CN102530858A - Method for preparing hydrogen by alcohol - Google Patents
Method for preparing hydrogen by alcohol Download PDFInfo
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- CN102530858A CN102530858A CN201110111467XA CN201110111467A CN102530858A CN 102530858 A CN102530858 A CN 102530858A CN 201110111467X A CN201110111467X A CN 201110111467XA CN 201110111467 A CN201110111467 A CN 201110111467A CN 102530858 A CN102530858 A CN 102530858A
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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 the organic synthesis field, be specifically related to a kind of method of pure hydrogen.
Background technology
The energy is the important substance basis of human survival and development, and the main at present oil that uses of people, Sweet natural gas, coal etc. all belong to non-renewable fossil energy.Because human unconfined exploitation, fossil energy is gradually in exhaustion.On the other hand, do not add these fuel of use of restriction, bring serious environmental problem yet, like acid rain, Greenhouse effect etc.Therefore seek the extremely urgent problem that new reproducible clear energy sources is a face of mankind.
Hydrogen will bring new change for the clean utilization of the energy as the desirable energy carrier that can obtain from number of ways.Fuel with routine is compared, and hydrogen is people's ideal oil substitutes in the heart as clean non-pollution of renewable energy always.See that from the development trend of world energy sources the development and utilization work of Hydrogen Energy has obtained to develop rapidly over nearly 20 years.Therefore, research Hydrogen Energy and correlation technique thereof are of great immediate significance.
At present, the industrial hydrogen of most domestic makes by brine electrolysis, though this method raw material is easy to get, can consume a large amount of electric energy, and can not get higher purity.Because the alcohols wide material sources, nontoxic and the hydrogen productive rate is higher, be the method that alternative electrolytic process prepares hydrogen, thereby the development of pure hydrogen producing technology receive special concern.The low temperature highly selective obtains emphasis and the difficult point that hydrogen is hydrogen producing technology research from alcohol.In order to reach the purpose of low temperature highly-selective preparation hydrogen, the most frequently used technology is in the presence of noble metal catalyst, to obtain hydrogen through the reformation to alcohol at present, but the hydrogen of this method preparation can generate CO simultaneously
2, and association CO, wherein the CO amount is relevant with catalyst system therefor and reaction conditions.Make in this way the hydrogen of preparation if be applied in the preparation of fuel cell, CO will certainly make the battery noble metal catalyst poison and have a strong impact on the performance of battery.
Under mild conditions, produce hydrogen and suppress aspect the CO generation, people such as G.A.Deluga adopt rhodium/cerium dioxide as catalyzer, and catalyzed oxidation absolute ethyl alcohol or aqueous ethanol obtain hydrogen and CO and CO
2Mixture, through follow-up high-temperature water gas conversion can to obtain purity be 95% hydrogen and CO
2By product (Renewable Hydrogen from Ethanol byAutothermal Reforming.Science 2004,303:993).Employed noble metal catalyst can significantly increase product hydrogen cost in the process, has a small amount of CO on the other hand and produces.
Summary of the invention
It is a kind of with the pure method for preparing hydrogen that the technical problem that the present invention will solve is to provide, and the prior art of comparing is not used noble metal catalyst.Do not contain CO and CO in the hydrogen of preparation
2By product.
In order to solve the prior art problem, the invention provides a kind of method of using alcohol to prepare hydrogen, comprising:
Pure and mild alkali is mixed, obtain solidliquid mixture;
Pure and mild alkali in the said solidliquid mixture reacts, and obtains reaction product; Said reaction product comprises hydrogen; Said blended temperature is 100～400 ℃.
Preferably, said blended temperature is 120～240 ℃.
Preferably, said reaction product also comprises carboxylate salt and a small amount of CH of alkali-metal carboxylate salt and/or earth alkali metal
4, C
2H
6。
Preferably, said alcohol is 1～18 monobasic or polyvalent alcohol for the carbon atom number.
Preferably, said alkali is the oxyhydroxide or the alcoholate of basic metal or earth alkali metal.
Preferably, reaction times of reacting of said pure and mild alkali is 0.1～6h.
Preferably, also be included in the said solidliquid mixture and add catalyzer.
Preferably, said catalyzer comprises: any one or more in nickel, palladium, platinum, ruthenium, rhodium, iridium, cobalt, iron, the osmium.
Preferably, said catalyzer also comprises one or more in IB family, IIB family, group vib, VIIB family and group of the lanthanides, actinium series rare earth metal or the rare-earth oxide.
Provided by the invention is that pure and mild alkali is mixed down at 100～400 ℃ with the pure method for preparing hydrogen, and pure and mild alkali reaction obtains comprising in the reaction product hydrogen.Preparing method provided by the invention, the hydroxide radical attack alcoholic extract hydroxyl group in the alkali generates a part water and a pure ion.Alcohol ion and water rapid reaction generate hydrogen, aldehyde and hydroxide ion.Hydroxide ion is added on the carbonyl carbon of aldehyde through nucleophilic addition(Adn) again, obtains the pure and mild a part carboxylate salt of a part through Connizzaro (Cannizzaro) reaction.Therefore do not contain CO and CO in the gaseous product of the present invention's preparation
2Deng by product, need not remove miscellaneous operation to product again, reduced cost.Preparing method's condition provided by the invention in addition is gentle, does not need noble metal catalyst just can prepare hydrogen.
Description of drawings
The gas chromatogram of gas in the reaction product that Fig. 1 embodiment of the invention 1 obtains
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiments of the invention are described, but should be appreciated that these just restriction for further specifying feature and advantage of the present invention rather than patent of the present invention being required is described.
The invention provides the method for the pure hydrogen of a kind of usefulness, use alcohol and alkali 100～400 ℃ of following hybrid reactions, obtain reaction product, said reaction product comprises solid product and gaseous product.Wherein, said solid product comprises the carboxylate salt of basic metal and/or earth alkali metal, and gaseous product comprises hydrogen and a small amount of CH
4, C
2H
6In order to further specify alkali of the present invention and pure reaction process, preferably use the reaction process of ethanol and sodium hydroxide to set forth.
Below be the reaction formula of ethanol and sodium hydroxide:
C
2H
5OH+NaOH → 2H
2Individual+CH
3COONa.
Reaction mechanism is suc as formula shown in (1) and the formula (2):
Through type (1) and formula (2) can find out that at a certain temperature, alkali attack alcoholic extract hydroxyl group generates a part water and a pure ion, and unstable meeting of pure ion and water rapid reaction generate hydrogen, aldehyde and hydroxide ion.Hydroxide ion is added on the carbonyl carbon of aldehyde through nucleophilic addition(Adn) again, obtains the pure and mild a part carboxylate salt of a part through Connizzaro (Cannizzaro) reaction.Can learn that through above-mentioned reaction formula preparation method provided by the invention can also obtain carboxylate salt when obtaining hydrogen, and the carbon in the raw alcohol can be fixed on fully in the carboxylate salt, can be with CO or CO
2Form exist, fuel cell is poisoned, said 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, has practiced thrift cost.
According to the present invention, the blended temperature of said pure and mild alkali is 100～400 ℃, and actual temp is with the kind of the kind of alcohol, alkali and whether add catalyzer etc. and decide, and then temperature alkali and pure mixing temperature reduce if add catalyzer.The present invention is preferably 120～240 ℃, and this temperature range prepares the high temperature more than 600 ℃ that hydrogen needs in prior art, reduced energy consumption.Mixing temperature presentation mode of the present invention can also can be mixed alcohol heating back for pure and mild alkali blended is heated simultaneously with alkali.Being preferably the carbon atom number according to alcohol according to the invention is 1～18 monobasic or polyvalent alcohol, more preferably methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, hexalin etc.The alcohol that the present invention uses can also can be the aqueous alcohol of water cut as 20wt%～50wt% as absolute alcohol.
According to the present invention, said alkali is preferably the oxyhydroxide or the alcoholate of basic metal and/or earth alkali metal, more preferably sodium hydroxide, Pottasium Hydroxide, calcium hydroxide or sodium ethylate etc.Select the stronger alkali of alkalescence, promptly hydroxide radical and basic metal or alkaline earth metal ion easily ionizable make reaction carry out easily.
According to the present invention, the reaction times that said pure and mild alkali reacts is preferably 0.1～6h.0.5～3h more preferably.Concrete reaction is with the kind of the kind of alcohol, alkali and whether add catalyzer etc. and decide, if add the then corresponding minimizing of reaction times meeting of catalyzer.
According to the present invention, though preparation method provided by the invention can not use catalyzer, whether can not use catalyzer, add catalyzer and can further reduce temperature of reaction, accelerate speed of reaction and improve hydrogen purity.Whether the interpolation of catalyzer is looked production cost and is decided.The present invention adds catalyzer in solidliquid mixture.Said catalyzer comprises by any one or more Primary Catalysts formed in nickel, palladium, platinum, ruthenium, rhodium, iridium, cobalt, iron, the osmium, has also preferably included the cocatalyst of one or more compositions in IB family, IIB family, group vib, VIIB family and group of the lanthanides, actinium series rare earth metal or the rare-earth oxide.Said catalyzer can appendix on micropore or mesoporous carrier.
The method of the pure hydrogen of a kind of usefulness provided by the invention can not used noble metal catalyst, and is with low cost.The H that produces
2Purity is higher, and does not contain CO in the gas, CO
2, can directly be used for fuel cell field.The coproduction carboxylate salt does not have greenhouse gas emission in the whole process in the time of preparation hydrogen, and the theoretical yield of carbon is 100%.Technology is simple, and is low for equipment requirements, can large-scale industrial production.
In order to further specify scheme of the present invention, below will set forth with specific embodiment.Need to prove that the raw material that the present invention uses is all available from Chemical Reagent Co., Ltd., Sinopharm Group.
Embodiment 1
Take by weighing 1 part of 10 parts of absolute ethyl alcohols and sodium hydrate solid respectively in reaction kettle, with air emptying in the still, airtightly be warming up to 220 ℃, keep 2h with nitrogen.Be cooled to room temperature and collect gas.
Gaseous product to the present embodiment preparation carries out gas chromatographic analysis, obtains a result shown in embodiment in the table 11.Fig. 1 is the gc spectrogram of the gaseous product of present embodiment preparation.
Embodiment 2
Take by weighing 1 part of 10 parts of absolute ethyl alcohols and sodium hydrate solid respectively in reaction kettle, with air emptying in the still, airtightly be warming up to 240 ℃, keep 2h with nitrogen.Be cooled to room temperature and collect gas.Gaseous product to the present embodiment preparation carries out gas chromatographic analysis, obtains a result shown in embodiment in the table 12.
Embodiment 3
Take by weighing 1 part of 10 parts of moisture 20% ethanol and sodium hydrate solid respectively in reaction kettle, with air emptying in the still, airtightly be warming up to 240 ℃, keep 2h with nitrogen.Collect gas after being cooled to room temperature.Gaseous product to the present embodiment preparation carries out gas chromatographic analysis, obtains a result shown in embodiment in the table 13.
Embodiment 4
Take by weighing 1 part of 10 parts of no moisture 50% ethanol and sodium hydrate solid respectively in reaction kettle, with air emptying in the still, airtightly be warming up to 240 ℃, keep 2h with nitrogen.Collect gas after being cooled to room temperature.Gaseous product to the present embodiment preparation carries out gas chromatographic analysis, obtains a result shown in embodiment in the table 14.
Embodiment 5
Take by weighing 1 part of 10 parts of anhydrous methanols and sodium hydrate solid respectively in reaction kettle, with air emptying in the still, airtightly be warming up to 240 ℃, keep 2h with nitrogen.Be cooled to room temperature and collect gas.Gaseous product to the present embodiment preparation carries out gas chromatographic analysis, obtains a result shown in embodiment in the table 15.
Embodiment 6
Take by weighing 1 part of 10 parts of USP Kosher and sodium hydrate solid respectively in reaction kettle, with air emptying in the still, airtightly be warming up to 190 ℃, keep 2h with nitrogen.Collect gas after being cooled to room temperature.Gaseous product to the present embodiment preparation carries out gas chromatographic analysis, obtains a result shown in embodiment in the table 16.
Embodiment 7
Take by weighing 1 part of 10 parts of absolute ethyl alcohols and calcium hydroxide solid respectively in reaction kettle, with air emptying in the still, airtightly be warming up to 240 ℃, keep 2h with nitrogen.Be cooled to room temperature and collect gas.Gaseous product to the present embodiment preparation carries out gas chromatographic analysis, obtains a result shown in embodiment in the table 17.
Take by weighing 1 part of 10 parts of absolute ethyl alcohols and sodium hydrate solid respectively in reaction kettle, add a small amount of Pd/C catalyzer again, with air emptying in the still, airtightly be warming up to 200 ℃, keep 2h with nitrogen.Be cooled to room temperature and collect gas.Gaseous product to the present embodiment preparation carries out gas chromatographic analysis, obtains a result shown in embodiment in the table 18.
Take by weighing 1 part of 10 parts in anhydrous butanols and sodium hydrate solid respectively in reaction kettle, with air emptying in the still, airtightly be warming up to 200 ℃, keep 1h with nitrogen.Be cooled to room temperature and collect gas.Gaseous product to the present embodiment preparation carries out gas chromatographic analysis, obtains a result shown in embodiment in the table 19.
Take by weighing 1 part of 10 parts of anhydrous hexalin and sodium hydrate solid respectively in reaction kettle, with air emptying in the still, airtightly be warming up to 180 ℃, keep 1h with nitrogen.Be cooled to room temperature and collect gas.Gaseous product to the present embodiment preparation carries out gas chromatographic analysis, obtains a result shown in embodiment in the table 1 10.
Ethanol heating is become steam through being heated to 240 ℃ and be equipped with the tube furnace of sodium hydroxide, in the outlet cooling and collect noncondensable gas, detect and be mainly hydrogen.
The gaseous product of table 1 embodiment 1～8 preparation is formed and content
Other is other hydro carbons
Can find out by table 1, in alcohol, add entry the purity of hydrogen is increased, thereby can use cheap bio-ethanol (aqueous ethanol) to replace absolute ethyl alcohol, can reduce cost.And do not detect CO, CO in the gas that produces
2So the hydrogen that obtains can be applicable to fuel cell.
The solid product that reaction obtains is the corresponding metal carboxylate salt.
Provided by the invention is that pure and mild alkali is mixed down at 100～400 ℃ with the pure method for preparing hydrogen, and pure and mild alkali reaction obtains comprising in the reaction product hydrogen.Preparing method provided by the invention, the hydroxide radical attack alcoholic extract hydroxyl group in the alkali generates a part water and a pure ion.Alcohol ion and water rapid reaction generate hydrogen, aldehyde and hydroxide ion.Hydroxide ion is added on the carbonyl carbon of aldehyde through nucleophilic addition(Adn) again, obtains the pure and mild a part carboxylate salt of a part through Connizzaro (Cannizzaro) reaction.Therefore do not contain CO and CO in the gaseous product of the present invention's preparation
2Deng by product, need not remove miscellaneous operation to product again, reduced cost.Preparing method's condition provided by the invention in addition is gentle, does not need noble metal catalyst just can prepare hydrogen.
More than a kind of method for preparing hydrogen with alcohol provided by the invention has been carried out detailed introduction; Having used concrete example among this paper sets forth principle of the present invention and embodiment; The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (9)
1. one kind prepares the method for hydrogen with alcohol, it is characterized in that, comprising:
Pure and mild alkali is mixed, obtain solidliquid mixture;
Pure and mild alkali in the said solidliquid mixture reacts, and obtains reaction product; Said reaction product comprises hydrogen; Said blended temperature is 100～400 ℃.
2. according to claim 1 with the pure method for preparing hydrogen, it is characterized in that 120～260 ℃ of said blended temperature.
3. according to claim 1 with the pure method for preparing hydrogen, it is characterized in that said reaction product also comprises the carboxylate salt and the CH of alkali-metal carboxylate salt and/or earth alkali metal
4, C
2H
6
4. according to claim 1 with the pure method for preparing hydrogen, it is characterized in that said alcohol is 1～18 monobasic or polyvalent alcohol for the carbon atom number.
5. according to claim 1 with the pure method for preparing hydrogen, it is characterized in that said alkali is the oxyhydroxide or the alcoholate of basic metal or earth alkali metal.
6. according to claim 1 with the pure method for preparing hydrogen, it is characterized in that the reaction times that said pure and mild alkali reacts is 0.1～6h.
7. the method for using alcohol to prepare hydrogen according to claim 1 is characterized in that, also is included in the said solidliquid mixture to add catalyzer.
8. according to claim 8 with the pure method for preparing hydrogen, it is characterized in that said catalyzer comprises: any one or more in nickel, palladium, platinum, ruthenium, rhodium, iridium, cobalt, iron, the osmium.
9. root preparation method according to claim 8 is characterized in that, said catalyzer also comprises one or more in IB family, IIB family, group vib, VIIB family and group of the lanthanides, actinium series rare earth metal or the rare-earth oxide.
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| CN102530858B CN102530858B (en) | 2015-01-07 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111491888A (en) * | 2017-10-18 | 2020-08-04 | 原子能与替代能源委员会 | Apparatus for generating gas |
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|---|---|---|---|---|
| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111491888A (en) * | 2017-10-18 | 2020-08-04 | 原子能与替代能源委员会 | Apparatus for generating gas |
| CN111491888B (en) * | 2017-10-18 | 2022-07-15 | 原子能与替代能源委员会 | Apparatus for generating 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 |
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