CN102530858B - Method for preparing hydrogen by alcohol - Google Patents
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- CN102530858B CN102530858B CN201110111467.XA CN201110111467A CN102530858B CN 102530858 B CN102530858 B CN 102530858B CN 201110111467 A CN201110111467 A CN 201110111467A CN 102530858 B CN102530858 B CN 102530858B
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Abstract
The invention provides a method for preparing hydrogen by alcohol, which comprises the steps of: mixing the alcohol with alkali under the temperature of 100-400 DEG C, and reacting the alcohol with the alkali to obtain the hydrogen in reaction products. According to the preparation method provided by the invention, the gaseous product does not contain by-products such as CO and CO2, and impurity removal operation is not needed to be carried out on the products again, so that the cost is reduced. In addition, the preparation method provided by the invention is milder in condition, and can be used for preparing the hydrogen without needing noble metal catalyst, so that the cost is remarkably reduced.
Description
Technical field
The present invention relates to organic synthesis field, be specifically related to a kind of method of alcohol hydrogen.
Background technology
The energy is the important substance basis of human survival and development, and the oil that people mainly use at present, Sweet natural gas, coal etc. all belong to non-renewable fossil energy.Due to the unconfined exploitation of the mankind, fossil energy is gradually in exhaustion.On the other hand, these fuel of use without restriction, also bring serious environmental problem, as acid rain, and Greenhouse effect etc.Therefore the extremely urgent problem that new reproducible clear energy sources is facing mankind is found.
Clean utilization for the energy, as the desirable energy carrier that can obtain from number of ways, is brought new change by hydrogen.Fuel with routine is compared, and hydrogen is the oil substitutes that people are desirable in the heart as the free of contamination renewable energy source of cleaning always.From the development trend of world energy sources, over nearly 20 years, the development and utilization work of Hydrogen Energy has obtained and has developed rapidly.Therefore, research Hydrogen Energy and correlation technique thereof are of great immediate significance.
At present, the industrial hydrogen of most domestic obtains by brine electrolysis, although this method raw material is easy to get, can consume a large amount of electric energy, and can not get higher purity.Due to alcohols wide material sources, nontoxic and hydrogen productive rate is higher, be the method that alternative electrolytic process prepares hydrogen, thus the development of alcohol hydrogen producing technology receives special concern.Low temperature highly selective obtains the Focal point and difficult point that hydrogen is hydrogen producing technology research from alcohol.Prepare the object of hydrogen to reach low temperature highly selective, technology the most frequently used is at present by obtaining hydrogen to the reformation of alcohol under the existence of noble metal catalyst, but hydrogen prepared by this method can generate CO simultaneously
2, and association CO, wherein CO amount is relevant with used catalyst and reaction conditions.The hydrogen prepared in this way if make is applied in the preparation of fuel cell, and CO will certainly make cell noble metal catalysts poisoning and have a strong impact on the performance of battery.
Hydrogen making suppress CO generation aspect in a mild condition, the people such as G.A.Deluga adopt rhodium/cerium dioxide as catalyzer, and catalyzed oxidation dehydrated alcohol or aqueous ethanol obtain hydrogen and CO and CO
2mixture, hydrogen and the CO that purity is 95% can obtained through subsequent high temperature water-gas shift
2by product (Renewable Hydrogen from Ethanol byAutothermal Reforming.Science 2004,303:993).The noble metal catalyst used in process significantly can increase product hydrogen cost, has a small amount of CO on the other hand and produces.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of alcohol to prepare the method for hydrogen, and prior art of comparing, does not use noble metal catalyst.Not containing CO and CO in the hydrogen of preparation
2by product.
In order to solve prior art problem, the invention provides a kind of method that hydrogen prepared by alcohol, comprising:
By alcohol and alkali mixing, obtain solidliquid mixture;
Alcohol in described solidliquid mixture and alkali react, and obtain reaction product; Described reaction product comprises hydrogen; The temperature of described mixing is 100 ~ 400 DEG C.
Preferably, the temperature 120 ~ 240 DEG C of described mixing.
Preferably, described reaction product also comprises the carboxylate salt of alkali-metal carboxylate salt and/or alkaline-earth metal and a small amount of CH
4, C
2h
6.。
Preferably, described alcohol to be carbon atom number be 1 ~ 18 unitary or polyvalent alcohol.
Preferably, described alkali is oxyhydroxide or the alcoholate of basic metal or alkaline-earth metal.
Preferably, the reaction times that described alcohol and alkali react is 0.1 ~ 6h.
Preferably, be also included in described solidliquid mixture and add catalyzer.
Preferably, described catalyzer comprises: any one or more in nickel, palladium, platinum, ruthenium, rhodium, iridium, cobalt, iron, osmium.
Preferably, described catalyzer also comprises one or more in IB race, IIB race, group vib, VIIB race and group of the lanthanides, actinium series rare earth metal or rare-earth oxide.
The method that hydrogen prepared by alcohol provided by the invention is mixed at 100 ~ 400 DEG C alcohol and alkali, and alcohol and alkali reaction obtain reaction product and comprise hydrogen.Preparation method provided by the invention, the hydroxide radical attack alcoholic extract hydroxyl group in alkali, generates a part water and an alcohol ion.Alcohol ion and water rapid reaction generate hydrogen, aldehyde and hydroxide ion.Hydroxide ion is added in the carbonyl carbon of aldehyde by nucleophilic addition(Adn) again, is obtained by reacting a part alcohol and a part carboxylate salt through Connizzaro (Cannizzaro).Therefore CO and CO is not contained in the gaseous product that prepared by the present invention
2deng by product, need not carry out, except miscellaneous operation, reducing cost to product again.Preparation method's condition provided by the invention is gentleer in addition, does not need noble metal catalyst just can prepare hydrogen.
Accompanying drawing explanation
The gas chromatogram of gas in the reaction product that Fig. 1 embodiment of the present invention 1 obtains
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiments of the invention are described, but should be appreciated that these describe just as further illustrating the features and advantages of the present invention instead of the restriction to patent requirements of the present invention.
The invention provides a kind of method of alcohol hydrogen, use alcohol and alkali hybrid reaction at 100 ~ 400 DEG C, obtain reaction product, described reaction product comprises solid product and gaseous product.Wherein, described solid product comprises the carboxylate salt of basic metal and/or alkaline-earth metal, and gaseous product comprises hydrogen and a small amount of CH
4, C
2h
6.In order to further illustrate alkali of the present invention and alcohol reaction process, the reaction process of ethanol and sodium hydroxide is preferably used to set forth.
Be below the reaction formula of ethanol and sodium hydroxide:
C
2h
5oH+NaOH → 2H
2individual+CH
3cOONa.
Reaction mechanism is such as formula shown in (1) and formula (2):
Through type (1) and formula (2) can be found out, at a certain temperature, alkali attack alcoholic extract hydroxyl group, generates a part water and an alcohol ion, and the meeting of alcohol ion instability and water rapid reaction generate hydrogen, aldehyde and hydroxide ion.Hydroxide ion is added in the carbonyl carbon of aldehyde by nucleophilic addition(Adn) again, is obtained by reacting a part alcohol and a part carboxylate salt through Connizzaro (Cannizzaro).Can be learnt by above-mentioned reaction formula, preparation method provided by the invention can also obtain carboxylate salt while obtaining hydrogen, and the carbon in raw alcohol can be fixed in carboxylate salt completely, can not with CO or CO
2form exist, fuel cell can not be made poisoning, and described gaseous product can directly use, and without removal of impurities.In addition, preparation method provided by the invention only can carry out at a certain temperature, can not use noble metal catalyst, save cost.
According to the present invention, the temperature of the mixing of described alcohol and alkali is 100 ~ 400 DEG C, and actual temp is with the kind of alcohol, the kind of alkali and whether add catalyzer etc. and fixed, if add catalyzer, temperature alkali and alcohol mixing temperature reduce.The present invention is preferably 120 ~ 240 DEG C, and this temperature range prepares the high temperature of more than 600 DEG C of hydrogen needs in prior art, reduces energy consumption.Mixing temperature presentation mode of the present invention can be by heating while alcohol and alkali mixing, also can mix after alcohol heating with alkali.Be preferably according to alcohol of the present invention unitary or the polyvalent alcohol that carbon atom number is 1 ~ 18, be more preferably methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, hexalin etc.The alcohol that the present invention uses can be the aqueous alcohol that absolute alcohol can be also 20wt% ~ 50wt% for water content.
According to the present invention, described alkali is preferably oxyhydroxide or the alcoholate of basic metal and/or alkaline-earth metal, is more preferably sodium hydroxide, potassium hydroxide, calcium hydroxide or sodium ethylate etc.Select the stronger alkali of alkalescence, namely hydroxide radical and basic metal or alkaline-earth metal ions easily ionizable, easily make reaction carry out.
According to the present invention, the reaction times that described alcohol and alkali react is preferably 0.1 ~ 6h.Be more preferably 0.5 ~ 3h.Concrete reaction is with the kind of alcohol, the kind of alkali and whether add catalyzer etc. and fixed, if add catalyzer, the reaction times can corresponding minimizing.
According to the present invention, although preparation method provided by the invention can not use catalyzer, whether can not use catalyzer, add catalyzer and can reduce temperature of reaction further, accelerate speed of reaction, and improve hydrogen purity.Whether the interpolation of catalyzer is depending on production cost.The present invention adds catalyzer in solidliquid mixture.Described catalyzer comprises by any one or more Primary Catalysts formed in nickel, palladium, platinum, ruthenium, rhodium, iridium, cobalt, iron, osmium, has also preferably included the cocatalyst of one or more compositions in IB race, IIB race, group vib, VIIB race and group of the lanthanides, actinium series rare earth metal or rare-earth oxide.Described catalyzer can appendix on micropore or mesoporous supports.
The method of a kind of alcohol hydrogen provided by the invention, can not use noble metal catalyst, with low cost.The H produced
2purity is higher, and not containing CO, CO in gas
2, can fuel cell field be directly used in.Coproduction carboxylate salt while preparing hydrogen, without greenhouse gas emission in whole process, the theoretical yield of carbon is 100%.Technique is simple, low for equipment requirements, can large-scale industrial production.
In order to further illustrate the solution of the present invention, below will set forth with specific embodiment.It should be noted that, the raw material that the present invention uses is all purchased from Chemical Reagent Co., Ltd., Sinopharm Group.
Embodiment 1
Take dehydrated alcohol 10 parts and sodium hydrate solid 1 part respectively in reactor, with nitrogen by emptying for air in still, be airtightly warming up to 220 DEG C, keep 2h.Be cooled to room temperature and collect gas.
Gas chromatographic analysis is carried out to gaseous product prepared by the present embodiment, obtains a result as shown in embodiment in table 11.Fig. 1 is the gas-chromatography spectrogram of gaseous product prepared by the present embodiment.
Embodiment 2
Take dehydrated alcohol 10 parts and sodium hydrate solid 1 part respectively in reactor, with nitrogen by emptying for air in still, be airtightly warming up to 240 DEG C, keep 2h.Be cooled to room temperature and collect gas.Gas chromatographic analysis is carried out to gaseous product prepared by the present embodiment, obtains a result as shown in embodiment in table 12.
Embodiment 3
Take moisture 20% ethanol 10 parts and sodium hydrate solid 1 part respectively in reactor, with nitrogen by emptying for air in still, be airtightly warming up to 240 DEG C, keep 2h.Gas is collected after being cooled to room temperature.Gas chromatographic analysis is carried out to gaseous product prepared by the present embodiment, obtains a result as shown in embodiment in table 13.
Embodiment 4
Take respectively without moisture 50% ethanol 10 parts and sodium hydrate solid 1 part in reactor, with nitrogen by emptying for air in still, be airtightly warming up to 240 DEG C, keep 2h.Gas is collected after being cooled to room temperature.Gas chromatographic analysis is carried out to gaseous product prepared by the present embodiment, obtains a result as shown in embodiment in table 14.
Embodiment 5
Take anhydrous methanol 10 parts and sodium hydrate solid 1 part respectively in reactor, with nitrogen by emptying for air in still, be airtightly warming up to 240 DEG C, keep 2h.Be cooled to room temperature and collect gas.Gas chromatographic analysis is carried out to gaseous product prepared by the present embodiment, obtains a result as shown in embodiment in table 15.
Embodiment 6
Take glycerol 10 parts and sodium hydrate solid 1 part respectively in reactor, with nitrogen by emptying for air in still, be airtightly warming up to 190 DEG C, keep 2h.Gas is collected after being cooled to room temperature.Gas chromatographic analysis is carried out to gaseous product prepared by the present embodiment, obtains a result as shown in embodiment in table 16.
Embodiment 7
Take dehydrated alcohol 10 parts and calcium hydroxide solid 1 part respectively in reactor, with nitrogen by emptying for air in still, be airtightly warming up to 240 DEG C, keep 2h.Be cooled to room temperature and collect gas.Gas chromatographic analysis is carried out to gaseous product prepared by the present embodiment, obtains a result as shown in embodiment in table 17.
Embodiment 8
Take dehydrated alcohol 10 parts and sodium hydrate solid 1 part respectively in reactor, then add a small amount of Pd/C catalyzer, with nitrogen by emptying for air in still, be airtightly warming up to 200 DEG C, keep 2h.Be cooled to room temperature and collect gas.Gas chromatographic analysis is carried out to gaseous product prepared by the present embodiment, obtains a result as shown in embodiment in table 18.
Embodiment 9
Take 10 parts, anhydrous butanols and sodium hydrate solid 1 part respectively in reactor, with nitrogen by emptying for air in still, be airtightly warming up to 200 DEG C, keep 1h.Be cooled to room temperature and collect gas.Gas chromatographic analysis is carried out to gaseous product prepared by the present embodiment, obtains a result as shown in embodiment in table 19.
Embodiment 10
Take anhydrous hexalin 10 parts and sodium hydrate solid 1 part respectively in reactor, with nitrogen by emptying for air in still, be airtightly warming up to 180 DEG C, keep 1h.Be cooled to room temperature and collect gas.Gas chromatographic analysis is carried out to gaseous product prepared by the present embodiment, obtains a result as shown in embodiment in table 1 10.
Embodiment 11
Ethanol heating is become steam by being heated to 240 DEG C and being equipped with the tube furnace of sodium hydroxide, cool in outlet and collect noncondensable gas, detection is mainly hydrogen.
Gaseous product composition prepared by table 1 embodiment 1 ~ 8 and content
Other is other hydro carbons
As can be seen from Table 1, in alcohol, add water the purity of hydrogen can be made to increase, cheap bio-ethanol (aqueous ethanol) thus can be used to replace dehydrated alcohol, can reduce costs.And CO do not detected, CO in the gas produced
2, therefore the hydrogen obtained can be applicable to fuel cell.
The solid product be obtained by reacting is corresponding metal carboxylate.
The method that hydrogen prepared by alcohol provided by the invention is mixed at 100 ~ 400 DEG C alcohol and alkali, and alcohol and alkali reaction obtain reaction product and comprise hydrogen.Preparation method provided by the invention, the hydroxide radical attack alcoholic extract hydroxyl group in alkali, generates a part water and an alcohol ion.Alcohol ion and water rapid reaction generate hydrogen, aldehyde and hydroxide ion.Hydroxide ion is added in the carbonyl carbon of aldehyde by nucleophilic addition(Adn) again, is obtained by reacting a part alcohol and a part carboxylate salt through Connizzaro (Cannizzaro).Therefore CO and CO is not contained in the gaseous product that prepared by the present invention
2deng by product, need not carry out, except miscellaneous operation, reducing cost to product again.Preparation method's condition provided by the invention is gentleer in addition, does not need noble metal catalyst just can prepare hydrogen.
Above the method that hydrogen prepared by a kind of alcohol provided by the invention is described in detail; apply specific case herein to set forth principle of the present invention and embodiment; the explanation of above embodiment just understands method of the present invention and core concept thereof for helping; should be understood that; for those skilled in the art; under the premise without departing from the principles of the invention; can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (3)
1. prepare a method for hydrogen with alcohol, it is characterized in that, comprising:
By alcohol and alkali mixing, obtain solidliquid mixture;
Alcohol in described solidliquid mixture and alkali react, under the condition not using catalyzer, air is emptying, and airtight intensification obtains reaction product; Described alkali is oxyhydroxide or the alcoholate of basic metal or alkaline-earth metal; Described reaction product comprises carboxylate salt and the CH of hydrogen and alkali-metal carboxylate salt and/or alkaline-earth metal
4, C
2h
6; The temperature of described intensification is 180 ~ 400 DEG C.
2. the method for hydrogen prepared by alcohol according to claim 1, it is characterized in that, described alcohol to be carbon atom number be 1 ~ 18 unitary or polyvalent alcohol.
3. the method for hydrogen prepared by alcohol according to claim 1, it is characterized in that, the reaction times that described alcohol and alkali react is 0.1 ~ 6h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110111467.XA CN102530858B (en) | 2011-04-29 | 2011-04-29 | Method for preparing hydrogen by alcohol |
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|---|---|---|---|
| CN201110111467.XA CN102530858B (en) | 2011-04-29 | 2011-04-29 | Method for preparing hydrogen by alcohol |
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| CN102530858B true CN102530858B (en) | 2015-01-07 |
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| FR3072303B1 (en) * | 2017-10-18 | 2019-11-01 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | APPARATUS FOR GENERATING A GAS |
| CN111153788A (en) * | 2018-11-08 | 2020-05-15 | 中国科学院大连化学物理研究所 | Method for preparing organic acid through organic alcohol dehydrogenation reaction and method for thermodynamically controlling organic alcohol dehydrogenation reaction |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6607707B2 (en) * | 2001-08-15 | 2003-08-19 | Ovonic Battery Company, Inc. | Production of hydrogen from hydrocarbons and oxygenated hydrocarbons |
| US6994839B2 (en) * | 2001-08-15 | 2006-02-07 | Ovonic Battery Company, Inc. | Carbonate recycling in a hydrogen producing reaction |
| CN101248005A (en) * | 2005-06-23 | 2008-08-20 | Grdc有限责任公司 | Effective hydrogen production |
| CN101264447A (en) * | 2008-04-30 | 2008-09-17 | 复旦大学 | Nickel-boehmite composite catalyst for ethylene glycol liquid phase reforming reaction and preparation thereof |
| CN101275233B (en) * | 2007-12-27 | 2010-12-15 | 复旦大学 | Hydrogen production method using alcohol as raw material |
-
2011
- 2011-04-29 CN CN201110111467.XA patent/CN102530858B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6607707B2 (en) * | 2001-08-15 | 2003-08-19 | Ovonic Battery Company, Inc. | Production of hydrogen from hydrocarbons and oxygenated hydrocarbons |
| US6994839B2 (en) * | 2001-08-15 | 2006-02-07 | Ovonic Battery Company, Inc. | Carbonate recycling in a hydrogen producing reaction |
| CN101248005A (en) * | 2005-06-23 | 2008-08-20 | Grdc有限责任公司 | Effective hydrogen production |
| CN101275233B (en) * | 2007-12-27 | 2010-12-15 | 复旦大学 | Hydrogen production method using alcohol as raw material |
| CN101264447A (en) * | 2008-04-30 | 2008-09-17 | 复旦大学 | Nickel-boehmite composite catalyst for ethylene glycol liquid phase reforming reaction and preparation thereof |
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