CN102417161B - Method for producing CO-free hydrogen by steam reformation based on biomass alcohol as raw material - Google Patents
Method for producing CO-free hydrogen by steam reformation based on biomass alcohol as raw material Download PDFInfo
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- CN102417161B CN102417161B CN201110244643.7A CN201110244643A CN102417161B CN 102417161 B CN102417161 B CN 102417161B CN 201110244643 A CN201110244643 A CN 201110244643A CN 102417161 B CN102417161 B CN 102417161B
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Abstract
The invention relates to a method for producing CO-free hydrogen by steam reformation based on biomass alcohol as a raw material. The method comprises the following steps: filling a Raney N or M/Raney N catalyst to a reactor, wherein N is Ni, Co or Cu, M is one of groups 8, 9 and 10 transition metals Fe, Cu, Co, Ni, Pt, Ru, Rh and Pd, and the addition amount of the second metal M in the catalyst is 0.5-50wt%; introducing a mixed gas of nitrogen and 10% by volume of hydrogen at the flow of 50ml/min, and pre-reducing the catalyst for 1 hour at the temperature of 400 DEG C; and introducing biomass alcohol aqueous solution steam with a water-carbon ratio (a number ratio of water molecule to carbon atom) of (2:1)-(9:1) at the air speed of 40000-120000h<-1>, and carrying out steam reformation at the temperature of 300-700 DEG C at normal pressure so as to produce CO-free hydrogen. CO-free hydrogen prepared by using the method provided by the invention has available raw materials, can be renewable and clean and has no pollution; and the catalyst preparation process is simple and convenient for operation; and the prepared catalyst has high catalytic activity, good selectivity and strong stability.
Description
Technical field
The present invention relates to a kind of steam reformation hydrogen production technology, particularly a kind ofly take the method that biomass alcohol is raw material steam reformation hydrogen making, by biomass alcohol steam reformation, produce the hydrogen without CO.
Background technology
In the last few years, a large amount of exploitations and use due to fossil energy, the energy dilemma and the ecocrisis that have caused frequent appearance, people are in the urgent need to developing renewable energy source to substitute fossil energy, biomass alcohol is a kind of renewable energy source of arising at the historic moment, and biomass ethanol is the most representative biomass alcohol; Biomass ethanol relative combustion efficiency is lower, in order to improve the efficiency of combustion of biomass ethanol, it being carried out to further exploitation and to obtain high energy clean fuel, also seem particularly necessary, is one of the most promising exploitation mode by the hydrogen manufacturing of biomass ethanol steam reforming in conjunction with hydrogen energy fuel battery.[U.Eberle，M.Felderhoff，and F.Schüth.Chemical and Physical Solutions for Hydrogen Storage.Angewandte Chemie-International Edition.2009，48，6608-6630]。
Hydrogen energy fuel battery applications scope is wide, and energy utilization efficiency is high, and does not produce pollution, is to meet the clean energy that Green Chemistry requires.But because fuel cell is used Pt electrode, the existence of CO can cause Pt electrode poisoning, and therefore developing a kind of technique of producing without CO hydrogen has great economic worth and environmental benefit.In steam reformation process, the water gas shift reation meeting of CO produces H simultaneously
2, the minimizing of CO also means H
2optionally improve.
The people such as J.A.Dumesic [Catalytic Reforming of Oxygenated Hydrocarbons for Hydrogen with Low Levels of Carbon Monoxide.Angewandte Chemie-International Edition.2003,42,4068-4071] first reported that the aqueous phase reforming on the catalyzer such as Pt, Ni is produced the hydrogen without CO by biomass alcohol.When adopting 3wt%Pt/Al
2o
3catalyzer also be take the glycerine solution of 10wt% during as raw material, and glycerol conversion yield is 77%, and hydrogen selective is 70%, but hydrogen-producing speed is only 2 * 10
4μ molg
-1h
-1, suitable with the speed of glucose fermentation hydrogen manufacturing.When adopting the Ni catalyzer of Sn modification, can when keeping good scission of link performance, reduce the selectivity of alkane, and can obtain good catalytic stability.Although can obtain lower CO level, higher active and selectivity to hydrogen by aqueous-phase reforming, but can produce more liquid phase alkane product simultaneously, raw material availability is lower, and simultaneous reactions need to carry out under the pressure higher than 2MPa, to having relatively high expectations of equipment.
The people such as Llorca [CO-free hydrogen from steam-reforming of bioethanol over ZnO-supported cobalt catalysts.Applied Catalysis B:Environmental.2003,43,355-369] pass through Co
2(CO)
8co (CO)/ZnO catalyst ethanol steam reforming at 350 ℃ of preparation has been prepared and has not been contained the hydrogen of CO, but charging air speed is less, is 5000h
-1, when air speed is increased to 30000h
-1time there is CO.The people such as Chen [Carbon monoxide-free hydrogen production via low-temperature steam reforming of ethanol over iron-promoted Rh catalyst.Journal of Catalysis.2010,276,197-200] employing Rh-Fe/Ca-Al
2o
3catalyzer has been prepared the hydrogen without CO by the steam reformation of ethanol in the temperature range of 300-400 ℃.When charging air speed is 0.54g
etOHg
cat/ h, under 400 ℃ of reaction conditionss, ethanol conversion is 100%, H
2selectivity is 72%.Although this catalyzer has higher activity and selectivity, because Rh is precious metal, catalyzer cost is higher, is unfavorable for large-scale industrial application.
Summary of the invention
The object of the invention is to provide a kind of take biomass alcohol and produces the method without CO hydrogen as raw material steam reformation, and the method adopts thunder Thessaloniki catalyzer, has process simple, raw material is renewable, catalyst activity advantages of higher, biomass alcohol transformation efficiency can reach 100%, and hydrogen selective can reach more than 80%.
Provided by the inventionly take the method that biomass alcohol prepares hydrogen as raw material steam reformation and comprise the following steps:
First to loading Raney N (N=Ni, Co, Cu) or M/Raney N (in M=8,9,10 group 4 transition metal Fe, Cu, Co, Ni, Pt, Ru, Rh, Pd a kind of) catalyzer in reactor, in catalyzer, the second metal M addition is: 0.5～50wt%.To passing into hydrogen volume mark in reactor, be 10% hydrogen and nitrogen mixture, mixed gas flow is 50ml/min, at 400 ℃, catalyzer is carried out to prereduction 1h, then to reactor with air speed 5000～60000h
-1pass into steam/hydrocarbons ratio (water molecules and carbon atom number ratio) and be 2～9: 1 biomass alcohol aqueous solution steam, at normal pressure, steam reformation hydrogen making under the condition of 300～700 ℃, the reaction times is not less than 10h; Obtain not containing the H of CO
2.Adopt gas chromatograph to carry out on-line analysis.
Wherein, the catalyzer in above-mentioned steps adopts RaneyNi or M/RaneyNi (M=Cu, Co, Pt), and metal M addition is 2-10wt%, and alcohol steam steam/hydrocarbons ratio is 4～6: 1; Alcohol steam air speed is 60000～100000h
-1; Temperature of reaction is 300～500 ℃.
The invention has the advantages that take biology alcohol processed has made the hydrogen without CO as raw material, raw material is easy to get, renewable, cleanliness without any pollution.The method both can improve the energy efficiency of biological ethanol processed, had developed again new producing without CO hydrogen route, for the development of hydrogen energy fuel battery lays the foundation.Catalyzer adopts leaching preparation, in ethanolic soln, preserves, and the second metal promoter adopts pickling process load, and catalyst preparation process is simple, easy to operate, and it is high that the catalyzer making has catalytic activity, and selectivity is good, and stability is strong.Biomass alcohol transformation efficiency can reach 100%, and hydrogen selective can reach more than 80%.
Embodiment
By following examples, illustrate prepared by method of the present invention and catalyzer, but the present invention is not limited to following examples.
Embodiment 1:
Drop is got alloyage and is prepared Raney Ni catalyzer, and pickling process is prepared M/Raney Ni (M=Cu, Co, Pt etc.) catalyzer.
Preparation 20%NaOH aqueous solution 120ml, and in water-bath, be heated to 50 ℃, the Ni-Al alloy of 2g is poured in above-mentioned solution, heating in water bath to 80 ℃ subsequently, and stirring 3h at 80 ℃, gained precipitation is RaneyNi, and precipitation is washed to neutrality (PH < 7), use again washing with alcohol, and be put under ethanol and preserve.[The nature ofRaney nickel，its adsorbed hydrogen and its catalytic activity for hydrogenation reactions.Applied Catalysis，1983，8，1-42]
Prepare the second metal promoter ethanolic soln (Cu (CH
3cOO)
2, Co (CH
3cOO)
2and Pt (NO
3)
2deng), making additive dosage is 2-10wt%, pour in Raney Ni, keep given volume, in water-bath, be heated to 70 ℃, and stir 1h at 70 ℃, gained catalyzer is used to washing with alcohol until occur without unnecessary ion in solution, and preserve under ethanol, gained catalyzer is M/Raney Ni (M=Cu, Co, Pt etc.), M/Ni=2-10wt%.[Synthesis of cis-and trans-octadecenes.Selective catalytic hydrogenation of actylenes.Journal of Chemical society.1953，3156-3160]
Embodiment 2:
Raney Ni catalyzer is pulled out; 80 ℃ of dry 5h in vacuum drying oven; taking afterwards 100mgRaney Ni catalyzer packs in the reactor that internal diameter is 8mm; at 400 ℃, adopting hydrogen volume mark is that 10% hydrogen and nitrogen mixture carry out the prereduction of 1h; mixed gas flow is 50ml/min; in nitrogen protection, drop to 300 ℃, subsequently with air speed 100000h
-1the aqueous ethanolic solution steam that is 4: 1 by steam/hydrocarbons ratio (water molecules and carbon atom number ratio) passes into reactor, carries out steam reformation hydrogen making.Reaction end gas (containing various gas and steam state product) was sampled and adopts gas chromatograph (6820, Agilent) to carry out on-line analysis every half an hour.
Ethanol conversion rate H
2and carbonaceous products selectivity is with following various calculating:
H
2selectivity (%)=[(H of generation
2mole number)/(C mole number in product gas)] * (2/6) * 100
Wherein j represents the carbon species that contains in product, comprises CO, CO
2cH
4, C
2h
4, C
2h
6, CH
3cHO, and CH
3cOCH
3deng, i is containing the contained carbonatoms of carbon species.
Embodiment 3:
Adopt embodiment 2 methods to react, difference is that temperature of reaction is 350 ℃.
Embodiment 4:
Adopt embodiment 2 methods to react, difference is that temperature of reaction is 400 ℃.
Embodiment 5:
Adopt embodiment 2 methods to react, difference is that temperature of reaction is 450 ℃.
Embodiment 6:
Adopt embodiment 2 methods to react, difference is that temperature of reaction is 500 ℃.
Embodiment 7:
Adopt embodiment 3 to react, difference is that catalyzer adopts 2%Cu/Raney Ni.
Embodiment 8:
Adopt embodiment 3 to react, difference is that catalyzer adopts 2%Co/Raney Ni.
Embodiment 9:
Adopt embodiment 3 to react, difference is that catalyzer adopts 2%Pt/Raney Ni.
Embodiment 10:
Adopt embodiment 3 to react, difference is that catalyzer adopts 10%Cu/Raney Ni.
Embodiment 11:
Adopt embodiment 3 methods to react, difference is that charging air speed is 60000h
-1.
Embodiment 12:
Adopt embodiment 3 methods to react, difference is that feed ethanol aqueous solution steam water carbon ratio is 6: 1
Embodiment 13:
Temperature of reaction is for the impact (table one) of RaneyNi catalyst reaction activity.Reaction conditions is with embodiment 2,3,4,5,6.
At table one differential responses temperature, Raney Ni catalyst reaction is active
| Temperature of reaction/℃ | Ethanol conversion/% | H 2Selectivity/% | CO selectivity/% | CO 2Selectivity/% | CH 4Selectivity/% |
| 300 | 90 | 23 | 15 | 11 | 73 |
| 350 | 100 | 32 | 0 | 47 | 53 |
| 400 | 100 | 37 | 0 | 49 | 50 |
| 450 | 100 | 58 | 5 | 63 | 32 |
| 500 | 100 | 85 | 10 | 72 | 18 |
From above result, can see, for Raney Ni catalyzer, its transformation efficiency after temperature is higher than 350 ℃ is just 100%, H
2selectivity is along with temperature raises and increases, and CO selectivity in 350-400 ℃ of interval is 0, and now the selectivity of methane is the highest, and CO
2selectivity, along with temperature raises and increases, illustrates that optimal production is without the H of CO
2temperature be 350-400 ℃.
Embodiment 14:
Add auxiliary agent for reactive behavior and H
2optionally impact (table two).Reaction conditions is with embodiment 3,7,8,9.
The different auxiliary agents of table two add rear catalyst reactive behavior
As can be seen from the above results, add different metal promoters, have different effects, Cu, Pt can suppress methanation reaction, thereby make H
2selectivity raises, and Co can promote methanation reaction, thereby reduces H
2selectivity, the selectivity of CO is 0 in the time of 350 ℃.So it is more favourable to add Cu or Pt auxiliary agent.
Embodiment 15:
Add auxiliary agent content for reactive behavior and H
2optionally impact (table three).Reaction conditions is with embodiment 7,10.
The impact of table three additive dosage on reactive behavior
Result from table can be found out, after the increase of auxiliary agent Cu addition, more can suppress methanation, thereby make H
2selectivity raises, but while activity decreased, ethanol conversion reduces to 95%.So the addition of auxiliary agent is unsuitable excessive.
Embodiment 16:
Charging air speed is for reactive behavior with to H
2optionally impact (table four).Reaction conditions is with embodiment 3,11.
The impact of table four charging air speed on Raney Ni catalyst reaction activity
| Charging air speed/h -1 | Ethanol conversion/% | H 2Selectivity/% | CO selectivity/% | CO 2Selectivity/% | CH 4Selectivity/% |
| 60000 | 100 | 36 | 0 | 49 | 51 |
| 100000 | 100 | 32 | 0 | 47 | 53 |
Result from table can be found out, increases air speed H
2selectivity can be to a certain degree reduction.
Embodiment 17:
Feed water carbon ratio is for reactive behavior with to H
2optionally impact (table five).Reaction conditions is with embodiment 3,12.
The impact of table five feed water carbon ratio on Raney Ni catalyst reaction activity
Result from table can be found out, increases feed water carbon ratio and more can promote the conversion of CO and methane, makes H
2selectivity raises.
Claims (4)
1. take biomass alcohol as the method for raw material steam reformation preparation without CO hydrogen, it is characterized in that comprising the following steps:
In reactor, fill thunder Thessaloniki catalyzer, take biomass alcohol and water vapor carries out steam reformation hydrogen production reaction as reaction raw materials, the catalyzer first part adopting is thunder Buddhist nun type catalyzer Raney Ni, Raney Cu or Raney Co, and second section is a kind of as catalyst adjuvant in transition-metal Fe, Cu, Co, Ni, Pt, Ru, Rh, Pd; Before reaction, to passing into hydrogen volume mark in reactor, be first 10% hydrogen and nitrogen mixture, mixed gas flow 50ml/min carries out prereduction 1h to catalyzer at 400 ℃, then in reactor with air speed 5000～60000h
-1pass into water molecules and carbon atom number than the biomass alcohol aqueous solution steam that is 2～9:1, reaction pressure is normal pressure, steam reformation hydrogen making under the temperature condition of 300～500 ℃, and the reaction times is not less than 10h; The weight percent of second section catalyst adjuvant and first part's catalyzer is between 0.5-10%; Adopt gas chromatograph to carry out on-line analysis.
2. the method for claim 1, is characterized in that: described catalyzer first part is Raney Ni catalyzer, and described catalyst adjuvant second section component is Cu, Co or Pt, and wherein, the weight percent of second section and first part is 2-10%.
3. the method for claim 1, is characterized in that: described biomass alcohol is biomass ethanol.
4. method as claimed in claim 3, is characterized in that: the water molecules of described aqueous ethanolic solution steam and carbon atom number ratio are 4～6:1.
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| CN102417161B true CN102417161B (en) | 2014-03-12 |
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| CN103586029B (en) * | 2013-10-29 | 2015-06-17 | 天津大学 | Catalyst for hydrogen production by water-phase reforming of biomass depolymerization product and preparation method thereof |
| CN103908967B (en) * | 2014-04-01 | 2016-04-06 | 广西科技大学 | For the Catalysts and its preparation method of carbon monoxide aqueous vapor reformation hydrogen production |
| CN107552071A (en) * | 2017-09-26 | 2018-01-09 | 安徽国星生物化学有限公司 | A kind of preparation method for the Raney's nickel that cobalt salt is modified and the method for synthesizing glufosinate-ammonium |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020141A (en) * | 2006-12-15 | 2007-08-22 | 天津大学 | Catalyst for water vapor reformation of ethanol to prepare hydrogen and its prepn and use |
| CN101157444A (en) * | 2002-10-18 | 2008-04-09 | 孟山都技术公司 | Use of metal supported copper catalysts for reforming alcohols |
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- 2011-08-25 CN CN201110244643.7A patent/CN102417161B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157444A (en) * | 2002-10-18 | 2008-04-09 | 孟山都技术公司 | Use of metal supported copper catalysts for reforming alcohols |
| CN101020141A (en) * | 2006-12-15 | 2007-08-22 | 天津大学 | Catalyst for water vapor reformation of ethanol to prepare hydrogen and its prepn and use |
Non-Patent Citations (3)
| Title |
|---|
| David A. Morgenstern and James P. Fornango.Low-Temperature Reforming of Ethanol over Copper-Plated Raney Nickel: A New Route to Sustainable Hydrogen for Transportation.《Energy& * |
| David A. Morgenstern and James P. Fornango.Low-Temperature Reforming of Ethanol over Copper-Plated Raney Nickel: A New Route to Sustainable Hydrogen for Transportation.《Energy&Fuels》.2005,第19卷1708-1716. |
| Fuels》.2005,第19卷1708-1716. * |
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