TW200946450A - Process and apparatus for production of hydrogen - Google Patents

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

200946450 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a mixture of at least a mixture of smoke and water, @μα, by the presence of a recombination catalyst (rerforming catalysi;) to a small size, / ^ 'When performing a steam ref orming reaction system to produce gas ▲ gas ,, use

CuO alone catalyst is used as a method for producing hydrogen deoxygenation of the above-mentioned recombination catalyst. In particular, the present invention relates to a raw material comprising ~~3⁄4 σ containing hydrocarbons, oxygen and water, by a partial oxidation oxidative recombination reaction and a vapor recombination reaction, and a thermothermal recombination method (Day 111: 〇1: ] 16〇131^{〇〇1丨1^) A method of producing hydrogen. Further, the present invention relates to a hydrogen producing apparatus for carrying out the hydrogen production method of the above modes. [Prior Art] As a method of industrially producing hydrogen, an autothermal reforming method combining a partial oxidation method and a gas recombination method is known. Here, in the autothermal recombination method, hydrocarbon is used as a source of hydrogen generation. In a partial oxidation process, a partial oxidation oxidative recombination reaction by an exothermic reaction produces hydrogen and carbon dioxide from a hydrocarbon and oxygen. On the other hand, in the steam reforming process, hydrogen and carbon dioxide are generated from hydrocarbons and water by a vapor recombination reaction of an endothermic reaction. The autothermal recombination method is a method in which the exothermic amount derived from partial oxidative recombination is balanced with the endothermic amount derived from vapor recombination, and it is desirable to carry out a thermoreactive recombination reaction without external heating. For example, when methanol is used as the hydrocarbon, the reaction formula of the partial oxidation recombination reaction and the vapor recombination reaction is represented by the following formulas (1) and (2). CH3〇H + 1/2〇2 — 2H2 + C〇2 + Exothermic · · · (1)

2215-10343-PF 200946450 CH3〇H + h2〇 — 3H2 + c〇2 + endothermic · · · (2) These reactions are all carried out by recombination catalyst. In the autothermal recombination method, a copper/zinc containing catalyst (Cu/Zn ruthenium catalyst) is generally used.

The Cu/ZnO catalyst can be reduced by reducing Cu 〇/Zn 〇 catalyst (copper oxide/zinc oxide catalyst), etc., and the catalyst efficiency is improved by increasing the specific surface area, for example, by fine powder. The oxidized product is used as a dispersing agent in a state of being formed into a small granular shape. In the autothermal recombination method, if the endothermic reaction represented by the above formula (2) occurs in the vicinity of the exothermic reaction represented by the above formula (1), the heat transfer efficiency can be favorably performed. Therefore, it is attempted to carry out a partial oxidation recombination reaction and a vapor recombination reaction simultaneously by a common recombination catalyst. However, in fact, the partial oxidation recombination reaction is faster than the vapor recombination reaction. Therefore, for example, when a mixed raw material containing a hydrocarbon and oxygen and water is supplied to the reforming reactor, the partial oxidation recombination reaction takes place more preferentially than the vapor recombination reaction on the upstream side of the gas passage in the recombination reactor, and becomes a cause. Excessive temperature rises. As a result, it becomes a recombination catalyst in an excessively high temperature region, and the catalyst activity due to a decrease in specific surface area due to sintering is impaired, and it is difficult to continue the autothermal recombination reaction for a long period of time. On the other hand, in the downstream side of the gas passage in the recombination reactor, the vapor recombination reaction due to the endothermic reaction is more preferential than the partial oxidation recombination reaction, and the temperature is gradually lowered. Here, since the steam recombination reaction is sufficiently carried out in the autothermal recombination reaction, it is estimated that the heat absorption derived from the vapor recombination reaction is excessively high in the high temperature region when the heat source derived from the heat of the partial oxidation recombination reaction is supplied. Prone to achieve a self-heating recombination reaction 'inevitably produces partial over-prone

2215-10343-PF 4 200946450 South Temperature Zone. For the problem of reduced catalyst activity at high temperatures, the proposal is used by

A composite recombination catalyst in which a metal such as a noble metal or the like is added to the Cu/ZnO catalyst. The method of suppressing the decrease in the catalytic activity and improving the durability of the recombination catalyst (see, for example, Patent Documents 1 and 2). [Patent Document] Japanese Laid-Open Patent Publication No. 2002-791-01 (Patent Document 2) Japanese Laid-Open Patent Publication No. 2003-144931, No. 2003-144931: Actually, it is not possible to sufficiently solve the self-heating recombination via the above composite recombination catalyst. The problem in the law. Namely, with the above composite recombination catalyst, there was no significant improvement in the durability in the excessively high temperature region generated by the partial oxidation recombination reaction. Furthermore, the above-mentioned composite recombination catalyst has a reaction selectivity lower than that of a general Cu/Zn antimony catalyst, and the hydrogen generation efficiency is lowered, and there is a problem that an undesired by-product is liable to occur. . Further, the above composite recombination catalyst itself is not suitable for the price side. SUMMARY OF THE INVENTION The present invention is conceived under such circumstances, in the manufacture of hydrogen by autothermal recombination in the presence of a recombination catalyst, to prevent catalyst activity in the 'watch & _, to make the autothermal recombination reaction last for a long time. According to a first aspect of the present invention, there is provided a method for producing hydrogen gas, comprising: mixing a raw material of smoke and water, and producing a hydrogen gas by a reaction system for performing a steam reforming reaction; The above "recombination catalyst system is formed by CU0 alone catalyst. In particular, in the present invention,

2215-10343-PF 5 200946450 The above-mentioned swaying raw material progress contains oxygen, and the above reaction is particularly excellent when the partial oxidation recombination reaction and the vapor recombination reaction are carried out in the presence of the recombination catalyst. The present inventors have made efforts to solve the above problems, and have found that the present invention can be suitably carried out using a CuO single catalyst as a recombination catalyst in an autothermal recombination reaction. In other words, based on the conventional knowledge, it is considered that the Cu/Zn ruthenium catalyst is suitable for the steam recombination reaction, and attempts have been made to improve the addition of other metal species based on the Cu/ZnO catalyst. Contrary to these prior knowledge, the inventors have unexpectedly discovered that a CuO alone catalyst can be applied to a recombination catalyst as a vapor recombination reaction. Therefore, when a Cu singly-catalyzed catalyst was used as a recombination catalyst in the autothermal recombination reaction, even if a high-temperature region derived from the partial oxidation recombination reaction was generated, no good result of a decrease in catalytic activity was observed after a long period of time. Preferably, the recombinant catalyst is supported on a carrier selected from the group consisting of alumina, cerium oxide, zeolite and activated carbon. Preferably, the above hydrocarbons are selected from the group consisting of methanol, ethanol, dimethyl ether, decane, propylene carbonate, and butyl sulphide. 5至2. 〇. The ratio of the molar ratio of the water to the methanol is 1.5 to 2. 〇. When the hydrocarbon is methanol, it is preferred to select methanol and oxygen in the mixed raw material in such a manner that the ratio of the partial oxidation recombination reaction is 20 to 30%, and the ratio of the vapor reforming reaction is 8 to 70%. And the proportion of water. More specifically, 5, the ratio of the hydrocarbon, oxygen and water in the mixed raw material is selected in such a manner that the proportion of the partial oxidation recombination reaction is up to the above, and the ratio of the oxygenation recombination reaction is 8 〇 7 7 〇 %.

2215-10343-PF 6 200946450 According to a third aspect of the present invention, there is provided a hydrogen production apparatus comprising a recombination reactor having a gas passage through which a recombination catalyst is disposed, comprising a mixed raw material containing hydrocarbons, oxygen and water. A hydrogen production apparatus for producing a reformed gas containing hydrogen by a partial oxidation recombination reaction and a vapor recombination reaction. The above-mentioned recombination catalyst is composed of CuO alone catalyst. The production method of the first aspect of the present invention can be suitably carried out by using the hydrogen production apparatus constructed in this manner. Other features and advantages of the present invention will be described in more detail hereinafter with reference to the appended claims. [Embodiment] Fig. 1 is a view showing a schematic configuration of a recombination reactor 1 which is a main part of a hydrogen producing apparatus of the present invention. The recombination reaction gastric system produces a hydrogen-containing gas by a self-heating recombination reaction comprising a partial oxidation oxidative recombination reaction and a vaporized gas heavy reaction by a mixed raw material containing smoke which has become a vaporized state. The insect group reactor 1 includes a tube body 2 and a recombination reaction unit 3. The fistula body 2 has a closed-end tubular structure, and a raw material introduction port 21' is provided at the upper end thereof, and a recombination gas outlet is provided at the lower end thereof. ? In the interior, the original dragon and the Di body outlet 22. The rolling body 2 of the tube body 2, the weir introduction port 21, and the recombination gas outlet port are formed to be formed, for example, in a non-recorded steel. = Reaction part 3 is the position of the catalyst in the gas passage inside the pipe body 2, the chain 汹 更 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ It is defined by the IW 4 material 4 in the direction between the middle and the middle. The granules formed by Cu 〇 alone are filled with granules. / The recombination catalyst is a granular granule, which is, for example, planted in an oxidized carrier.

2215-10343-PF 7 200946450 The partition member 4 can be a mixed raw material or a reformed gas which has been vaporized, and is sealed with a recombination catalyst, for example, as a perforated sheet. e ❹ In the recombination reactor 1 having the above configuration, the mixed raw material is introduced into the tubular body 2 through the raw material gas introduction port via the operation of the hydrogen producing apparatus including the reforming reactor 1. The mixed raw material contains smoke, oxygen and water, and is heated in advance, for example, in a gasifier (not shown) to be in a vaporized state. In the recombination reaction of the subsequent recombination reactor i in the gasifier, if necessary, it is heated to a desired reaction temperature (for example, 2 to 26 (rc). The above hydrocarbons may, for example, be methanol, ethanol, akizaki, or A. Institute, Ding Yuan. The following section describes the use of alcohol smoke. The oxygen source contained in the mixed raw materials, for example, air or oxygen-rich gas (oxygen concentration is higher than air)., through the raw material gas introduction π 21 The mixing state of the gasification state supplied to the reforming reactor is guided to the recombination gas outlet port 22 through the recombination reaction portion 3 in the pipe body 2. The recombination reaction portion 3 is, for example, surrounded by the pipe body 2 A heater (not shown) is provided to heat the temperature necessary for the initial partial oxidation recombination reaction (for example, 22 (rc or more). In the recombination reaction section 3, by recombination catalyst (Cu〇 alone catalyst) The effect of the partial oxidation oxidative recombination reaction of the exothermic reaction methanol and the vapor recombination reaction of the methanol of the endothermic reaction simultaneously, and the synthesis gas is produced from the mixed raw material containing hydrogen. Specifically, the recombination reaction section 3 On the upstream side, a partial oxidation recombination reaction of methanol is mainly carried out, that is, an exothermic reaction represented by the following formula (1) occurs by oxidation of a Cu crucible catalyst. Since the partial oxidation recombination reaction is relatively the reaction rate Fast, on the upstream side of the recombination reaction unit 3, via the opposite

22I5-10343-PF 8 200946450 should cause an imminent temperature rise' to produce excessively high temperature areas. CH3〇fl + 1/2〇2 — 2H2 + C〇2 + Exothermic · · · On the other hand, on the downstream side of the recombination reaction unit 3, a steam recombination reaction of methanol is mainly carried out. That is, an endothermic reaction represented by the following formula (2) occurs by the action of a Cu 〇 catalyst. More specifically, the reaction of the formula (2) is a reaction of two stages of the reaction represented by the following formula (3) and the reaction represented by the following formula (4) (c〇 shift reaction). CHsOH + HzO — 3H2 + C02 · + endothermic · · · (2) CHsOH — H2 + CO + endothermic · · · (3) CHsOH + H20 -> H2 + C〇2 + exotherm • · · (4) This implementation In the form, the temperature of the recombination reaction unit 3 can be maintained within a prescribed range by appropriately adjusting the ▼, "々 々 V V* to your L / 入 "© and vapor recombination reaction introduced into the recombination reaction portion. . That is, in the recombination reaction section 3, an autothermal recombination reaction is carried out.比例 The proportion of 'partial oxidation recombination reaction and steam recombination reaction in the autothermal recombination reaction of methanol, the methanol consumption per lm〇1 using the partial oxidation recombination reaction and the methanol consumption per hour in the steam recombination reaction When the heat is calculated in a heat balance-dependent manner, the proportion of the partial oxidation recombination reaction is about 2%%, and the ratio of the vapor weight is about 8 (%). This assumes that the amount of heat released via the partial oxidation recombination reaction is entirely spent on the theoretical proportion of the endotherm of the vapor recombination reaction. However, 'actually, the temperature of the mixed raw material introduced into the gasification state of the recombination reactor 或 or the heat released to the outside by the recombination reaction sputum' is also entangled as the condition of the heat calculation +. In this case, since the vapor recombination reaction of the endothermic reaction proceeds sufficiently, it is derived from partial oxidation.

2215-10343-PF 9 200946450 The heat dissipation of the recombination reaction must be slightly more than the theoretical value. The mixing ratio of oxygen is slightly higher than the theoretical value to adjust the proportion of partial oxidation recombination reaction to about 2〇 to 30%, and the proportion of steam recombination reaction. It is preferably from about 8 〇 to about 70%. Further, regarding the steam recombination reaction, the reaction ratio of water to methanol is theoretically molar ratio ι:ι according to the above formula (2), but actually, a side reaction is likely to occur when the vapor is insufficient. Therefore, it is preferable to have a condition that the vapor is excessive compared to the theoretical value. However, when the proportion of steam is too high, the energy consumed is too large.

The mixing ratio of water to methanol in the mixed raw material (steam By Methanol: S/Μ ratio) is preferably about 1 to 5 to 2. 〇 (mol/mol). The reformed gas containing hydrogen produced in the reforming reactor of this mode is purified by an appropriate method. When a chemical method is used, for example, a carbon monoxide, carbon monoxide, and carbon monoxide are mainly treated with an alkali solution to remove carbon dioxide and carbon monoxide. Further, when air is used as the oxygen source of the mixed raw material, from the viewpoint of efficiently removing nitrogen, for example, a plurality of adsorption columns filled with an adsorbent which selectively adsorbs nitrogen are used to carry out PSA gas separation to remove nitrogen gas. The hydrogen can be concentrated. In the autothermal recombination reaction, the partial oxidative recombination reaction represented by the above formula (1) is carried out until the oxygen in the system is completely consumed. The vapor recombination reaction represented by the above formula (2) is carried out in the same manner as or in parallel with the partial oxidation recombination reaction. When using Cu 〇 alone catalyst as the recombination catalyst, it is necessary to adjust the conditions to ensure that the reaction temperature (for example, 25 〇t or more) is suitable for the progress of the vapor recombination reaction, for example, the sterol reaction rate of the first stage represented by the above formula (3). Up to 99% or more, the second stage represented by the above formula (4) = C〇 fluctuation reaction rate may be 95% or more. That is, it can be considered as (5) alone

2215-10343-PF 10 200946450 The 2-stage reaction of the vapor recombination reaction is excellent in selectivity, and the recombination catalyst as a vapor recombination reaction also has catalytic properties comparable to that of the Cu/Zn crucible in the net. Further, in the recombination catalyst of the present embodiment, since the Cu catalyst is supported by a unit catalyst such as Oxide, the preparation method is relatively easy, and it is also advantageous in terms of the raw material price. Further, the recombination catalyst (Cu〇 alone catalyst) of the present embodiment is stable in physical properties than Cu because it is used in the oxide state of metallic copper (Cu). Because of φ, the Cu0 single catalyst is less prone to sintering than the Cu/ZnO catalyst, and it also has a long-lasting enthalpy at high temperatures. In this way, the recombination catalyst (CuO alone catalyst) of the present embodiment can perform a catalyst for a long period of time with respect to both the partial oxidation recombination reaction in the high temperature region and the vapor recombination reaction in the endothermic reaction. performance. In addition, compared with the conventional Cu/Zn() catalyst method, which is formed into a small particle shape by using a fine powder of oxidized or the like as a dispersing agent, it is less likely to cause pulverization due to thermal history. Expect a long life. That is, when (5) a single catalyst is used as a recombination catalyst, when the hydrogen is produced in the form of the present embodiment, the combined partial oxidation recombination reaction and the vapor weight = should be, and the autothermal recombination reaction can be carried out appropriately over a long period of time. It can increase the efficiency of hydrogen generation. Further, according to the present embodiment, since the catalyst life of the long-term one can be expected in the autothermal recombination reaction, and the generated reformed gas is subjected to hydrogen separation by the gas separation method, the PSA gas separation device can be stably operated for a long period of time. 'It is better. Although the embodiment of the present invention is described, the scope of the present invention is the above-described embodiment. Recombination reactor of the present invention and the present

2215-10343-PF 200946450 Various changes can be made without departing from the scope of the specific configuration of the hydrogen production method of the present invention. The recombination catalyst (Cu0 alone catalyst) used in the present invention may be in a form not supported by the Oxidation Carrier, or may be a carrier supported on Oxidation (for example, cerium oxide, zeolite or active). Carbon). Next, the usefulness of the present invention will be described by way of examples and comparative examples. [Example 1] φ In this example, a recombination reactor (Fig. 1) of the following specific specifications was used, which consisted of methanol and air. The original one is mixed to produce a reformed gas containing hydrogen. The tube body 2 of the recombination reactor i is composed of stainless steel f (inner diameter: 23 dragons, full length: 400). The recombination reaction unit 3 is filled with a granular catalyst (particle diameter L2 to 2.5 mm) which is a catalytic catalyst supported by Cu 〇 alone as a recombination catalyst by filling height _ off. Here, the recombination reaction portion 3 is provided with an electric heater (holding temperature of 250 t) surrounding the outer side of the stainless steel pipe so that the upper end thereof is lowered from the upper end of the stainless steel pipe. The supply amount of the mixed raw material supplied to the reforming reactor was 4.9611101^, the water was 7 44m〇1/h (s/M ratio=15), and the air was 1/dm Ν/h (converted to pure oxygen) · 72m〇1/h) flow. This mixed raw material is supplied to the reforming reactor 1 after being heated to a vaporized state in a gasifier.胄 Recombination reaction 11 1 The temperature of the mixed raw material at the time of introduction was 260 c, and the pressure in the recombination reactor 1 was maintained at 800 kPa (pressure gauge). In this example, investigation of normal operation (mixing of the recombination reactor 1)

2215-I0343-PF 12 200946450 The temperature distribution of the recombination reaction section 3 after about 5 hours from the start of introduction of the raw material. The investigation of the temperature fraction is performed by measuring the temperature of a plurality of measurement points set in the recombination reaction section 3. The measurement point is set in the recombination reaction unit 3 by a plurality of points along the central axis in the gas flow direction, and the movable reaction unit 3 is disposed with a movable thermometer along the central axis. Therefore, the plurality of measurement points on the central axis of the temperature measurement portion are sequentially shifted, and the temperature of the measurement point is measured. The measurement results are shown in Fig. 2. The horizontal axis of the same figure indicates the measurement point, and the upstream end (upper end) of the recombination reaction unit 3 is used as a base point and is expressed by the amount of displacement in the gas flow direction. The vertical axis of the same graph indicates the measured temperature of the measurement point. The reformed gas derived from the recombination reactor 1 was cooled to room temperature by a heat exchanger, and the condensed liquid component was separated and removed by a gas-liquid separator, and then subjected to composition analysis using a gas chromatography apparatus. The analysis of the recombinant gas is carried out in the above-mentioned recombinant gas obtained during normal operation. The composition of the reformed gas, the main component of the hydrogen is about 63%, although other carbon dioxide, nitrogen, carbon monoxide, and argon are recognized, but by-products such as methane or dimethyl group are not confirmed. Further, it is considered that the total reaction rate (the total sterol reaction rate) is 99.5%, and it is considered that all of the methanol to be charged is consumed by the reaction. The C反应 variable reaction rate also gave a good result of 96.8%. [Comparative Example 1] In the comparative example, the same recombination reactor 1 as in Example 1 was used, and the same raw material supply state as in Example 1 was used, and a hydrogen-containing reformed gas was produced from the oil-mixed raw material. However, as a recombination catalyst filled in the recombination reaction section 3,

2215-10343-PF 13 200946450 Instead of the recombination catalyst to which Example i is applied, a Cu/ZnO catalyst is used. The recombination catalyst system Cu/ZnO is added with a fine powder of oxidized infusion as a dispersing agent. Further, in the same manner as in Example 1, the temperature distribution of the recombination reaction unit 3 was measured. The measurement results are shown in Fig. 2. In the comparative example, the results of the formation of the condensate and the reformed gas derived from the recombination reactor i during the normal operation were analyzed in the same manner as in the example '. The total methanol reaction rate was 98·8%, c. The 〇 change reaction rate was 96.1%. Further, the composition of the reformed gas, the main component of hydrogen gas was about 62%, and other carbon dioxide, nitrogen, carbon monoxide, and argon gas were also recognized, but by-products such as methane or dimethyl ether were not confirmed. From the results of the first embodiment and the comparative example, it is understood that the Cu〇 alone catalyst acts as a recombination catalyst in the autothermal recombination method, and similarly to the Cu/Zn〇 catalyst, the temperature regulation in the recombination reactor can be performed. It was confirmed that it has excellent catalytic properties comparable to Cu/Zn〇 catalyst. G [Comparison of durability of recombination catalyst] The same conditions as in the example j and the comparative example j were used, using the recombination catalyst (Cu〇 alone catalyst and Cu/ZnO catalyst) used in the above examples and comparative examples. Durability tests to implement catalyst performance. The results are shown in Fig. 3, and the horizontal axis represents the operation time (the elapsed time from the start of the recombination of the recombination gas by the recombination reactor), and the slave axis indicates the total methanol reaction rate at the elapse of the operation time. In the case of the CuO alone catalyst of the present invention, the methanol reaction rate at the time of passage at 7 亦 is also maintained at a value of about 99%. In contrast, in the case of Cu/ZnO catalyst, the total methanol reaction rate is at the beginning of the operation.

2215-10343-PF 14 200946450 shows a value of about 99% South, but it shows a slow decrease as time passes. Please decrease to about 8〇% at the time of passage of 700 hours. In the case of using any of the catalysts, the peak temperature in the high temperature region of the recombination reaction unit 3 is about 400 ° C. It is considered that the Cu/ZnO catalyst system is degraded by the catalytic activity through sintering, and the total methanol reaction rate is lowered. [Simple description of the map]

Fig. 1 is a cross-sectional view showing the schematic structure of a reforming reactor constituting a main portion of the hydrogen producing apparatus of the present invention. Fig. 2 is a graph showing the temperature distribution of an embodiment and a ratio of the present invention. 7 liters, and Han Ying state Figure 3 shows the durability map of the recombination catalyst. [Explanation of main component symbols] 1 Recombination reactor 〇 2 Tube 3 Recombination reaction section 4 Spacer 21 Raw material gas inlet 22 Recombinant gas outlet

2215-10343-PF 15

Claims (1)

200946450 VII. Patent application scope: 1. A method for producing hydrogen, comprising at least a mixed raw material of hydrocarbon and water: hydrogen is produced by a reaction enthalpy of at least a steam reforming reaction in the presence of a recombination catalyst, wherein The group of catalysts is composed of Cu0 alone catalyst. 2. The method of producing hydrogen according to the ninth aspect of the invention, wherein the tail material further comprises oxygen, and the reaction is carried out in the presence of a ruthenium of the recombination catalyst to carry out a partial oxidation recombination reaction and a vapor heavy reaction. 3. The method for producing hydrogen according to the first aspect of the invention, wherein the recombination catalyst is carried by a carrier selected from the group consisting of oxidized, oxidized sand, buddha and activated carbon. 4. The method for producing hydrogen according to the ninth aspect of the invention, wherein the hydrocarbon is selected from the group consisting of methanol, ethanol, dimethyl ether, decane, propane and butane. 5. The method for producing hydrogen according to claim 1, wherein the & is methanol and the molar ratio of water to methanol in the mixed raw material is from 1. 5 to 2. 0. 6. The method for producing hydrogen according to the second aspect of the invention, wherein the mixed raw material is selected such that an exothermic amount derived from the partial oxidation recombination reaction is substantially equal to an endothermic amount derived from the vapor recombination reaction. The ratio of hydrocarbons, oxygen and water in the medium. 7. The method for producing hydrogen according to the first aspect of the invention, wherein the hydrocarbon is a f-alcohol and the ratio of the partial oxidation recombination reaction is 2 〇 to the ratio of the vapor recombination reaction to 80 to (4)* , select 2215-10343-PF 16 200946450 The ratio of methanol, oxygen and water in the mixed raw material. 8. A hydrogen production apparatus comprising a recombination reactor having a gas passage equipped with a recombination catalyst, comprising a hydrocarbon, a mixed raw material of oxygen and water, and a recombination reaction with a vapor by a partial oxidation recombination reaction to produce a recombination containing hydrogen a gas, wherein the recombination catalyst is composed of CuO alone catalyst. 2215-10343-PF 17