CN1291784C - Copper base catalyst in use for preparing hydrogen by reforming vapor of methanol and preparation method - Google Patents
Copper base catalyst in use for preparing hydrogen by reforming vapor of methanol and preparation method Download PDFInfo
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- CN1291784C CN1291784C CNB2004100178246A CN200410017824A CN1291784C CN 1291784 C CN1291784 C CN 1291784C CN B2004100178246 A CNB2004100178246 A CN B2004100178246A CN 200410017824 A CN200410017824 A CN 200410017824A CN 1291784 C CN1291784 C CN 1291784C
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Abstract
The present invention relates to a mesoporous silicon oxide modification copper-based catalyst for methanol steam reformation hydrogen production and a preparing method thereof. The catalyst is composed of active components of CuO / ZnO / Al2O3 and silicon oxide base mesoporous materials, wherein the weight percentage of mesoporous silicon oxides is from 1 to 30% of the total weight of the catalyst. In the active components, the molar ratio of the content of the CuO is from 30% to 70%, the molar ratio of the content of the ZnO is from 20% to 60%, and the molar ratio of the content of the Al2O3 is from 0% to 15%. The catalyst is prepared by a carbonate parallel flow coprecipitation method. Under the conditions of stir and temperature of 30 to 80 DEG C, nitrate solutions and sodium carbonate solutions are dripped into a reactor which is preliminarily provided with metering mesoporous silicon oxides in a constant speed and parallel flow way to carry out coprecipitation reaction, carbonate coprecipitates containing the mesoporous silicon oxides are obtained, and the catalyst is prepared through washing, drying, roasting, etc. The catalyst has the advantages of unique and large surface, porous structure, low temperature, high activity, good stability, high selectivity for hydrogen, high hydrogen content of 75% in reforming products, and low CO content below 0.1%.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to copper-based catalysts that a kind of novel steam reformation of methanol to produce hydrogen uses and preparation method thereof.
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 multiple technologies problem, 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 steam reformation of methanol to produce hydrogen reaction and the reformation gas
2With CO content comparatively strict requirement is arranged all, especially more harsh to the CO content requirement, very easily cause the permanent poisoning of PEM types of fuel cells (PEMFC) anode catalyst because of CO.By copper-based catalysts catalysis methanol steam reforming hydrogen manufacturing 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 steam reformed hydrogen-producing catalyst that has high activity, high hydrogen selectivity and stability concurrently has become vehicle-mounted hydrogen manufacturing system such as fuel cell and further moves towards the extremely important research topic that practicability faces.
At present, the research for application and development of novel copper-based catalyst for steam reformation of methanol to produce hydrogen 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 steam reformation of methanol to produce hydrogen 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.The large pore volume of novel silicon oxide mesoporous molecular sieve such as its uniqueness that is possessed such as SBA-15, MCM-41, high-specific surface area and good thermal stability have caused extensive concern [Nature, 1992,359:710 in recent years as potential new catalytic material; Science 1998,282:2244.].With novel silica-based mesoporous material is structural promoter, can prepare the novel copper-based catalyst of Large ratio surface and copper/zinc active component high degree of dispersion, is expected to realize 230 ℃ of high activity, high selectivity preparing hydrogen by reforming methanol under the cryogenic conditions of the left and right sides.
Summary of the invention
The objective of the invention is to propose a kind of be used for steam reformation of methanol to produce hydrogen, have low-temperature catalyzed high activity, stable performance, a novel copper-based Catalysts and its preparation method that the hydrogen selectivity is high, this catalyst can significantly improve the content of hydrogen in the reformation aerogenesis, reduce the content of CO, thereby satisfy the actual demand of vehicle-mounted hydrogen production.
The copper-based catalysts that is used for steam reformation of methanol to produce hydrogen that the present invention proposes is by CuO/ZnO/Al
2O
3Active component and silicon oxide mesoporous molecular screen material combine, wherein, and CuO/ZnO/Al
2O
3The weight percentage of active component is 70-99wt%, and remaining 1-30wt% is silicon oxide mesoporous molecular sieve.The weight content of mesopore silicon oxide component is best between 3-12wt%.
Above-mentioned silicon oxide mesoporous molecular sieve modified copper-based catalysts, CuO/ZnO/Al wherein
2O
3CuO content is preferably the 45-60% mol ratio in the 30-70% mol ratio in the component; ZnO content is preferably the 30-45% mol ratio in the 20-60% mol ratio; Al
2O
3Content is preferably 5～12% mol ratios in the 0-15% mol ratio.Three's total amount satisfies 100% mol ratio.
The copper-based catalysts of above-mentioned meso pore silicon oxide material modification, meso pore silicon oxide material wherein are mesoporous silica gel (specific area 400-500m
2/ g), MCM-41 (specific area 800-1000m
2/ g), SBA-15 (specific area 700-1000m
2/ g), SiO
2Aeroge (specific area 100-1200m
2/ g) wait one or more.
The copper-based catalysts that the mesopore silicon oxide that the present invention proposes promotes can adopt traditional carbonate and flow the coprecipitation preparation.Its concrete steps are: according to usage ratio, under stirring, 30-80 ℃ condition, with the aqueous solution of sodium carbonate and contain copper, zinc and aluminium nitrate the aqueous solution with and the stream mode join in the pre-dispersed aqueous solution that the silicon oxide mesoporous molecular sieve of specified rate arranged, carry out coprecipitation reaction, wear out, obtain containing the carbonate coprecipitation thing of mesopore silicon oxide; Wash again, drying, roasting, granulation promptly gets this catalyst.
Among the above-mentioned preparation method, the aqueous solution of the nitrate of sodium carbonate and cupric, zinc and aluminium can once add, and also can slowly drip by certain speed.The concentration of sodium carbonate and nitrate solution is between the 0.05M-0.5M, is preferably 0.1M-0.3M.Nitrate solution and sodium carbonate liquor constant speed and drip are gone into to preset in the reactor of metering mesopore silicon oxide to carry out coprecipitation reaction, pH value is controlled to be 7.0-7.2, and reaction finishes the back and continues stirring 3-5 hour.Precipitated liquid is washed through distilled water, fully making beating, filtration.Baking is dry then, baking temperature 100-120 ℃.Dried catalyst is roasting under given atmosphere again.The atmosphere of roasting is generally air, oxygen, nitrogen, argon gas or carbon dioxide, is preferably air.Sintering temperature is generally 250～600 ℃, and reasonable temperature is 300～400 ℃.Roasting time is 2-10 hour.It is 60～80 purpose samples that catalyst after the roasting is made particle mean size through compressing tablet, granulation supervisor.
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 * Ф 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, and catalyst preparation process is simple, good reproducibility.Hydrogen content 50-75vol% in the reformation aerogenesis, CO concentration is 0.08-0.3vol%, easily purified treatment.
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 7.42gAR level
2CO
3Be mixed with the solution of 0.1M.Then under the strong mixing condition, above-mentioned nitrate solution and sodium carbonate liquor and drip to be gone into to preset in the 100mL aqueous solution of 0.16g SBA-15 (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; in 110 ℃ of dry 12h, under nitrogen protection,, prepare catalyst oxidation attitude presoma at last at 360 ℃ of roasting 4h; Cu/Zn/Al=45/45/10 in the sample (mol ratio), the SBA-15 weight content is 3wt% in the catalyst oxidation attitude presoma.
Catalyst carries out (300mm * Ф 10mm) to the steam reformation of methanol to produce hydrogen activity rating in atmospheric fixed bed continuous flow reactor system, catalyst amount is 0.5 g.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 89.9%, the hydrogen productive rate is 0.3037, hydrogen selective is 99.6%, 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, a spot of SBA-15 modification rear catalyst low temperature active improves, and 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 traditional C u/ZnO/Al of monox mesoporous material
2O
3Catalyst.Catalytically active assessment 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 condition under, methanol conversion is 83.1%, the hydrogen productive rate is 0.2808, 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 0.3M respectively, again with the anhydrous Na of 7.42g AR level
2CO
3Be mixed with the solution of 0.3M.Then under the strong mixing condition, above-mentioned nitrate solution and sodium carbonate liquor and drip to be gone into to preset in the 100mL aqueous solution of 0.27g SBA-15, solution temperature is controlled at 30 ℃, and pH is 7.0-7.2.Reaction finishes the back and continues to stir 4h; spend deionised water then; fully making beating; filter; in 120 ℃ of dry 12h, under the nitrogen atmosphere protection,, prepare catalyst oxidation attitude presoma at last 300 ℃ of roastings 5 hours; Cu/Zn/Al=45/45/10 in the sample (mol ratio), the SBA-15 weight content is 5wt% in the catalyst oxidation attitude presoma.Catalyst activity is estimated with embodiment 1, and test 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 93.4%, the hydrogen productive rate is 0.3156, hydrogen selective is 99.9%, CO
2Selectivity is 99.3%, and CO content is 0.16% 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 0.5M respectively, again with the anhydrous Na of 7.42g AR level
2CO
3Be mixed with the solution of 0.5M.Then under the strong mixing condition, above-mentioned nitrate solution and sodium carbonate liquor and drip to be gone into to preset in the 100mL aqueous solution of 0.45g SBA-15, solution temperature is controlled at 80 ℃, and pH is 7.0-7.2.Reaction finishes the back and continues to stir 4h; spend deionised water then; fully making beating; filter; in 100 ℃ of dry 12h, under nitrogen protection,, prepare catalyst oxidation attitude presoma at last at 250 ℃ of roasting 5h; Cu/Zn/Al=45/45/10 in the sample (amount of substance ratio), the SBA-15 weight content is 8wt% in the catalyst oxidation attitude presoma.Catalyst activity is estimated with embodiment 1, and test 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 97.1%, the hydrogen productive rate is 0.3281, hydrogen selective is 99.9%, CO
2Selectivity is 99.4%, and CO content is 0.15% 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, above-mentioned nitrate solution and sodium carbonate liquor and drip to be gone into to preset in the 100mL aqueous solution of 0.71g SBA-15, solution temperature is controlled at 55 ℃, and pH is 7.0-7.2.Reaction finishes the back and continues to stir 4h; spend deionised water then; fully making beating; filter; in 100 ℃ of dry 12h, under nitrogen protection,, prepare catalyst oxidation attitude presoma at last at 600 ℃ of roasting 3h; Cu/Zn/Al=45/45/10 in the sample (mol ratio), the SBA-15 weight content is 12wt% in the catalyst oxidation attitude presoma.Catalyst activity is estimated with embodiment 1, and test 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 95.2%, the hydrogen productive rate is 0.3217, hydrogen selective is 99.9%, CO
2Selectivity is 99.6%, and CO content is 0.11% 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, above-mentioned nitrate solution and sodium carbonate liquor and drip to be gone into to preset in the 100mL aqueous solution of 0.99g SBA-15, 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; in 110 ℃ of dry 12h, under nitrogen protection,, prepare catalyst oxidation attitude presoma at last at 500 ℃ of roasting 3h; Cu/Zn/Al=45/45/10 in the sample (mol ratio), the SBA-15 weight content is 16wt% in the catalyst oxidation attitude presoma.Catalyst activity is estimated with embodiment 1, and test result shows: at normal pressure, and 230 ℃ of low temperature, n (H
2O)/n (CH
3OH)=and 1.1/1.0, WHSV=3.61 h
-1Reaction condition under, methanol conversion is 87.5%, the hydrogen productive rate is 0.2956, hydrogen selective is 99.9%, CO
2Selectivity is 99.5%, and CO concentration is 0.12% 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 0.05M respectively, again with the anhydrous Na of 7.42g AR level
2CO
3Be mixed with the solution of 0.01M.Then under the strong mixing condition, above-mentioned nitrate solution and sodium carbonate liquor and drip are gone into to preset 0.45g SiO
2The 100mL aqueous solution in, solution temperature is controlled at 60 ℃, pH is 7.0-7.2.Reaction finishes the back and continues to stir 4h, spend deionised water then, fully making beating, filter, in 110 ℃ of dry 12h, under air atmosphere,, prepare catalyst oxidation attitude presoma at last at 360 ℃ of roasting 4h, Cu/Zn/Al=45/45/10 in the sample (mol ratio), SiO in the catalyst oxidation attitude presoma
2The aeroge weight content is 8wt%.Catalyst activity is estimated with embodiment 1, and test 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 86.3%, the hydrogen productive rate is 0.2916, hydrogen selective is 99.6%, CO
2Selectivity is 99.4%, and CO content is 0.14% 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, above-mentioned nitrate solution and sodium carbonate liquor and drip to be gone into to preset in the 100mL aqueous solution of 0.45g MCM-41, solution temperature is controlled at 65 ℃, and pH is 7.0-7.2.Reaction finishes the back and continues to stir 4h; spend deionised water then; fully making beating; filter; in 110 ℃ of dry 12h, under argon shield,, prepare catalyst oxidation attitude presoma at last at 400 ℃ of roasting 4h; Cu/Zn/Al=45/45/10 in the sample (mol ratio), the MCM-41 weight content is 8wt% in the catalyst oxidation attitude presoma.Catalyst activity is estimated with embodiment 1, and test 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 87.9%, the hydrogen productive rate is 0.2970, hydrogen selective is 99.7%, CO
2Selectivity is 99.5%, and CO content is 0.13% in the reformation aerogenesis.With reference to contrast experiment one, the low-temperature catalyzed performance of MCM-41 modification rear catalyst is improved, and the content of CO obtains the reduction of certain degree in the reformation aerogenesis.
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, above-mentioned nitrate solution and sodium carbonate liquor and drip to be gone into to preset in the 100mL aqueous solution of 0.45g mesoporous silica gel, solution temperature is controlled at 50 ℃, and pH is 7.0-7.2.Reaction finishes the back and continues to stir 4h; spend deionised water then; fully making beating; filter; in 110 ℃ of dry 12h, under nitrogen protection,, prepare catalyst oxidation attitude presoma at last at 360 ℃ of roasting 4h; Cu/Zn/Al=45/45/10 in the sample (mol ratio), the mesoporous silica gel weight content is 8wt% in the catalyst oxidation attitude presoma.Catalyst activity is estimated with embodiment 1, and test 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 85.7%, the hydrogen productive rate is 0.2970, hydrogen selective is 99.7%, CO
2Selectivity is 99.5%, and CO content is 0.19% in the reformation aerogenesis.
Embodiment 9
At first with 9.68g Cu (NO
3)
23H
2O, 5.94g 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, above-mentioned nitrate solution and sodium carbonate liquor and drip to be gone into to preset in the 100mL aqueous solution of 0.71g SBA-15, 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, in 110 ℃ of dry 12h, under air atmosphere,, prepare catalyst oxidation attitude presoma at last at 360 ℃ of roasting 4h, Cu/Zn/Al=60/30/10 in the sample (mol ratio), the SBA-15 weight content is 12wt% in the catalyst oxidation attitude presoma.Catalyst activity is estimated with embodiment 1, and test 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 90.2%, the hydrogen productive rate is 0.3048, hydrogen selective is 99.9%, CO
2Selectivity is 99.6%, and CO content is 0.08% 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 0.3M respectively, again with the anhydrous Na of 7.42g AR level
2CO
3Be mixed with 0.3] solution of M.Then under the strong mixing condition, above-mentioned nitrate solution and sodium carbonate liquor and drip to be gone into to preset in the 100mL aqueous solution of 1.48g SBA-15, 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 500 ℃ of roasting 4h, prepare catalyst oxidation attitude presoma, Cu/Zn/Al=45/45/10 in the sample (mol ratio), the SBA-15 weight content is 25wt% in the catalyst oxidation attitude presoma.Catalyst activity is estimated with embodiment 1, and test 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 89.2%, the hydrogen productive rate is 0.3007, hydrogen selective is 99.9%, CO
2Selectivity is 99.6%, and CO content is 0.13% in the reformation aerogenesis.
Embodiment 11
At first with 11.30g Cu (NO
3)
23H
2O, 5.94g Zn (NO
3)
26H
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, above-mentioned nitrate solution and sodium carbonate liquor and drip to be gone into to preset in the 100mL aqueous solution of 0.71g SBA-15, 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, in 110 ℃ of dry 12h, under carbon dioxide atmosphere,, prepare catalyst oxidation attitude presoma at last at 360 ℃ of roasting 4h, Cu/Zn/Al=70/30/0 in the sample (mol ratio), the SBA-15 weight content is 12wt% in the catalyst oxidation attitude presoma.Catalyst activity is estimated with embodiment 1, and test 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 84.2%, the hydrogen productive rate is 0.2838, hydrogen selective is 99.9%, CO
2Selectivity is 99.6%, and CO content is 0.18% in the reformation aerogenesis.
The low-temperature catalyzed performance of the copper base catalyst for steam reformation of methanol to produce hydrogen of more various novel meso pore silicon oxide material modifications as can be known, novel mesoporous molecular sieve SBA-15 with regular mesopore orbit structure, the copper base catalyst for steam reformation of methanol to produce hydrogen activity of MCM-41 modification is improved, the content of CO is reduced in the aerogenesis, especially New type of S BA-15 mesopore molecular sieve modification copper-based catalysts shows best catalytic performance, and the content of SBA-15 behaves oneself best for the 3-12wt.% catalyst performance.
Claims (6)
1, the silicon oxide mesoporous molecular sieve modified copper-based catalysts used of a kind of steam reformation of methanol to produce hydrogen is characterized in that by CuO/ZnO/Al
2O
3Active component and silicon oxide mesoporous molecular sieve are formed, wherein active component CuO/ZnO/Al
2O
3Weight percentage be 70-99wt%; Remaining 1-30wt% is silicon oxide mesoporous molecular sieve; Said CuO/ZnO/Al
2O
3CuO content is in the 30-70% mol ratio in the active component, and ZnO content is at 20-60% mol ratio, Al
2O
3Content is in the 0-15% mol ratio, and three's total amount satisfies 100% mol ratio.
2,, it is characterized in that said silicon oxide mesoporous molecular sieve is a kind of among SBA-15, the MCM-41 according to the described catalyst of claim 1.
3, the preparation method of the silicon oxide mesoporous molecular sieve modified copper-based catalysts used of a kind of steam reformation of methanol to produce hydrogen as claimed in claim 1, it is characterized in that: by usage ratio, under stirring, 30-80 ℃ condition, with the aqueous solution of sodium carbonate and contain copper, zinc and aluminium nitrate the aqueous solution with and the stream mode join in the pre-dispersed aqueous solution that the silicon oxide mesoporous molecular sieve of specified rate arranged, carry out coprecipitation reaction, aging; Wash again, drying, roasting, granulation promptly gets this catalyst.
4, Preparation of catalysts method according to claim 3, the concentration that it is characterized in that sodium carbonate and nitrate aqueous solution is 0.01-0.5M.
5, Preparation of catalysts method according to claim 3 is characterized in that calcination atmosphere is air, nitrogen, argon gas or carbon dioxide.
6, Preparation of catalysts method according to claim 3 is characterized in that sintering temperature is 250-600 ℃, and roasting time is 2-10 hour.
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| CN100548478C (en) * | 2006-12-05 | 2009-10-14 | 中国科学院山西煤炭化学研究所 | A kind of catalyst and method for making and application by the synthesis gas synthesizing methanol |
| CN100457262C (en) * | 2006-12-15 | 2009-02-04 | 天津大学 | Catalyst for water vapor reformation of ethanol to prepare hydrogen and its prepn and use |
| CN101306369B (en) * | 2008-07-11 | 2010-04-14 | 西南化工研究设计院 | Catalyst for synthesizing methanol and preparing process thereof |
| EP2382682A4 (en) * | 2008-12-23 | 2014-07-16 | SOCIéTé BIC | Hydrogen generator with aerogel catalyst |
| CN102688759B (en) * | 2012-05-28 | 2015-03-25 | 中国科学院山西煤炭化学研究所 | Catalyst for hydrogen production from methanol reforming as well as preparation method and application of catalyst |
| CN106378141B (en) * | 2016-11-14 | 2019-04-05 | 中国科学技术大学 | ZnO/Cu nanocrystalline composite material and its preparation method and application |
| CN107159217A (en) * | 2017-04-25 | 2017-09-15 | 江苏大学 | A kind of Cu ZnO/SiO2Aeroge bimetallic catalyst and its production and use |
| CN108745363A (en) * | 2018-05-14 | 2018-11-06 | 中国科学院山西煤炭化学研究所 | It is a kind of for the copper-based catalysts and preparation method of hydrogen from methyl alcohol and application |
| CN111378511B (en) * | 2018-12-28 | 2021-05-04 | 中国石油化工股份有限公司 | Biomass microwave gasification utilization method and system |
| CN110743586B (en) * | 2019-09-02 | 2022-04-15 | 宁夏大学 | Na salt modified Cu/SiO2Preparation method and application of catalyst |
| CN111804326A (en) * | 2020-07-01 | 2020-10-23 | 广东能创科技有限公司 | Preparation method of copper-based composite metal catalyst |
| CN115364863B (en) * | 2021-05-18 | 2024-03-26 | 中国科学院大连化学物理研究所 | Double-function catalyst, preparation method and application thereof in methanol synthesis and hydrogen production by reforming |
| CN114160182A (en) * | 2021-12-03 | 2022-03-11 | 江苏三吉利化工股份有限公司 | Catalyst for methanol steam reforming hydrogen production and preparation and hydrogen production methods thereof |
| CN114632530B (en) * | 2022-04-20 | 2023-07-14 | 刘盛楹 | Copper-based catalyst for preparing hydrogen by reforming methanol, preparation method and application |
| CN115057466B (en) * | 2022-08-04 | 2024-03-08 | 安徽进化硅纳米材料科技有限公司 | Modified nano zinc oxide composite material and preparation method and application thereof |
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