CN1792766A - Process for reforming mfg. hydrogen by ethyl alcohol vapour - Google Patents
Process for reforming mfg. hydrogen by ethyl alcohol vapour Download PDFInfo
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- CN1792766A CN1792766A CN 200610013035 CN200610013035A CN1792766A CN 1792766 A CN1792766 A CN 1792766A CN 200610013035 CN200610013035 CN 200610013035 CN 200610013035 A CN200610013035 A CN 200610013035A CN 1792766 A CN1792766 A CN 1792766A
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Abstract
A process for preparing H2 by reforming the vapor of alcohol includes such steps as loading the mm-class Co3O4-CeO2 catalyst in reactor, reducing reaction in H2-Ar gas mixture, filling the aqueous solution of alcohol and N2 proportionally, and reforming reaction of alcohol vapor to generate H2. It has high activity, selectivity and stability.
Description
Technical field
The present invention relates to a kind of method of hydrogen production by ethanol steam reforming, belong to the hydrogen production by ethanol steam reforming technology.
Background technology
The main method that now is used for the hydrogen production by ethanol steam reforming reaction has:
(1) method of employing noble metal catalyst
Noble metal catalyst early is applied to the ethanol steam reforming reaction, and such catalyzer comprises that noble metal supports such as Pt, Ru, Rh, Pd are at Al
2O
3, CeO
2, ZrO
2, MgO, TiO
2, CeO
2-ZrO
2On oxide compound or composite oxides.J.P.Breen etc.
[1]Prepared with Al respectively
2O
3Or CeO
2-ZrO
2Be Pt, Rh, Pd, the Ni catalyzer of carrier, experimental result shows that Pt, Rh have higher activity with respect to Pd, Ni, can reach 100% transformation efficiency under 650 ℃ and high-speed condition.Dimitris K.Liguras etc.
[2]Studied Ru, Rh, Pt, Pd load on Al
2O
3, MgO, TiO
2Last noble metal catalyst is to the performance of ethanol steam reforming reaction, and experimental result shows 5%Ru/Al
2O
3Near T=800 ℃, not only activity is very high, and hydrogen selective almost can reach 100%, and stability test to test this catalyzer very stable under stringent condition, can be used for fuel cell hydrogen manufacturing and Ru/Al
2O
3Compare Ru/TiO
2, Ru/MgO activity higher.S.Cavallaro etc.
[3-4]Systematic study Rh/Al
2O
3The application of catalyzer in ethanol steam reforming reaction, when T=734～923K, ethanol is restructured as principal reaction, and as T=780～850K, ethanol conversion is 100%.C.Diagne etc.
[5]Discover Rh/CeO
2, Rh/ZrO
2, Rh/CeO
2-ZrO
2Three kinds of catalyzer all demonstrate high activity and selectivity in the time of 400～500 ℃, in the time of 450 ℃, and Rh/ZrO
2During as catalyzer, H
2The output ratio reaches 71.7%.
Therefore reaction has certain activity to ethanol steam reforming to adopt noble metal catalyst, and wherein Ru, Rh's is active higher.But the temperature of reaction of noble metal catalyst is all very high, about about 600～800 ℃, is not suitable for the low temperature environment of fuel cell greatly; And the precious metal cost is high, and cost is too high, is difficult to realize in generally promoting the use of.
(2) adopt the catalyst based method of Cu
The Cu series catalysts is widely used in the reaction of methyl alcohol catalyzing manufacturing of hydrogen, because the similarity of ethanol and methyl alcohol, investigators study the Cu catalyzer.Mario etc.
[6]Studied Cu/Ni/K/ γ-Al under low temperature, the normal pressure
2O
3The alcohol steam reformed reactive activity of catalyzer has confirmed the Cu/Ni/K/ γ-Al of different activities component concentration
2O
3Catalyzer shows similar activity, has disclosed the dispersity that low Cu loading helps improving Cu.But the easy carbon distribution of Cu series catalysts, and generate more by product, as ethene etc., be unfavorable for hydrogen production process.
(3) adopt the catalyst based method of Ni
Jos é Comas etc.
[7]Investigated Ni/ γ-Al
2O
3Catalyzer experimental results show that in comparatively high temps (more than the 773K), higher H the activity of steam reforming reaction
2O/EtOH (6: 1), H
2The selection performance reach 91%, and strengthened the methane vapor reaction, limited the deposition of charcoal.But CO's is dense, is not suitable for the use of fuel cell.S.Freni etc.
[8,9]Having studied the Ni/MgO catalyzer has good reforming activity to ethanol steam reforming reaction discovery Ni/MgO catalyzer, and product hydrogen rate is very high, and selectivity can reach 95%.The alkali-metal structure that helps regulating catalyst that is added with, the adding of Li and Na has strengthened the reducing power of NiO, has influenced the distribution of Ni/MgO.Though and the adding of K has reduced the sintering of metal to the form and the not significantly effect that distributes, and has improved activity of such catalysts, stability, has reduced carbon distribution.C.V.V.Satyanarayana etc.
[10]Systematic study NiO-CeO
2-ZrO
2Catalyzer discovers that NiO (40wt%)-CeO2 (30wt%)-ZrO2 (30wt%) catalyzer shows good activity and stable in the reaction of ethanol steam reforming.Freni S.J. etc.
[11]With Ni/La
2O
3Be used for the alcoholic acid steam reforming reaction, when temperature reached 873K, ethanol conversion reached 100%, and the selectivity of hydrogen surpasses 90%, but this catalyzer needs that good catalytic performance is just arranged more than 823K, and temperature is high slightly.
Reaction has higher activity to the Ni series catalysts to ethanol steam reforming.Ethanol conversion and H
2Productive rate is all higher, and with respect to noble metal catalyst, temperature of reaction is lower, is ideal fuel cell catalyst for preparing hydrogen.But the selectivity of Ni series catalysts is undesirable, CH
4Relative with CO content more, methane competition hydrogen atom, CO are poisoned the Pt electrode of fuel cell, all are undesirable byproducts; And Ni series catalysts carbon distribution very easily.
(3) adopt the catalyst based method of Co
In the recent period, in alcohol steam reformed reaction, adopt the Co series catalysts method, attract much attention with its highly selective, methanation and the alcoholic acid of this highly selective by suppressing CO decomposes and shows
[12]The Co/Al that is studied at present
2O
3, Co/SiO, Co/MgO catalyzer all have higher initial activity and selectivity, but because the generation of carbon deposit can make catalyst stability not high, work-ing life is short
[13-14]In the recent period, most representative is kohei etc.
[15]The Co/SrTiO of research
3Catalyzer, this catalyzer has higher initial activity and selectivity, and has long stability.The Co series catalysts is to have the very ethanol steam reforming catalysts of high value in a word, if can make it to obtain at low temperatures higher activity, and overcome the catalyst deactivation that carbon distribution brings, and improve its stability, then will in fuel cell hydrogen manufacturing, occupy very important position.
Reference
[1]Breen?J?P，Burch?R，Coleman?H?M.Applied?Catalysis?B：Environmental，2002，39：65-74.
[2]Dimitris?K，Liguras，Dimitris?I，Kondarides，Xenophon?E，Verykios.AppliedCatalysis?B：Environmental，2003，43：345-354
[3]Cavallaro?S，Chiodo?V，Vita?V，Freni?S.Journal?of?Power?Sources，2003，123：10-16
[4]Cavallaro?S，Chiodo?V，Freni?S，Mondello?S，Frusteri?F.Applied?Catalysis?A：General，2003，249：119-128.
[5]Diagne?C，Idriss?H，Kiennemann?A.Catalysis?Communications，2002，3：565-571.
[6]Marino?F，Boveri?M，Baronetti?G，Laborde?M.Int.J.Hydrogen?Energy，2001，26：665-668
[7]JoséComas，Fernando
Miguel?Laborde，Norma?Amadeo.ChemicalEngineering?Journal，2004，98：61-68.
[8]Freni?S，Caval?laro?S，Mondello?N，Spadaro?L，Frusteri?F.Journal?of?PowerSources，2002，108：53-57.
[9]Frusteri?F，Freni?S，Chiodo?V，Spadaro?L，Bonura?G，Cavallaro?S.Journal?ofPower?Sources，2004，132：139-144.
[10]Srinivas?D，Satyanarayana?C?V?V，Potdar?H?S，Ratnasamy?P.Applied?CatalysisA：General，2003，246：323-334
[11]Freni?S.J.Power?Sources，2001，14-19
[12]Haga?F，Nakajima，Miyah，et?al[J]Catal?Lett，1997，48：223-227
[13]Marcelo?S，Batista，Rudye?K.S.Santos，Elisabete?M，Assaf，JoséM，Assaf，Edson?A，Ticianelli?Journal?of?Power?Sources，2003，124：99-103
[14]Marcelo?S，Batista，Rudye?K.S.Santos，Elisabete?M，Assaf，JoséM，Assaf，Edson?A，Ticianelli?Journal?of?Power?Sources，2004，134：27-32
[15]Kohei?Urasaki，Kazuhisa?Tokunaga，et?al.Chemistry?letters，2005，34(5)：668~669
Summary of the invention
The object of the present invention is to provide a kind of alcohol steam reformed method, this method has higher ethanol conversion and hydrogen selective and stable preferably.
The present invention is realized that by following technical proposals a kind of method of alcohol steam reformed hydrogen-producing is characterized in that comprising following process:
Be 0.1mm～10mm, Co at first with median size
3O
4Mass content is 5～30%, consumption is 50～500mg/cm
2Co
3O
4-CeO
2The catalyzer reactor of packing into, the H 5～20%
2-Ar gas mixture, 350 ℃～650 ℃ are reduced pre-treatment 40～120min; Feeding air speed to reactor then is 4,000ml/hgcat～120, and 000ml/hgcat, to consist of 10～30vol.% ratio be that 1: 1～1: 15 aqueous ethanolic solution and all the other are N
2Unstripped gas, realize the reactions of alcohol steam reformed hydrogen-producings normal pressure and 350～600 ℃.
The present invention has the following advantages: catalyzer is made up of cobalt, cerium mixed oxide, and cost of material is relatively low; Be used for the hydrogen production by ethanol steam reforming reaction and have high reactivity, highly selective and satisfactory stability, wherein coprecipitation method prepares 10wt% cobalt, cerium mixed oxide catalyst, and in the time of 450 ℃, ethanol conversion reaches 100%, every mol ethanol hydrogen output is 3.91mol, and every mol ethanol produces CH
4Amount is lower than 2%.
Embodiment
Embodiment 1:
Coprecipitation method prepares cobalt, cerium mixed oxide catalyst
Preparation process: (1) preparation 0.5mol/LCe (NO
3)
3Solution and 0.5mol/L Co (NO
3)
2Solution; (2) according to Co
3O
4Mass content is 1%～30%, measures quantitative Co (NO
3)
2Solution and Ce (NO
3)
3Solution mixes, and is mixed with different Co
3O
4The cobalt of mass content, cerium mixing solutions; (3) with yellow soda ash be precipitation agent, sodium carbonate solution and cobalt, cerium mixing solutions and the stream of 4mol/l is titrated to the pH value in the water of 7.5-8.5, constantly stir simultaneously, stir speed (S.S.) is about 100N/min.After titration finishes, through stir, aging, washing, dry, roasting, promptly obtain cobalt, the cerium mixed oxide catalyst of different cobalt contentss.
The catalyzer that adopts aforesaid method to make is used for the alcohol steam reformed hydrogen-producing process: at first with 10wt% cobalt, cerium mixed oxide catalyst 150mg/cm
3Pack in the reactor, use N
2Purged 10 minutes, and be converted to H then with 5%
2-Ar gas mixture with the temperature rise rate temperature programming to 650 of 10 ℃/min ℃, reduced 40 minutes under reducing atmosphere, realized catalyst reduction.Catalyzer cools to 350 ℃ under reducing atmosphere, feeding 20vol.% ratio is 3: 1 water and ethanol and 80vol.%N
2Unstripped gas, begin the reaction.The unstripped gas air speed is 40,000ml/h gcat, realize the alcohol steam reformed hydrogen-producing reaction at 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃ respectively, reactant gases enters SP2100 type gas-chromatography and carries out on-line analysis behind condensing works, discolour silica gel water absorber.Reaction result is as follows: when temperature of reaction is 350 ℃, and ethanol conversion 58.0%, every mol ethanol hydrogen output is 2.15mol, every mol ethanol produces CH
4Amount is 0.043mol; When temperature of reaction is 400 ℃, ethanol conversion 92.8%, every mol ethanol hydrogen output is 2.75mol, every mol ethanol produces CH
4Amount is 0.035mol; When temperature of reaction is 450 ℃, ethanol conversion 100%, every mol ethanol hydrogen output is 3.31mol, every mol ethanol produces CH
4Amount is 0.040mol; When temperature of reaction is 500 ℃, ethanol conversion 100%, every mol ethanol hydrogen output is 3.53mol, every mol ethanol produces CH
4Amount is 0.099mol; When temperature of reaction is 550 ℃, ethanol conversion 100%, every mol ethanol hydrogen output is 3.95mol, every mol ethanol produces CH
4Amount is 0.181mol; When temperature of reaction is 600 ℃, ethanol conversion 100%, every mol ethanol hydrogen output is 3.15mol, every mol ethanol produces CH
4Amount is 0.20mol.
Embodiment 2: reaction is preceding with 5wt% cobalt, cerium mixed oxide catalyst 150mg/cm
3Pack in the reactor, the reduction of catalyzer and other experiment condition are with embodiment 1, and reaction result is as follows: when temperature of reaction is 350 ℃, and ethanol conversion 42.1%, every mol ethanol hydrogen output is 2.11mol, does not have CH
4Generate; When temperature of reaction is 400 ℃, ethanol conversion 64.5%, every mol ethanol hydrogen output is 2.31mol, every mol ethanol produces CH
4Amount is 0.042mol; When temperature of reaction is 450 ℃, ethanol conversion 97.9%, every mol ethanol hydrogen output is 2.74mol, every mol ethanol produces CH
4Amount is 0.183mol; When temperature of reaction is 500 ℃, ethanol conversion 100%, every mol ethanol hydrogen output is 2.75mol, every mol ethanol produces CH
4Amount is 0.25mol; When temperature of reaction is 550 ℃, ethanol conversion 100%, every mol ethanol hydrogen output is 2.78mol, every mol ethanol produces CH
4Amount is 0.29mol; When temperature of reaction is 600 ℃, ethanol conversion 100%, every mol ethanol hydrogen output is 2,90mol, every mol ethanol produces CH
4Amount is 0.29mol.
Embodiment 3: reaction is preceding with 30wt% cobalt, cerium mixed oxide catalyst 150mg/cm
3Pack in the reactor, the reduction of catalyzer and other experiment condition are with embodiment 1, and reaction result is as follows: when temperature of reaction is 350 ℃, and ethanol conversion 47.6%, every mol ethanol hydrogen output is 2.15mol, every mol ethanol produces CH
4Amount is 0.042mol; When temperature of reaction is 400 ℃, ethanol conversion 78.9%, every mol ethanol hydrogen output is 2.34mol, every mol ethanol produces CH
4Amount is 0.035mol; When temperature of reaction is 450 ℃, ethanol conversion 97.0%, every mol ethanol hydrogen output is 2.60mol, every mol ethanol produces CH
4Amount is 0.043mol; When temperature of reaction is 500 ℃, ethanol conversion 100%, every mol ethanol hydrogen output is 2.85mol, every mol ethanol produces CH
4Amount is 0.170mol; When temperature of reaction is 550 ℃, ethanol conversion 100%, every mol ethanol hydrogen output is 2.98mol, every mol ethanol produces CH
4Amount is 0.22mol; When temperature of reaction is 600 ℃, ethanol conversion 100%, every mol ethanol hydrogen output is 3.15mol, every mol ethanol produces CH
4Amount is 0.29mol.
Embodiment 4: implementation process just changes reduction temperature into 350 ℃ with embodiment 1, and reaction result is as follows: when temperature of reaction is 350 ℃, and ethanol conversion 48.0%, every mol ethanol hydrogen output is 1.50mol, does not have CH
4Generate; When temperature of reaction is 400 ℃, ethanol conversion 69.8%, every mol ethanol hydrogen output is 2.48mol, every mol ethanol produces CH
4Amount is 0.024mol; When temperature of reaction is 450 ℃, ethanol conversion 95.4%, every mol ethanol hydrogen output is 2.46mol, every mol ethanol produces CH
4Amount is 0.043mol; When temperature of reaction is 500 ℃, ethanol conversion 98.5%, every mol ethanol hydrogen output is 2.68mol, every mol ethanol produces CH
4Amount is 0.075mol; When temperature of reaction is 550 ℃, ethanol conversion 100%, every mol ethanol hydrogen output is 3.06mol, every mol ethanol produces CH
4Amount is 0.156mol; When temperature of reaction is 600 ℃, ethanol conversion 100%, every mol ethanol hydrogen output is 3.11mol, every mol ethanol produces CH
4Amount is 0.248mol.
Embodiment 5: implementation process just becomes 120 with the unstripped gas air speed with embodiment 1,000ml/h gcat, and reaction result is as follows: when temperature of reaction is 350 ℃, ethanol conversion 35.8%, every mol ethanol hydrogen output is 0.39mol, does not have CH
4Generate; When temperature of reaction is 400 ℃, ethanol conversion 56.1%, every mol ethanol hydrogen output is 1.51mol, does not have CH
4Generate; When temperature of reaction is 450 ℃, ethanol conversion 82.1%, every mol ethanol hydrogen output is 2.20mol, does not have CH
4Generate; When temperature of reaction is 500 ℃, ethanol conversion 85.7%, every mol ethanol hydrogen output is 2.39mol, every mol ethanol produces CH
4Amount is 0.027mol; When temperature of reaction is 550 ℃, ethanol conversion 91.5%, every mol ethanol hydrogen output is 3.11mol, every mol ethanol produces CH
4Amount is 0.10mol; When temperature of reaction is 600 ℃, ethanol conversion 100%, every mol ethanol hydrogen output is 3.10mol, every mol ethanol produces CH
4Amount is 0.25mol.
Embodiment 6: implementation process is with embodiment 1, and just the ratio with water and alcoholic acid mixture becomes 8: 1, and reaction result is as follows: when temperature of reaction is 350 ℃, and ethanol conversion 60.1%, every mol ethanol hydrogen output is 2.26mol, does not have CH
4Generate; When temperature of reaction is 400 ℃, ethanol conversion 96.8%, every mol ethanol hydrogen output is 2.93mol, every mol ethanol produces CH
4Amount is 0.031mol; When temperature of reaction is 450 ℃, ethanol conversion 100%, every mol ethanol hydrogen output is 3.91mol, every mol ethanol produces CH
4Amount is 0.038mol; When temperature of reaction is 500 ℃, ethanol conversion 100%, every mol ethanol hydrogen output is 4.01mol, every mol ethanol produces CH
4Amount is 0.10mol; When temperature of reaction is 550 ℃, ethanol conversion 100%, every mol ethanol hydrogen output is 3.95mol, every mol ethanol produces CH
4Amount is 0.165mol; When temperature of reaction is 600 ℃, ethanol conversion 100%, every mol ethanol hydrogen output is 3.91mol, every mol ethanol produces CH
4Amount is 0.23mol.
Embodiment 7: experiment condition is with embodiment 1, and just in reaction, each was reacted 1 hour down at 350 ℃ and 400 ℃ by elder generation, reacted 10h down at 450 ℃ then, continued to react 50h down at 500 ℃ again.Reaction result is as follows: 450 ℃ of reactions 10 hours, ethanol conversion slightly dropped to 90% from 100%, and when continuing to be warmed up to 500 ℃, ethanol conversion reaches 100%, and remained to and do not change in 50 hours; H in the product
2Content remains on more than 60%, CO
2Content is more than 20%, and methane content remains on below 4%.Produce H from the mol ethanol of reaction
2And CO
2Take temperature molH in the time of 450 ℃
2Output is at 2.5mol/mol C
2H
5About OH, molH in the time of 500 ℃
2Output is at 3mol/mol C
2H
5More than the OH, molCO
2Output is at 1mol/mol C in the time of 500 ℃
2H
5More than the OH, be much higher than the catalyzer of other carrier.Experimental result shows, the Co/CeO of our preparation
2Catalyzer has shown reasonable stability, and in test process, kept higher activity and preferably product form.CeO is described
2The adding of carrier has improved the stability of catalyzer significantly.
Claims (1)
1. the method for an alcohol steam reformed hydrogen-producing is characterized in that comprising following process: be 0.1mm～10mm, Co with median size at first
3O
4Mass content is 5～30%, consumption is 50～500mg/cm
2Co
3O
4-CeO
2The catalyzer reactor of packing into, the H 5～20%
2-Ar gas mixture, 350 ℃～650 ℃ are reduced pre-treatment 40～120min; Feeding air speed to reactor then is 4,000ml/hg
Cat～120,000ml/hg
Cat, to consist of 10～30vol.% ratio be that 1: 1～1: 15 aqueous ethanolic solution and all the other are N
2Unstripped gas, realize the reactions of alcohol steam reformed hydrogen-producings normal pressure and 350～600 ℃.
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|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100130354A CN100395174C (en) | 2006-01-12 | 2006-01-12 | Process for reforming mfg. hydrogen by ethyl alcohol vapour |
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| Publication Number | Publication Date |
|---|---|
| CN1792766A true CN1792766A (en) | 2006-06-28 |
| CN100395174C CN100395174C (en) | 2008-06-18 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103752318A (en) * | 2013-12-26 | 2014-04-30 | 内蒙古工业大学 | Mesoporous Co/CeO2 catalyst for hydrogen preparation reaction by reforming ethanol vapor and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63182033A (en) * | 1987-01-21 | 1988-07-27 | Mitsubishi Heavy Ind Ltd | Ethanol reforming catalyst |
| FR2795339B1 (en) * | 1999-06-24 | 2001-09-21 | Peugeot Citroen Automobiles Sa | CATALYST AND METHOD FOR REFORMING ETHANOL AND FUEL CELL SYSTEM USING THE SAME |
| CN1544310A (en) * | 2003-11-26 | 2004-11-10 | 北京理工大学 | Ethanol vapour reforming reaction catalyzer for making hydrogen and its use method |
-
2006
- 2006-01-12 CN CNB2006100130354A patent/CN100395174C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103752318A (en) * | 2013-12-26 | 2014-04-30 | 内蒙古工业大学 | Mesoporous Co/CeO2 catalyst for hydrogen preparation reaction by reforming ethanol vapor and preparation method thereof |
| CN103752318B (en) * | 2013-12-26 | 2016-03-16 | 内蒙古工业大学 | For the mesoporous Co/CeO of hydrogen production by ethanol steam reforming reaction 2catalysts and its preparation method |
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|---|---|
| CN100395174C (en) | 2008-06-18 |
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