CN101965311B - Process and apparatus for production of hydrogen - Google Patents
Process and apparatus for production of hydrogen Download PDFInfo
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- CN101965311B CN101965311B CN2009801062553A CN200980106255A CN101965311B CN 101965311 B CN101965311 B CN 101965311B CN 2009801062553 A CN2009801062553 A CN 2009801062553A CN 200980106255 A CN200980106255 A CN 200980106255A CN 101965311 B CN101965311 B CN 101965311B
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Abstract
Disclosed is a hydrogen production process which can produce hydrogen from a raw material mixture comprising at least a hydrocarbon and water through a reaction system for carrying out at least a steam reforming reaction in the presence of a reforming catalyst. In the process, a CuO single catalyst is used as the reforming catalyst. The raw material mixture may additionally comprise an oxygen, and the reaction system may be one which can achieve a partial oxidative reforming reaction and a steam reforming reaction in the presence of the reforming catalyst.
Description
Technical field
The present invention relates to a kind of under the existence of modified catalyst the reaction system by carrying out at least the water vapour modified-reaction made the method for hydrogen by the mixing raw material that contains at least hydrocarbon and water.In particular, the present invention relates to a kind of by containing the method for hydrogen of being made by the mixing raw material that contains hydrocarbon, oxygen and water from the heat modification method of partical oxidizing modifying reaction and water vapour modified-reaction.In addition, the invention still further relates to a kind of hydrogen producing apparatus for implementing this hydrogen manufacture method.
Background technology
As the method for industrial manufacturing hydrogen, known have built-up section oxidation style and water vapour modification method from the heat modification method.In the heat modification method, use hydrocarbon as the generation source of hydrogen at this.In partial oxidation process, the partical oxidizing modifying reaction by as thermopositive reaction produces hydrogen and carbonic acid gas by hydrocarbon and oxygen.On the other hand, in water vapour modification method, by the water vapour modified-reaction as thermo-negative reaction, by hydrocarbon and water generates hydrogen and carbonic acid gas.Be to make the thermal discharge of partical oxidizing modifying reaction and the caloric receptivity balance of water vapour modified-reaction from the heat modification method, do not need indirect heating ideally and carry out the method for the modified-reaction of hot self-support type.For example, in the situation that use methyl alcohol as hydrocarbon, the reaction formula of partical oxidizing modifying reaction and water vapour modified-reaction is with following formula (1) and (2) expression.
CH
3OH+1/2O
2→ 2H
2+ CO
2+ heat release ... (1)
CH
3OH+H
2O → 3H
2+ CO
2+ heat absorption ... (2)
These reactions are all undertaken by the participation of modified catalyst.In the heat modification method, the general catalyzer (Cu/ZnO catalyzer) that contains copper/zinc that uses.The Cu/ZnO catalyzer obtains by reduction CuO/ZnO catalyzer (cupric oxide/Zinc oxide catalytic) etc., improve the viewpoint of catalytic efficiency etc. according to the increase specific surface area, for example with the aluminum oxide of micropowder as dispersion agent, be shaped to granular state and utilize.
In the heat modification method, think that heat gives and accepts and can carry out efficiently if in the thermopositive reaction that above-mentioned formula (1) expression occurs, the thermo-negative reaction of above-mentioned formula (2) occurs nearby at once.Therefore, attempted by general modified catalyst, partical oxidizing modifying reaction and water vapour modified-reaction being carried out simultaneously.But in fact, the partical oxidizing modifying reaction is compared with the water vapour modified-reaction, and speed of response is fast.Therefore, for example, if the mixing raw material that will contain hydrocarbon, oxygen and water supply with to the modified-reaction device, the upstream side of the gas flow path in the modified-reaction device, the partical oxidizing modifying reaction is preponderated than water vapour modified-reaction, causes the excessive rising of local temperature.Its result for the modified catalyst in the zone that formed high temperature, exists the minimizing of the specific surface area that causes due to sintering to damage the worry of catalytic activity, is difficult to make the self-heating modified-reaction to continue for a long time to carry out.On the other hand, the downstream side of the gas flow path in the modified-reaction device, because the water vapour modified-reaction as thermo-negative reaction is preponderated than the partical oxidizing modifying reaction, temperature reduces gradually.Here, in order fully to carry out the water vapour modified-reaction in the heat modification method, when the heat release that produces with the partical oxidizing modifying reaction provided the heat of the caloric receptivity that comprises this water vapour modified-reaction, there was the tendency that forms excessive temperature in high-temperature area.In order to realize the self-heating modified-reaction, inevitably can partly produce too high temperature province.
The problem that reduces at high temperature catalytic activity, the composite modified catalyst be added with other metals such as precious metal by using in the Cu/ZnO catalyzer has been proposed, suppress the reduction of catalytic activity, and improve the method (for example, with reference to patent documentation 1,2) of the weather resistance of modified catalyst.
Patent documentation 1: TOHKEMY 2002-79101 communique
Patent documentation 2: TOHKEMY 2003-144931 communique
But, in fact, even utilize above-mentioned composite modified catalyst, can not fully solve the problem from the heat modification method.That is, even use above-mentioned composite modified catalyst, can not substantially improve the weather resistance in the too high temperature province that is caused by the partical oxidizing modifying reaction.In addition, above-mentioned Composite modified catalyst exist in the water vapour modified-reaction reaction preference be inferior to the formation efficiency of common Cu/ZnO catalyzer, hydrogen low, easily produce the such problem of unwanted by product simultaneously.In addition, also there is the inconvenience of itself costliness of above-mentioned composite modified catalyst.
Summary of the invention
The present invention is based on such situation and makes, and its purpose is, when utilization under the existence of modified catalyst is made hydrogen from the heat modification method, prevents that catalytic activity from reducing, and makes the self-heating modified-reaction continue for a long time to carry out.
According to the 1st aspect of the present invention, a kind of method for preparing hydrogen is provided, this manufacture method is made hydrogen by following reaction system, above-mentioned reaction system is under the existence of modified catalyst, at least carry out the water vapour modified-reaction by the mixing raw material that contains at least hydrocarbon and water, wherein, above-mentioned modified catalyst is made of the CuO single component catalyst.Particularly, in the present invention, above-mentioned mixing raw material also contains aerobic, and above-mentioned reaction system is under the existence of above-mentioned modified catalyst, and when carrying out partical oxidizing modifying reaction and water vapour modified-reaction, performance is the effect of excellence especially.
The inventor conducts in-depth research in order to solve above-mentioned problem, found that, the modified catalyst that the CuO single component catalyst is suitable as the self-heating modified-reaction uses, thereby completes the present invention.That is, in existing viewpoint, think in the water vapour modified-reaction to be fit to use the Cu/ZnO catalyzer, and attempt adding take the Cu/ZnO catalyzer as the basis improvement of other metal etc.Opposite with existing viewpoint, the inventor is unexpected to be found, as the modified catalyst of water vapour modified-reaction, can be suitable for the CuO single component catalyst.And, when the CuO single component catalyst is used as the modified catalyst of self-heating modified-reaction, even can access the high-temperature area that generating portion oxidation modification reaction causes, also can find hardly the so good result of catalytic activity reduction after long-time.
Preferred above-mentioned modified catalyst is supported at the carrier that is selected from aluminum oxide, silicon-dioxide, zeolite and gac.
Preferred above-mentioned hydrocarbon is selected from methyl alcohol, ethanol, dme, methane, propane and butane.
When above-mentioned hydrocarbon was methyl alcohol, the water in preferred above-mentioned mixing raw material and the molar ratio of methyl alcohol were 1.5～2.0.
When above-mentioned hydrocarbon is methyl alcohol, preferably select the ratio of methyl alcohol, oxygen and water in above-mentioned mixing raw material, making the ratio of above-mentioned partical oxidizing modifying reaction is 20～30%, and the ratio of above-mentioned water vapour modified-reaction is 80～70%.More specifically, select the ratio of hydrocarbon, oxygen and water in above-mentioned mixing raw material, making the ratio of above-mentioned partical oxidizing modifying reaction is 20～30%, and the ratio of above-mentioned water vapour modified-reaction is 80～70%.
According to the 3rd aspect of the present invention, a kind of hydrogen producing apparatus is provided, it comprises the modified-reaction device of the gas flow path with configuration modified catalyst, be used for reacting by partical oxidizing modifying and produced the modified gas that contains hydrogen with the water vapour modified-reaction by the mixing raw material that contains hydrocarbon, oxygen and water, wherein, above-mentioned modified catalyst is made of the CuO single component catalyst.By using the hydrogen producing apparatus of this structure, can suitably carry out the manufacture method of the 1st aspect of the present invention.
Below, other features and advantages of the present invention are by the reference accompanying drawing and carry out following detailed description with more than you know.
Description of drawings
Fig. 1 means the sectional view of simple structure of the modified-reaction device of the major portion that consists of hydrogen producing apparatus of the present invention.
Fig. 2 means the coordinate diagram of temperature distribution of the modified-reaction section of embodiments of the invention and comparative example.
Fig. 3 means the coordinate diagram of the weather resistance of modified catalyst.
Embodiment
Fig. 1 represents the simple structure as the modified-reaction device 1 of the major portion of hydrogen producing apparatus of the present invention.This modified-reaction device 1 has the self-heating modified-reaction of partical oxidizing modifying reaction and water vapour modified-reaction by combination, produced the modified gas that contains hydrogen by the mixing raw material that contains the hydrocarbon that forms vaporized state.Modified-reaction device 1 possesses body 2 and modified-reaction section 3.
Modified-reaction section 3 is the position of filling-modified catalyzer in the gas flow path of body 2 inside, is made of with a pair of isolated part 4 that separates setting along short transverse in the inboard of body 2 body 2.The pelleted catalyst of the modified catalyst of filling for being made of the CuO single component in fact for example is supported at alumina supporter.Isolated part 4 can make the mixing raw material and the modified gas that form vaporized state pass through, and encloses simultaneously modified catalyst, for example is made of pressed sheet.
In the modified-reaction device 1 of above-mentioned formation, comprise the hydrogen producing apparatus of this modified-reaction device 1 by startup, mixing raw material imports in body 2 from unstripped gas introducing port 21.Mixing raw material contains hydrocarbon, oxygen and water, for example heats in advance in not shown gasifier and forms vaporized state.In this gasifier, be heated to after modified-reaction device 1 in the needed goal response temperature of modified-reaction (for example 200～260 ℃).As above-mentioned hydrocarbon, can enumerate for example methyl alcohol, ethanol, dme, methane, propane, butane.Below, to using the situation of methyl alcohol to describe as hydrocarbon.As oxygen source contained in mixing raw material, can enumerate air and oxygen enrichment oxidizing gases (oxygen concn is higher than airborne oxygen concn).
The mixing raw material of the vaporized state of supplying with to modified-reaction device 1 via unstripped gas introducing port 21 imports to modified gas export mouth 22 by the modified-reaction section 3 in body 2.The well heater (not shown) that modified-reaction section 3 for example arranges by the mode with the periphery of coiling body 2 is heated to cause partical oxidizing modifying reaction needed temperature (for example more than 220 ℃).In modified-reaction section 3, effect by modified catalyst (CuO single component catalyst), occur simultaneously as the partical oxidizing modifying reaction of the methyl alcohol of thermopositive reaction with as the water vapour modified-reaction of the methyl alcohol of thermo-negative reaction, and produced the modified gas that contains hydrogen by mixing raw material.
Particularly, the upstream side in modified-reaction section 3 mainly carries out the partical oxidizing modifying reaction of methyl alcohol.That is by the oxygenizement of CuO catalyzer, the thermopositive reaction shown in above-mentioned formula (1) occurs.Because the partical oxidizing modifying reacting phase is very fast to speed of response, the upstream side in modified-reaction section 3 causes temperature sharply to rise by this reaction, produces too high temperature province.
In addition, the water vapour modified-reaction of methyl alcohol is mainly carried out in the downstream side in modified-reaction section 3.That is by the effect of CuO catalyzer, the thermo-negative reaction shown in above-mentioned formula (2) occurs.More specifically, the reaction of formula (2) is through the reaction shown in following formula (3) and the two stage reaction of reaction (CO conversion reaction) shown in formula (4).
CH
3OH → 2H
2+ CO+ heat absorption ... (3)
CO+H
2O → H
2+ CO
2+ heat release ... (4)
In the present embodiment, import the mixture ratio etc. of methyl alcohol, oxygen and the water of modified-reaction section 3 by appropriate regulation, can control section oxidation modification reaction and water vapour modified-reaction, the temperature in modified-reaction section 3 are kept within the limits prescribed.That is, in modified-reaction section 3, carry out the self-heating modified-reaction.
In the self-heating modified-reaction of methyl alcohol, the caloric receptivity of the every 1mol methanol consumption amount in the thermal discharge that the ratio of partical oxidizing modifying reaction and water vapour modified-reaction uses every 1mol methanol consumption amount of partical oxidizing modifying in reacting and water vapour modified-reaction and when calculating in the consistent mode of hot revenue and expenditure, the ratio of partical oxidizing modifying reaction is approximately 20%, and the ratio of water vapour modified-reaction is approximately 80%.This is thermal discharge of supposition partical oxidizing modifying reaction theoretic ratio when all being consumed in the heat absorption of water vapour modified-reaction.But, in fact, import modified-reaction device 1 vaporized state mixing raw material temperature and be released to outside heat from modified-reaction device 1, the condition element of also calculating as heat and closely related.Under such De Zhuan Condition, in order fully to carry out the water vapour modified-reaction as thermo-negative reaction, need to make the thermal discharge of partical oxidizing modifying reaction slightly more than theoretical value, make the mixture ratio of oxygen slightly higher than theoretical value, preferably the ratio with partical oxidizing modifying reaction is adjusted into 20～30% left and right, and the ratio of water vapour modified-reaction is adjusted into 80～70% left and right.In addition, about the water vapour modified-reaction, the reactive ratio of water and methyl alcohol is according to above-mentioned formula (2), and mol ratio is 1: 1 in theory, in fact, when water vapour is not enough, easily produces side reaction.Therefore, preferably compare the condition of water vapour surplus with theoretical value.But if due to the ratio that makes water vapour when too high, consumed energy is excessive, so the mixture ratio of the water in mixing raw material and methyl alcohol (Steam By Methanol:S/M ratio) is preferably 1.5～2.0 (mol/mol) left and right.
The modified gas that contains hydrogen that operates like this and produce in modified-reaction device 1 is made with extra care by appropriate means.In the situation that use chemical process, for example, use basic solution that the modified gas that mainly contains hydrogen, carbonic acid gas, carbon monoxide is processed and remove carbonic acid gas and carbon monoxide.In addition, when using air as the oxygen source of mixing raw material, consider from the viewpoint except denitrification effectively, for example, remove denitrification if be filled with the PSA gas separating method that a plurality of adsorption towers of the sorbent material of selective adsorption nitrogen carry out by use, can concentrate hydrogen.
As shown in present embodiment, in the self-heating modified-reaction, the oxygen that the partical oxidizing modifying reaction shown in above-mentioned formula (1) proceeds in system is consumed in fact fully.After partical oxidizing modifying reaction or with its simultaneously, carry out the water vapour modified-reaction shown in above-mentioned formula (2).When using the CuO single component catalyst as modified catalyst, if guarantee to be suitable for temperature of reaction (for example more than 250 ℃) and the regularization condition of the carrying out of water vapour modified-reaction, for example the methyl alcohol reactivity of the fs shown in above-mentioned formula (3) can reach more than 99%, and the CO conversion reaction rate of the subordinate phase shown in above-mentioned formula (4) also can reach more than 95%.That is, can think, the CuO single component catalyst is excellent in the selectivity of the reaction in two stages of water vapour modified-reaction, as the modified catalyst of water vapour modified-reaction, also has the catalytic performance that can compare with existing Cu/ZnO catalyzer.In addition, for the CuO single component being supported at the unit catalyzer of aluminum oxide etc., the preparation method also than being easier to, is favourable aspect cost of material due to the modified catalyst of present embodiment.
And because the modified catalyst (CuO single component catalyst) of the present embodiment state with the oxide compound of metallic copper (Cu) uses, physical property is more stable than Cu.Therefore, the CuO single component catalyst is compared with the Cu/ZnO catalyzer, is difficult for causing sintering, and has weather resistance at high temperature.Thus, the modified catalyst of present embodiment (CuO single component catalyst) can suitably be brought into play catalytic performance for a long time in the partical oxidizing modifying reaction that easily produces high-temperature area and the water vapour modified-reaction as thermo-negative reaction.In addition, with as the aluminum oxide of micropowder etc. be shaped to particulate state as dispersion agent compare of existing Cu/ZnO catalyzer, consider from being difficult for producing the efflorescence this point that is caused by thermal history, also can expect the high life.Namely, if utilizing as modified catalyst uses the present embodiment that the CuO single component catalyst carries out to make hydrogen, can make combination have the self-heating modified-reaction of partical oxidizing modifying reaction and water vapour modified-reaction suitably to carry out for a long time, can improve the formation efficiency of hydrogen.
In addition, according to present embodiment, due to the long catalytic life that can expect in the self-heating modified-reaction, even being carried out hydrogen by the PSA gas separating method, separates the modified gas that generates, also can make stably long-term continuous operation of PSA gas separation unit, be preferred.
Above, embodiments of the present invention are illustrated, but scope of the present invention is not limited to above-mentioned embodiment.In the scope that does not break away from thought of the present invention, the concrete structure of modified-reaction device of the present invention and method for preparing hydrogen of the present invention can carry out various changes.
The modified catalyst that uses in the present invention (CuO single component catalyst) also can for not being supported at the state of alumina supporter, in addition, also can be supported at aluminum oxide carrier (for example, silicon-dioxide, zeolite or gac) in addition.
Then, by embodiment and comparative example, practicality of the present invention is described.
Embodiment 1
In the present embodiment, use the modified-reaction device 1 (Fig. 1) of following specific specification, contain the modified gas of hydrogen from the mixing raw material manufacturing that is consisted of by methyl alcohol, empty G﹠W.
The body 2 of modified-reaction device 1 is by stainless steel tube (internal diameter: 23mm, total length: 400mm) consist of.In modified-reaction section 3, as modified catalyst, be filled with the pelleted catalyst (particle diameter: 1.2～2.5mm) that utilizes carrying alumina to hold the CuO single component with packing height 200mm.Here, modified-reaction section 3 is disposed at its upper end from the position of the upper end decline 110mm of above-mentioned stainless steel tube.In addition, dispose the electric heater (keeping 250 ℃ of temperature) of the periphery of surrounding stainless steel tube.
In the feed rate of the mixing raw material of supplying with to modified-reaction device 1, methyl alcohol is that flow, the water of 4.96mol/h is that flow, the air of 7.44mol/h (S/M ratio=1.5) is 76.71dm
3The flow of N/h (being scaled 0.72mol/h with pure oxygen).This mixing raw material is heated and forms vaporized state in gasifier, then, supply with to modified-reaction device 1.The temperature of the mixing raw material when importing modified-reaction device 1 is 260 ℃.Pressure in modified-reaction device 1 maintains 800kPa (gauge pressure).
The temperature distribution of in the present embodiment, research is normal when starting (1 imports mixing raw material to through approximately after 5 hours from beginning to the modified-reaction device) modified-reaction section 3.The research of temperature distribution is undertaken by the temperature that mensuration is set in a plurality of measuring points of modified-reaction section 3.Measuring point is a plurality of points that are set in along the central shaft on the gas flow direction of modified-reaction section 3, in modified-reaction section 3, and the thermometer that can move along above-mentioned central shaft arrangement.Then, the position of the determination part of this thermometer is moved in turn to a plurality of measuring points on above-mentioned central shaft, the temperature of each this measuring point is measured.This measurement result is shown in Fig. 2.The transverse axis of this figure represents measuring point, and expression is with the upstream-side-end (upper end) of modified-reaction section 3 displacement to the flow direction of gas as basic point.The longitudinal axis of this figure represents the mensuration temperature of this measuring point.
To the modified gas of deriving from modified-reaction device 1, use heat exchanger cooling to normal temperature, and condensing liquid component is being separated by gas-liquid separator on the basis of removing, use gas phase chromatographic device to carry out compositional analysis.The analysis of this modified gas is implemented the modified gas that obtains when above-mentioned normal start.In the composition of modified gas, be approximately 63% as the hydrogen of main component, also confirm in addition to have carbonic acid gas, nitrogen, carbon monoxide, argon, can not confirm to have the by products such as methane and dme.In addition, reach 99.5% with respect to the reactivity (total methyl alcohol reactivity) of the integral body of the quantity of methyl alcohol that drops into, think that the methyl alcohol that drops into is almost all consumed by reaction.CO conversion reaction rate also obtains 96.8% so good result.
Comparative example 1
In this comparative example, use the modified-reaction device 1 identical with embodiment 1, with the raw material supplying state identical with embodiment 1, contained the modified gas of hydrogen by the mixing raw material manufacturing.Wherein, as the modified catalyst that is filled in modified-reaction section 3, use the Cu/ZnO catalyzer to replace the modified catalyst that uses in embodiment 1.This modified catalyst is with add the micropowder of aluminum oxide as dispersion agent in Cu/ZnO, by carrying out the catalyzer that sintering forms after extrusion forming.In addition, in this comparative example, by the method identical with embodiment 1, the temperature distribution of modified-reaction section 3 is measured.Its measurement result is shown in Fig. 2.
In this comparative example, by the method identical with embodiment 1, the condensed liquid of deriving from modified-reaction device 1 when above-mentioned normal start and the composition of modified gas are analyzed, result, total methyl alcohol reactivity is that 98.8%, CO conversion reaction rate is 96.1%.In addition, in the composition of modified gas, be approximately 62% as the hydrogen of principal constituent, also confirm in addition to have carbonic acid gas, nitrogen, carbon monoxide, argon, can not confirm to have the by products such as methane and dme.
Result according to this embodiment 1 and comparative example 1, can confirm, the CuO single component catalyst is as the modified catalyst from the heat modification method, and is identical with the Cu/ZnO catalyzer, can control the temperature in modified-reaction section, have the catalytic performance that to compare with the Cu/ZnO catalyzer.
[weather resistance of modified catalyst relatively]
Use the modified catalyst (CuO single component catalyst and Cu/ZnO catalyzer) that uses in above-described embodiment and comparative example, implement the long duration test of catalytic performance under the condition identical with comparative example 1 with embodiment 1.Its result is shown in Fig. 3.In Fig. 3, transverse axis represents runtime (from stably discharged moment institute's elapsed time of modified gas by 1 beginning of modified-reaction device), the total methyl alcohol reactivity in the longitudinal axis represents between this on-stream period.When using CuO single component catalyst of the present invention, even through 700 hours, Zong the methyl alcohol reactivity is also kept approximately 99% so high value.With respect to this, when using the Cu/ZnO catalyzer, total methyl alcohol reactivity shows approximately 99% high numerical value at the running beginning initial stage, but in time through and show the tendency that reduces gradually, through moment of 700 hours, be reduced to 80% left and right.No matter use any catalyzer, the peak temperature of the high-temperature area of modified-reaction section 3 all reaches approximately 400 ℃ of left and right, but the reduction of the catalytic activity that the Cu/ZnO catalyzer causes due to sintering, total methyl alcohol reactivity reduces.
Claims (6)
1. method for preparing hydrogen is characterized in that:
This manufacture method is made hydrogen by following reaction system, and described reaction system is carried out the water vapour modified-reaction at least by the mixing raw material that contains at least the first alcohol and water in the modified-reaction section of the modified-reaction device that is filled with modified catalyst,
Described mixing raw material also contains aerobic,
Described modified catalyst is made of the CuO single component catalyst, and this CuO single component catalyst is used for carrying out the partical oxidizing modifying reaction of methyl alcohol at the upstream side of described modified-reaction section, carries out the water vapour modified-reaction in the downstream side of described modified-reaction section.
2. method for preparing hydrogen as claimed in claim 1 is characterized in that:
Described modified catalyst is supported at the carrier that is selected from aluminum oxide, silicon-dioxide, zeolite and gac.
3. method for preparing hydrogen as claimed in claim 1 is characterized in that:
Water in described mixing raw material and the molar ratio of methyl alcohol are 1.5～2.0.
4. method for preparing hydrogen as claimed in claim 1 is characterized in that:
Select the ratio of hydrocarbon, oxygen and water in described mixing raw material, make the caloric receptivity of the thermal discharge of described partical oxidizing modifying reaction and described water vapour modified-reaction equal in fact.
5. method for preparing hydrogen as claimed in claim 1 is characterized in that:
Select the ratio of methyl alcohol, oxygen and water in described mixing raw material, making the ratio of described partical oxidizing modifying reaction is 20～30%, and the ratio of described water vapour modified-reaction is 80～70%.
6. hydrogen producing apparatus is characterized in that:
Comprise the modified-reaction device with the gas flow path that disposes modified catalyst, be used for carrying out the partical oxidizing modifying reaction by the upstream side in described modified-reaction section, the water vapour modified-reaction is carried out in downstream side in described modified-reaction section, produced the modified gas that contains hydrogen by the mixing raw material that contains methyl alcohol, oxygen and water
Described modified catalyst is made of the CuO single component catalyst.
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| JPS58193736A (en) * | 1982-05-06 | 1983-11-11 | Mitsubishi Heavy Ind Ltd | Catalyst for production of gas enriched with hydrogen |
| JPH0427434A (en) * | 1990-05-23 | 1992-01-30 | Mitsubishi Heavy Ind Ltd | Catalyst for reforming methanol |
| JP3843196B2 (en) * | 1999-09-29 | 2006-11-08 | ダイハツ工業株式会社 | Dimethyl ether reforming catalyst and fuel cell device |
| JP4774197B2 (en) * | 2003-05-20 | 2011-09-14 | 出光興産株式会社 | Oxygen-containing hydrocarbon reforming catalyst, hydrogen or synthesis gas production method using the same, and fuel cell system |
| US20050229488A1 (en) * | 2004-04-19 | 2005-10-20 | Texaco Inc. | Method and apparatus for providing a continuous stream of reformate |
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