20 | Electrovac Ag | Process and apparatus for the production of hydrogen |
| AT502901B1 (en) | 2005-10-31 | 2009-08-15 | Electrovac Ag | DEVICE FOR HYDROGEN MANUFACTURE |
| CN102755897B (en) * | 2012-07-20 | 2014-02-12 | 西南化工研究设计院有限公司 | Method for preparing catalyst for methanol dehydrogenation to methyl formate through step coprecipitation-spray process |
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| CN117208845B (en) * | 2023-09-11 | 2025-07-25 | 大连大学 | Method for preparing hydrogen by catalytic reforming of methanol and steam |
| CN118663340B (en) * | 2024-07-03 | 2025-09-12 | 北京道思克能源设备有限公司 | Preparation method of low-copper methanol reforming hydrogen production catalyst |
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| CN1390640A (en) * | 2002-07-30 | 2003-01-15 | 复旦大学 | Nano CuZnAl catalyst for synthesizing methanol and dimethylether and its preparing process |
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