WO2006054527A1

WO2006054527A1 - Reforming catalyst for oxygen-containing hydrocarbon, method for producing hydrogen or synthesis gas using same, and fuel cell system

Info

Publication number: WO2006054527A1
Application number: PCT/JP2005/020871
Authority: WO
Inventors: Naonori Ryumon; Tetsuya Fukunaga
Original assignee: Idemitsu Kosan Co., Ltd.
Priority date: 2004-11-16
Filing date: 2005-11-14
Publication date: 2006-05-26
Also published as: TW200633777A; JPWO2006054527A1; KR20070084220A

Abstract

Disclosed is a reforming catalyst for oxygen-containing hydrocarbons which contains copper, a metal oxide having a spinel structure and a zeolite. Preferably, the reforming catalyst further contains alumina, a group VIII metal or a rare earth element. Also disclosed is a method for producing hydrogen or a synthesis gas by subjecting an oxygen-containing hydrocarbon to (1) steam reforming, (2) autothermal reforming, (3) partial oxidation reforming or (4) carbon dioxide reforming, while using the above-described reforming catalyst. Further disclosed is a fuel cell system using the reforming catalyst. The reforming catalyst has a high activity and excellent heat resistance. When the reforming catalyst further contains alumina, a group VIII metal or a rare earth element, the amount of coke generation is suppressed, thereby further improving durability of the catalyst. Consequently, hydrogen or a synthesis gas can be efficiently produced by subjecting an oxygen-containing hydrocarbon to various reforming using such a reforming catalyst, and thus the reforming catalyst is used in a fuel cell system or the like.

Description

Book

Raw material, hydrogen synthesis gas production process and fuel cell stem

Art field

001, hydrogen syngas production method and cell stem for hydrogen syngas, and more specifically, it contains high-temperature, high activity, and durability The present invention relates to a method for producing hydrogen syngas by making various modifications to hydrogen fluoride and oxygen, and to a battery system using this.

0002 gas is made up of oxygen and hydrogen, and is used as a gas for methano-, oxy-, and yat formations, and is widely used as a material for annealing and various products.

This gas has been produced by conventional methods, or steam or partial methods using natural gas as a raw material. However, the coal law has a problem that it requires a complex and expensive coal gas furnace and a large-scale plant. In addition, there is a problem that the reaction of the steam in this case requires a large degree of reaction, requiring 7 to 2 ° C in the reaction line, requiring special modifications, and requiring the heat to be used. You. In addition, since a high temperature is required, a special part is required, and a large amount of soot is generated with the reaction. Therefore, in order to solve this problem, in recent years,

Attempts have been made to produce syngas by using hydrogen fluoride as a raw material and applying various processes to it. On the other hand, in recent years, onion technology has been in the spotlight due to environmental problems, and fuel cells are attracting attention as an onion technology. This battery converts leeks into electric leeches by electrically reacting hydrogen and oxygen, and the rate of leeks is high. Some are actively researching practical applications for automobiles.

The fuel cell has been researched on hydrogen, such as gas mainly composed of methane and methane, city gas mainly composed of this gas, synthetic materials based on natural gas, and petroleum oil and NASA oil. It is.

In the case of producing elements using these hydrogen halides, in general, the elements are subjected to steaming or partial treatment, but in this case, the above-mentioned problems arise. Therefore, in the production of hydrogen, a method using raw materials such as metite as a raw material has been seen.

Various materials have been disclosed to be used in the production of hydrogen syngas by using various raw materials such as metite as raw materials. As a technique to modify hydrogen oxyhydride, for example, for C, a medium for producing gas from oxygen and dioxygen, and production of gas using the same (for example, a patent), C Thus, a medium for producing hydrogen from hydrogenated oxygen and water vapor and hydrogen using the medium (for example, Patent 2), and a material bearing a genus including solid C (for example, Patent 3, Patent 4), a medium for producing hydrogen from oxygen and water vapor, which is a mixture of a C-containing substance and a solid substance, and hydrogen produced using the medium.

(For example, Patent 5), a medium for producing a gas from oxygen and water vapor, and a gas production using the medium (for example, Patent 6) made of a mixture of a C-containing substance and a solid substance are disclosed. It is.

However, the C system used in these procedures is not sufficiently thermal, so increasing the reactivity to improve the reactivity.

There was a title that was not avoided. 0005 1 74869

2 7487

3 2 96 59

4 2 96 6

5 2 3 684

6 2 3 33656

Invention

Issues that Ming tries to solve

006, made under the above circumstances, containing copper, excellent thermal properties, high activity, long-lasting hydrogen fluoride

The purpose is to provide a method for producing hydrogen synthesis gas by making various modifications to oxygen. Also this excellent

An object of the present invention is to provide an excellent fuel cell system having a fuel cell using hydrogen produced as a fuel.

To solve the problem

007, as a result of repeated research to achieve the objective,

Combined with spine orite, the heat is increased and the activity is increased and the durability is improved. In addition, it contains anana, group 8 and rare earth elements. To oxygen

I found out that I was able to further control and achieve that goal. It was completed based on the look. In other words, the present invention provides a battery cell system for hydrogen synthesis gas having the following elements.

() An elemental material characterized by containing a metal oleite containing copper and having a structure.

(2) The ratio of the metal oleite containing copper and having the structure is elemental in () where the mass quasi is ~.

(3) Metal objects that contain copper and have a structure Element of () or (2).

(4) Olite is 5 () ~ (3) deviation element 0.99 (5) contains copper, contains metal, olite and analyse () ~ (4) deviation Of the element described in. (6) Olyte contains 8 and / or earth elements () to (5).

(7) The element of (6), wherein the genus 8 is at least one genus selected from P Pd R.

(8) The genus of (6) is a genus of at least one kind selected from e and Co.

(9) Obtained by taking the deviation from () to (8)

Primitive.

() Hydrogen fluoride is at least one of the elements selected from (1) to (9). 0010 () () () to () for the production of hydrogen synthesis gas, characterized in that oxygen is steamed.

(2) Production of hydrogen synthesis gas characterized by self-oxygenation for deviations from () to ().

(3) Production of hydrogen synthesis gas characterized by partial oxygen for the use of deviations from () to ().

(4) For the difference between () to ()

Production of hydrogen synthesis gas, characterized by

(5) A fuel cell system comprising: a fuel cell using hydrogen produced by (1) as a fuel provided in any of the deviations (1) to (5).

FIG. 11 is an abbreviated diagram of a clear battery stem.

Of the issue 001

Supply

2 21 Tank

twenty three

24 Pop

Three

31 Na

32 O

33 O

34 batteries

34A battery

34 batteries

34C battery polymer disassembly

35 watts

36 Separation

37

37A exchanger

37 Exchanger

37C

37 Pump

Good for carrying out Ming

0 In the clear invention, the element contains copper,

It contains metal oleite having a structure, preferably further containing anana, 8 and a portion of earth element.

As elements of light, I prefer methano, tano, etc., mechite, mechite, etc. be able to. Of these, methite and methite are particularly preferred. In particular, a metal having a spine structure is a metal mold.

It has a surface-shaped cube found in things. It is usually a divalent genus and is a genus of.

In the art, metal materials containing copper are used, and examples of metal materials include C-type spines, Ce-type spines, and CC-type spines. The C-type spin is preferred. An example of the C-type spin is C, and an example of the Ce-type spin is C. Examples of the C C type sp include C C. In addition, C 1

2 4 2 4 and C (eC) C (e) C (e)

2 4 2 4 2 4

Can do. C (e) Spi and

2 4 then C (e

5 05) 4 C (e 0 0) O, e

4 C (e

2 3 4 3) (

4 C 0 · 5 1).

・ 5 4

The metal structure containing copper is superior to the spine structure containing copper in that it has excellent thermal properties, and when used as a raw material, has a high unit surface area.

In the light, it is possible to use a material containing a spine-like copper as desired, as long as it does not impair the purpose of the light.

Next, a case of preparing C will be described as an example of a method for preparing a metal product containing copper, which is used for light. First, a soluble ngan salt such as ngan is used as a solubilizing material such as copper, and a solution containing these so that a substantial proportion thereof, that is, a ratio to C is substantially 2. In this solution, after adding a tonic agent such as oxalic acid, it is heated to evaporate the water to produce. Next, this powder is heat-treated and the powder obtained by decomposing nitric acid etc. in the powder is about 3-5 degrees in air at a temperature of 3-5 degrees Celsius. After that, C is obtained by further increasing the temperature by 5 to 5 degrees C. Also over 7 C

2 4 If

2 3 and

It is said to be a compound of 3 4 C 5 4

Five .

In this method, can be used so that C is in excess of the chemical ratio to. In this case, the obtained metal compound becomes a compound with copper acid (C or C 2 O or a compound thereof).

In addition, when preparing C, a soluble material such as iron may be used instead of the gun source. Further, by using a compound with an Ngan instead of the Ngan source, a metal material composed of C (e) can be obtained.

0017 Aluminium, made of the above-mentioned copper containing copper

In addition, it contains oleite. Olite includes ZS5, Denite, X-type, Mold, Mold, Mold,, Light, etc., and Denite ZS5 is preferred for durability, and ZS5 is particularly preferred.

Denite ZS 5 is preferably a type that is completely or partially converted to a proton rather than a cation in terms of sex.

Preferably, it is from mass to 2 and more preferably from 2 to 5 with C-type spiolite. Olite is more preferable than this because the smallness decreases and the number of causes causing the increase increases.

00118 Copper containing nelite Olite

It can be prepared by the following method. In other words, after mixing the powder of the metal product containing copper and the oleite powder to the quality, it is molded into an appropriate size, or the material of the product containing copper.

A clear preparation can be made by, for example, a method of mixing an appropriate size orite of an appropriate size.

0019 As an ana- lyte contained in the new Olite containing copper A V 0 X misaligned crystal form can be used. It is also possible to use baked anana such as Itoialite Gisite. In addition to this, you can add 8 ~ degree of aka to the aum to create a sinking thing. You can also use it. Also, aum soppod and other a are dissolved in 2 puno and other a, and an acid is prepared by adding water as a water splitting. I can do it.

Ana content is 5 to 5, preferably 8 to 4 and more preferably to 3 for a mixture of oleite and anana of copper. By having 5 to 5 ana, it is possible to obtain the results of the control without significantly reducing the activity.

The addition of anana may be performed simultaneously with the addition of neolite containing copper, or may be added before or after the addition of neolite containing copper.

Examples of 8 contained in 0020 oleite include metals such as platinum and radium, iron, iron and iron.

Examples of the metal include platinum, radium, um, and diadium, with platinum being particularly preferred.

Examples of platinum products are P C 4 2PC6 P (

3) 4C2 () PC P P (C) C P () (O)

2 P (

4 2 2 2 6 4 2 4 3 3 4 3) 2 (O2) and the like.

These gold compounds may be used alone or in combination of two or more. The same is true for the radiium, um, dium and iridium below.

Examples of radium which is radium include (

4) 2PdC

) PdC Pd () C PdC Pd () etc.

4 2 2 3 2 Yes.

2 4 3

For example, C R (

) R (O) C 7 3 O (C () () (C () 3 3 2 2 4 3 2 2 5 2 4 2 5 2 a (CO, RO aR OR (O) (O) O (O c) (5 3 2 2 4 3 3 3 6 O)) O c O ((C) O (() (O) (O)) ( (2 3 2 4 6 2 2 2 4

NH 3) 6 C,

3 ((

3) 6),

3 ((

3) 6 C2 ((

3 6 2 3O2 (3) 4) C O ((O) ()) C ((O) (O) () (

(4 O)

3 2 R C (6 2 3 5 3 3 2 PP) R C (PP) (C (PP) ・ C R (PP)

3 7 8 2 3 4 R C (CO) (3 3 2 3 4 3 P P)

3 R (

2 CO) (PP) (

3 3 C (co

2 d)) R (CO)

2 R (acac) ((3 3 C OO) (CO) R (P c e e)

2nd magnitude um

2 4 2 Salts can be mentioned. Among these um compounds, CR (

For example, aR C () R C

3 6 4 2 6 R () C, C and the like can be mentioned.

3 5 3 3

As an iridium product, for example, (

4) 2 C6 C3, 2 C, etc.

From the point of view of the metal content, the performance of the product and the balance of the performance, etc., it is preferred to be ~~, more preferably ~~ 5 for Olite.

There is no particular limitation on the method of preserving the precious metal content in the olite. If you take more than two minutes, you can take the minutes or at the same time. As the work of metal, heating, vacuum, normal,

Methods such as immersion, sp, and ion exchange methods such as ing, ing, and ncpen weness methods can be used, but impregnation and ion exchange methods using ing, ncpen weness methods are preferred.

The 8 minutes outside the noble metals contained in 00223 olite include e Co. The compound used as a material for the eCo component is not particularly limited but is preferably a soluble one, and an acid salt is generally used.

Olite's e N Co law is not particularly limited. In addition to the method described above for the metal component, a method such as addition from the oleite period can also be employed. Especially by ion exchange method, described below The addition of the Olite period by law is preferred.

The abundance of e N Co is 5 to 2 or more to orite. By adding 5 to 2 olite, it is possible to obtain additional results.

elite with the addition of e N Co, for example, air current, 2-8. C, 4 is preferred.

Addition of 3 or more at the C degree will further improve the additive effect.

In the case of adding Fe N Co from the 024Olite period, there is no particular limitation on the method of Olite, but for example, an organic compound such as prepared tetrapium ammonium is added, and organic substances are added to the preparation. A method of adding seeds such as denite without addition can be applied.

Before or after the charge, sodium for adjusting the amount of sodium (tempt) can be added, and further, an accelerator such as sodium can be added.

0025 In this case, for example, sodium, glass, powder, water-based mosquito, etc. can be mentioned, and in particular, aqueous reaction compound gate control, provision of acacion source and qualities. I prefer glass and idka. As the glass, those specified as Nippon Kogyo 3 are suitable.

As anana, anatomium, aum, active anna, and ana can be used, and anatomium, anoum, etc. are particularly preferred.

Acac can be supplied together with glass, idka, etc., or anana, etc., and examples thereof include sodium hydroxide, water hydroxide, etc. In particular, it is preferable to use sodium hydroxide.

The agent (template) is an organic substance. 2 3 Nnotanoan Nopnoan diguante tetrapiumum Tetrathianum and these amnesium ditin diananopun are used, especially diguantetrapium Is preferred.

As a matter of fact, the S 2 2 3 ratio is ~ 3, preferably 2 ~. If it does not progress further than this, the sex is bad and the sex is bad. Also, (M is e N Co.) The ratio is 5 ~ 2, preferably ~. If this is not the case, it will be less effective.

0026 As a rare earth component in Olite Sc a Ce P d P S

Gd b o is mentioned. These earth elements are not particularly limited. If the solubility is methanotanolytic, acid salts are generally used.

There are no particular restrictions on the law of soil. If it takes 2 minutes or more, the solution of the minute can be the methanotano solution or at the same time. As work

Ing ncpen weness method etc.

Methods such as sp-ion exchange can be used. The inc ncpen weness method is effective for impregnation with solution, and even more preferred for impregnation with methano and tano.

The earth's part is ~ 2 is preferred. -By setting ~ 2, the effect of rare earth elements can be obtained economically advantageously. In fact, the activity can be further improved by the above. In addition, there are a gas phase method that uses an air stream containing hydrogen and a wet method that uses a base material. The normal air flow is 5 to 5 C, preferably 2 to 3 C, and preferably 3 to 24, and preferably between. Gases such as nitrogen, um, and ann coexist outside the gas. Anyway.

As for the original method, the following are the origins of chan- nes that use an aa a ana, enkese that use a methiae, etc. There is a method of treating with a reducing agent such as horn or hydrazine. In this case, it is usually from room temperature to C, up to 24, preferably 3 to.

In addition, the catalyst is restored to the reaction by the generated hydrogen by flowing the reaction material.

In fact, it is removed by the former or generated gas, so that C is released from other elements and the spine part or all is not retained. First, it is important to use C, which has a structure.

In the production of hydrogen synthesis gas in the application of 0029

For light, hydrogen synthesis gas is produced by using () steam, (2), (3) part (4) for elements such as metite.

Next, we will explain the case of using metite in the law.

In the case of light use, it is thought that the reaction proceeds according to the reaction shown below.

C C 2C ()

3 3 2 3

2C O 2 O 2C 6 (2)

3 2 2 2

2C 2 2C 2 (3)

2 2 2

Therefore, when producing hydrogen, the reaction in (3) proceeds, that is,

C OC 3 O 2C 6 (4)

3 3 2 2 2 Select a response when the response occurs.

On the other hand, in the case of producing synthesis gas, the reaction of (, 2) and (3) occurs, that is,

C OC O 2 4 (5)

3 3 2 2

Select a response when the response occurs.

The ratio of water vapor methite is theoretically 3 when producing elemental gas, but 3 to 6 degrees is preferred. On the other hand, when producing synthesis gas, the ratio of water vapor methite is theoretically Is preferred, but 2 degrees is preferred.

It is usually selected in the range of 2 to 5 C, preferably 25 to 45 C. If the temperature is 2 C, there is a risk that the ratio of metite will be low, and if it exceeds 5, it will cause a problem. For GS (gas space), the MET range is preferred to OO range. The production rate of GS is low in OO, which is not practically preferable. If it exceeds OO, the rate of metite is too low, and it is not preferable in practical use. The reaction is usually from normal to Pa degrees. If this force is too high, the ratio of metite tends to decrease.

0032

In response, the reaction of methenite and water vapor occurs in the same actor or in successive actors. In this case, the reaction between hydrogen production and synthetic gas production will be slight, but in general, the oxygen methylate ratio is preferably selected in the range of ~, and the steam methylate ratio is preferably 5. It is selected in the range of ~ 3. If the metite ratio is •, the reaction due to exotherm may not be sufficiently supplied, and if the ratio exceeds 1, the completeness may occur and the element concentration may decrease. In addition, when the water vapor ratio is -5, the hydrogen concentration may decrease, while when it exceeds 3, there is a risk that the supply of heat will be insufficient.

Usually, it is selected in the range of 2 to 8 C, preferably 25 to 5 C. The GS force is the same as that of the steam. 003

However, in general, the ratio of oxygen metite is selected within the range of 3 to 5. . When the ratio of this metite is • 3, the rate of metitete may be sufficiently high, while when it exceeds • 5, completeness occurs and causes a decrease in the hydrogen concentration.

It is usually selected in the range of 2-9 C, preferably 25-6 C. Further, the G S force is the same as that of the steam.

003

However, in general, the ratio of CO metite is preferably 8-2, more preferably 9-9.・ Selected within 5. If the ratio of CO metite is -8, the ratio of metite may be sufficiently high, while if the ratio exceeds 2, it will cause a large amount of C to be produced, resulting in a decrease in hydrogen. May be necessary and is preferred. In this reaction, water vapor can be introduced, and the hydrogen concentration can be increased by this introduction. The reactivity and G S force are the same as in the case of steam.

The present invention has a fuel cell system characterized by having a fuel cell using hydrogen produced by the above-described preparation as described above.

Introduced into fuel desulfurization 23 in tank 2. Normally, it is not contained when using methyte suitable as oxygen, but desulfurization is effective when it contains a compound. 23 can be filled with, for example, sex charcoal, oleite or metal agents. After the pump 24 is mixed with water from the tank desulfurized in 23, it is introduced into the gas, vaporized, and sent to 3. 3 is filled as described above, and the compounds (elements and water vapor) sent to 3 are The raw material is produced by the steam reaction described above.

0036 Hydrogen produced in this way passes through 32 CO converter 33

The degree is reduced to the extent that it does not affect the performance of the fuel cell. For these, 32 includes cum-based or noble metals, and the converter 33 includes um-based, platinum or those. If the degree of hydrogen in the hydrogen produced is low, 32 may not be installed.

The 037 battery 34 is an example of a polymer electrolyte battery having a polymer electrolyte 34C between the negative electrode 34 and the positive electrode 34. In this case, the hydrogen switch obtained by the above method is inserted into the positive electrode, and the air sent from the air 35 is inserted into the positive electrode if necessary.

In this case, a reaction in which hydrogen gas becomes protons and emits electrons proceeds in the negative electrode, and a reaction in which oxygen gas obtains electrons and protons proceeds in the positive electrode, and a direct current is generated between both electrodes 3434. In this case, platinum or activated carbon P or P medium is used for the negative electrode, and platinum or activated carbon P medium is used for the positive electrode.

Hydrogen can be used as fuel, with the third na 3 connected to the 0038 34 side. In addition, an air separation 36 is connected to the positive electrode 34 side, and water and exhaust gas generated by the combination of hydrogen and air in the air supplied to the positive electrode 34 side are separated, and the water is used for the formation of water vapor. be able to. The battery 34 generates heat as it generates power.

37 can be attached to recover this heat for effective use. 37 is a heat exchanger attached to the fuel cell 34, an exchanger 37 for exchanging heat from the exchanger 37 with water, a cooling 37C, and these exchangers 37 37 37C. The water obtained in the heat exchanger 37 can be used effectively in other facilities.

Next, the present invention will be described in more detail by implementation, but is not limited by these examples. The catalyst SAP 8 (eCo) and earth (a Ce S) were measured by the following method using a CP optical spectroscopic analyzer.

0040 (CP) ・ S in ZS 5 and the law of

Sample 59 ・ Platinum 59 and titanium-titanium compound (9 and 5 are combined. 925C 2, bring to room temperature. Add tartaric acid 5 4 to 4 and dissolve again. Quantify S in this solution with CP.

2.P method in ZS 5

Sample 9 is taken in an analytical pot and heat-treated at 9 C for 6 hours. Then, the sample is taken into a ten () vessel and oxalic acid 4 is added. Next, add, and add 0, 2 of OOO as a watch cover, and adjust the volume to 5. Quantify P in this solution by CP. Add the same solution as above to P and measure. 3.Rare earth in ZS5 and 8 (eCo) method

Sample ・ Platinum 49 ・ Ion 3 Basic acid ・ 5

・ Add hydrochloric acid and heat until smoke is emitted. Add ion O and heat further. When it becomes transparent, stop heating and adjust to 5. The earth (a Ce S) and 8 (e Co) in this solution are quantified by CP.

004 (CP method)

For analysis, Seins Co., Ltd., SPS type 5, which is a multi-element CP optical spectroscopic analyzer specified in CPJ 6, is used.

2.

3 W Angus Plas… 6

Okity Gas ... ・ 2

A gas… ・ 4 ～・ 5 (2 2kg cm) Light height 2 (Wakui)

2 4 423 (P) 333 749 (a, 4 8 65 g (Ce) 359 25 g (S) 25 6 8 (S) 396 52 () 238 2 (e 23 6 4 (, 238 892 (Co)

004 (of)

And, as obtained in the examples, etc., the steam reaction of Mechite (described) was performed as follows.

Molded into 6 to 32 mesh obtained in () and examples, and filled into reaction.

(2) Before steaming, heat to 25 C in hydrogen gas () and restore.

(3) In implementation ~ 9 and ~ 2, the system

5. The quasi G S (gas space) was 9; the gas (O) quasi G S was 54; Also, implementation, 3, 4-36 and

For 3-4, the ratio of the king rate after steam 5 · O, quasi GS (gas space) 333, gas (O) quasi GS 2, reaction 28 () and after 8 Evaluation was performed.

The rate is the numerical value indicated by from the reaction gas.

() () X

C C C C C C () King () is the numerical value indicated by.

King () (C) X Medium amount including the amount of C formed by C 25 C ()

8 C at 25 C

(4) Durability, in implementations ~ 9 and ~ 2, the reaction rate is 333 for GS (gas space) of the 5th class, 2 for GS (gas space), 2 for the gas (O) level, and 25C for the reaction. The time required to fall below 9 5 was defined as the interval. Also, implementations 3 to 4 7 2 2 24 and 3 are steam 5 · O, quasi GS (gas space) 333, gas (O) quasi GS 2, reaction 28 C for 4 It was rated by later activity (after 4 minutes) and the above king ().

004 (C and 2 in ZS 5)

Bite of a lytesque, 99.

3 28 (55) Made by Ngan Adorn, 98

(

3 26 2 3 55 (8), 2 to 3 to 6C. Then, 34 65 (65) made by this quan-aduccin was added, and after 6 C, water was evaporated to 8 C.

The product thus produced was heated at 4 C for 7 minutes, and oxalic acid was decomposed to obtain a powder. Then, 2 at 4 C in air, and 9 at 9 C in air. It was. The obtained C nitride (compound of C) and ZS 5 (Zeo s

5, 1 ・ 5 5 2 3

C 2 ZS 5 2 was prepared by mixing 3 2) 5 with. The results of the obtained and the durability values are shown in Table.

0442 2 (2 of C and Denite) Denai (manufactured by Co., Ltd., SZ 64 A was ion-exchanged with 6 C 4 ion with Li Aum, dried at 2 C overnight, then baked to 5 C 3 to get Denite. By mixing C-nitride denite 5 prepared in the same manner as above, C-nitride and denite 2 were produced. The results of the values obtained are shown in Table.

004 (C and 2)

1 C-analyte prepared in the same manner (manufactured by Gaku Kogyo Co., Ltd.) PG 55 was mixed in to produce C-analyte and anana 2. The results of the values obtained are shown in Table 1.

046 2 (2 in C Z ZS 5)

C Z (catalyst, C 3) and ZS 5 (Zeo s, C 3 2) 5 are mixed with

ZS 5 2 manufactured. The results of the values obtained are shown in Table.

004 3 (C and ZS 5-8)

1 By mixing C nitride 2 and ZS 5 (Zeos, C 3 2) 2 5 prepared in the same manner, 8 of C nitride and ZS 5 were produced. The results of the obtained values are shown in Table.

004 4 (C and ZS 5 32)

(1) C nitride 32 and ZS 5 (Zeo s, C 3 2) prepared in the same manner as above were mixed in to produce 32 C nitride and ZS 5. The results of the durability values obtained are shown in Table 1.

049 5 (C and ZS 5 2)

1 C-N 2 and ZS 5 were prepared by mixing C-Ne5 prepared in the same way with ZS 5 (Zeos, C 3 2 O). The results are shown in Table.

00506 (C and PZS 5 2

)

Made by industry company, 98 ・ 5 C 6 27 (

2 6 2

・ 5) was dissolved in 35 tons, impregnated with ZS 5 (Z., C 3 2) O, 3 with 2 C, 3 with 4 C, and P ZS 5 was prepared.

C-Noise prepared in the same manner. By mixing PZS5 at 5 above, C-Nexide and PZS5-2 were produced. The results of the values obtained are shown in Table.

005 1 7 (C Net and P ZS 5 8

)

By mixing C nitride 6 and O • P ZS 5 prepared in the same manner in the above manner, 8 of C nitride and • P ZS 5 were produced. The results of the obtained and the durability values are shown in Table.

0052 8 (C Net ・ P ZS 5 2

)

Tetraann (School medicine, P ()

(3 4C)

2 86 (26) was added to 3 tons and 8 C. In this solution, ZS 5 (Zeos, C 3 2) was replaced with 9 ions at 5 and 8 C, dried overnight at 2 C, then baked at 4 C at 3 C.

P ZS 5 was obtained.

C-Noise prepared in the same manner By mixing the above-mentioned PZS5 with 5, CNexon and PZS52 were produced. The results of the values obtained are shown in Table. 0053 g (C Ne-P ZS 5 8 C prepared in the same manner 6 Ne 8 Performed in the same manner-By mixing P ZS 5 with C

Ne / P ZS 5 8 manufactured. The results of the obtained and the durability values are shown in Table.

0054

As a result of the activity values in Table 055, the C-neutral material is mixed with Olite such as ZS 5 denite, which has higher vapority than the C-Neana mixture, and the conventional C system

Compared with ZS 5, it shows the same vapority and less reaction. (~ 2, comparison ~ 2) In addition, as a result of evaluating the durability of the catalyst by changing from 2 to 32 of C ZS 5 in the table, the durability in mixing 2 was between 5 due to the key. On the other hand, in 2 to 32, the durability is 25 or more, and it is preferable to mix C neon with Olite. (3-5)

Furthermore, as a result of the activity values in the table, mixing C and Olite containing noble metal (P) improves the activity further compared to the Olite not containing noble metal, and lowers the King rate. I understand. (6, 8 implementation and 7, 9 implementation 3)

0056 (C Ne ZS 5-8 Ana 5)

C ne 6 ZS 5 (Zeos, C 3 2) 2 prepared in the same manner, and Ana (P 5 95 manufactured by Kogyo Co., Ltd.) were mixed with

(8) of ZS 5 was obtained. Table 2 shows the results of the durability values obtained.

0057 (C Ne ZS 5 8 Ana 8)

C Ne 6 ZS 5 (Zeos, C 3 2) 2 prepared in the same manner and Ana (PG 5) 6 manufactured by Kogyo Co., Ltd. (8 was obtained. Table 2 shows the results of the durability. 058 2 (C and ZS 5 8ana 2)

C Cnide 6 ZS 5 (Zeos, C 3 2) 2 prepared in the same manner, and Ana (PG 5) 4 5 made by Gana Kogyo Co. (8) of ZS 5 was obtained. Table 2 shows the results of the durability values obtained.

0059 3 (C and ZS 5 8ana5)

C N-salt 6 ZS 5 (Zeos, C 3 2) 2 prepared in the same manner and ANA (PG 5) 8 made by Gana Kogyo Co., Ltd. 5 of (8) was obtained. Table 2 shows the results of the durability values obtained.

00603 (8 of C Z ZS 5)

C Z (catalyst, C 3) 6 and ZS 5 (Zeo s, C 3 2) 2 are mixed with

Manufactured 8 of ZS 5. Table 2 shows the results of the durability values obtained.

006 1 2

Table 2 also shows the results of performing durability in the same way as in implementations 0 to 3. ~ 3 From implementation 3, C It is confirmed that the addition of the chemical compound and the ZS 5ana is less active and the kin rate is also reduced.

063 4 (C e e ZS 5 (S,

) (8))

99 e (g O 47 (

3 3 2 3 · 6) was dissolved in a ZS 5 (Z., C 3 2) 2 impregnated with 2 C and 3 with 4 C to obtain e ZS 5 (S). The obtained e ZS 5 (S) was subjected to 3 element reduction with 5 C before mixing with C ne.

C ne 6 prepared in the same way C e e ZS 5 (S,

) (8) was obtained. Table 3 shows the results obtained and the results of durability.

0064 5 (C Ne ZS 5 (S,

) (8))

98 (6 O 2 (

3 2 2 3 ・ 4) Dissolved in ZT 5 (Z., C 3 2) 2 impregnated in 2 C 3 in 4 C

ZS 5 (S) was obtained. The obtained ZS 5 (S) was subjected to 3 element reduction with 5 C before mixing with C ne.

C Ne 6 prepared in the same manner as described above By mixing ZS 5 (S) 2 with only hydrogen reduction obtained in the above order, C ne ZS 5 (S,

) (8) was obtained. Table 3 shows the results of the values obtained. 065 6 (C Net Co ZS 5 (S, ) (8))

98 Co 2 (3

・ 4) was dissolved in the ZT 5 (Z., C 3 2) 2 impregnated with 2 C and 3 with 4 C to obtain C ZS 5 (SA). The obtained Co ZS 5 (S) was subjected to 3 element reduction with 5 C before mixing with C ne.

C Ne 6 prepared in the same manner as above. By mixing the hydrogen reduction-only ZS 5 (S) 2 obtained in the above order with C Ne Co ZS 5 (S,

) (8) was obtained. Table 3 shows the results of the values obtained. 006 7 (C / e ZS 5 (S, ion) (8))

99 e ()

3 3 9 2 365 (・ 8 9) was added to 3 tons and 8 C. In this solution, ZS 5 (Z., C 3 2) was conducted at 5 98 C for 9 ion exchanges. After drying overnight with the above ion 2 C, 3 at 4 C

• e ZS 5 (S) was obtained.・ E ZS 5 (S) was subjected to 3 element reduction with 5 C before mixing with C ne.

C ne 6 prepared in the same way. By mixing the hydrogen reduction obtained in the above order with e ZS 5 (S) 2, C ne e ZS 5

(8) was obtained. Table 3 shows the results obtained and the results of durability.

067 8 (C, ZS 5 (S

(Ion) (8) 98 ()

3 26 2 253 (85) was added to 3 tons and 8C. In this solution, ZS 5 (Z., C 3 2) was conducted at 5 98 C for 9 ion exchanges. After drying overnight with the above-mentioned ion 2 C, 3 · ZS 5 (S) was obtained at 4 C.・

ZS 5 (S was subjected to 3 elemental reduction with 5 C before mixing with C nitride.

C Ne 6 prepared in the same manner was mixed with the hydrogen reduction-only ZS 5 (S) 2 obtained in the above order to obtain C Net ZS 5 (8). Table 3 shows the results of the values obtained. 068 9 (C Ne Co ZS 5 (S, Ion) (8))

98 Co., Ltd.

252 (85) was added to 3 tons at 8C. In this solution, ZS 5 (Z., C 3 2) was conducted at 5 98 C for 9 ion exchanges. After drying overnight with the above-mentioned ion 2 C, 3 · Co ZS 5 (S) was obtained at 4 C.・ Co ZS 5 (S) was subjected to 3 element reduction with 5 C before mixing with C ne.

C ne 6 prepared in the same way By mixing the hydrogen reduction-only Co ZS 5 (S) 2 obtained in the above order with C ne Co ZS 5

(8) was obtained. Table 3 shows the results of the values obtained.

069 2 C Neon ZS 5 (See 5 5, e when ZS 5 is formed) (8) Aum Industrial 99/5 (S) 8 9 5 (

2 4 3 2

3 ・ 7) 99 e ()

3 39 2 ・ 2 (27 ・ 4) 97 (99 ・) Tetrappiumum

The liquid obtained by mixing 26 8 (98 · 9) and 25 ton was designated as. The liquid obtained by mixing glass (S 3 SO 29 a 9 · 4 6 · 6) 5 6 manufactured by this chemical industry was used. Also, C was a liquid obtained by mixing 99 · 5 aC 4 2 (684) 2 tons manufactured by Sodium Industries. While stirring this liquid C, the above and liquids were combined in C at the same time. To this compound, add 97 2 (9, 8) manufactured by Sangyo Co., Ltd., and adjust to g ・ 5. 2 The mixture is cooled to warm and solid

Until g · 5. The recovered 2C was converted to C in the air in the 6th order.

Next, the ion exchange between 4 and 6C was carried out using the solution of Aritsu's ammonium. After the above ion-exchanged ion-exchanged product was dried at 2 C for 6 times, 4 Z was used to obtain 3 ZS 5 (e at the time of forming SeA e 55 zS 5). It was confirmed by CP that it was SO 57/7, e and by ZS5. ZS 5 (S e e 5 5)

Before mixing with hydrogen, hydrogen reduction treatment was performed at 5 C for 3 hours.

C Ne 6 prepared in the same manner and Z S 5 (S e A e 5 5) 2 obtained by mixing the hydrogen reduction-only ZS 5 (S e A e 5 5) 2 obtained in the above order with (8) was obtained. Made of and permanence The results are shown in Table 3.

0072 (C-Need ZS 5 (S e e g, e when ZS 5 is formed) (8))

Aum Industrial 99/5 SO

Four

4 ・ 6) 99 e ()

3 39 2 2 23 (5 47) 97 (99, manufactured by Terapia Mock Industry Co., Ltd.) 98 8 (98 · 9) and 25 tons were mixed to obtain a liquid. And solution C were prepared in the same manner as in Example 2.

While stirring this liquid C, the above and liquids were combined in C at the same time. To this compound, 97 4 (3. 9) manufactured by Sangyo Co., Ltd. was added to adjust to g. Then, it was prepared in the same manner as in Example 2 to obtain ZS5 (e when SeggS5 was formed).

CP for SO 35 ・ 7, eg ・ for ZS 5

2 2 3

It was confirmed that The obtained ZS 5 (S e A e g) was subjected to hydrogen reduction treatment at 5 C for 3 hours before being mixed with the C nitride.

C NeI prepared in the same way 6 By mixing ZS 5 (S e A eg) 2 of hydrogen reduction only obtained in the above order with (C) and ZS 5 (S e A e 9) 8) obtained. Table 3 shows the results obtained and the results of durability.

071 22 (C-Noise ZS 5 (when S A g zS 5 is formed) (8))

Aum Industrial 99/5 SO

4 ・ 6) 98 (O) 6 2 62 (5 47 97 (5 47)

2 4 99 ・) Tetrappianum 98 (CCC ) 26 8 (98 ・ 9) and 25 ton were mixed to obtain a liquid. And solution C were prepared in the same manner as in Example 2. While stirring this liquid C, the above and liquids were combined in C at the same time. To this compound, 97 2 4 (23 · 8) manufactured by Sangyo Co., Ltd. was added to adjust to g · 5. The same procedure as in Example 2 was carried out to obtain ZS 5 (when Sg ZS 5 was formed).

It was confirmed by CP that they were SO 2 2 3 35 ・ and 9 ・ 6. ZS 5 (S A g) was subjected to hydrogen reduction treatment at 5 C for 3 hours before mixing with C ne.

C 8 prepared in the same manner was mixed with hydrogen-reduced ZS 5 (S g) 2 obtained in the above order to obtain (8) of C 4 ZS 5 (S A 9). Table 3 shows the results of the values obtained.

072 23 (C Ne ZS 5 (S Co Co 9, Co when ZS 5 is formed) (8))

Aum Industrial 99/5 S

O4

4 ・ 6) Togyo 98 Co (O) 6 2 62 (5 47) Togyo 97 (

A liquid obtained by mixing 98 (C CC) 268 (98 · 9) and 25 tons produced by 2 4 99 ·) Tetrappianum Co., Ltd. was used. And solution C were prepared in the same manner as in Example 2. While stirring this liquid C, the above and liquids were combined in C at the same time. To this compound, 97 2 2 (2 · 8) manufactured by Sangyo Co., Ltd. was added to adjust to g · 5. Thereafter, ZS 5 (Co 3 when S C Co 9 zS 5 was formed) was prepared in the same manner as in Example 2.

The CP confirmed that it was SO 2 2 3 35 • 9, Co 9 •.

ZS 5 (S Co Co 9) Before combining, hydrogen reduction treatment was performed at 5 C for 3 hours.

C NeS prepared in the same way 6 By mixing hydrogen reduced ZS 5 (S Co Co 9) 2 obtained in the above order with (8) of C Ne ZS 5 (S Co A Co 9) Got. Table 3 shows the results of the values obtained.

Three

Note that the results of activity and endurance value in Example 3 are also shown in Table 3. From this, it is confirmed that the addition of C nitride and ZS 5 suppresses the formation and further improves the durability. 075 24 (C 5a ZS 5 (

8))

Lanterns made by company 99

Dissolve 8 in Tano Sangyo Co., Ltd. 99 ・ 5 Co 5 Lily Add ZS 5 (Zeo C 3 2) O to scatter the Tano to the 3 C pot. Overnight at 4 C 3 5 at 2 C In C, row 5 a ZS 5 was obtained.

Similarly prepared C nitride 6 5 a ZS 52 obtained in the above order was mixed with C to obtain (8) of 5 a ZS 5. Table 4 shows the results of the obtained and durability values.

0076 25 (C Neonide 5 Ce ZS 5 (

8))

Made by Cem

9) Dissolved in Tano Sangyo Co., Ltd. 99 ・ 5 CO 75 to which ZS 5 (Zeo C 3 2) O was added, and the Tano was spattered into the 3 C pot. Line 5 C with 5 C gave 5 Ce ZS 5.

1 C-Needron 6 prepared in the same manner 5 Ce ZS 52 obtained in the above order was mixed with C to obtain (8) of C-Ne and 5 Ce ZS 5. Table 4 shows the results obtained.

007 26 (C N-oxide 5 S ZS 5 ( 8))

Made by Samum 99/5 S ()

3 36 2 56 (3 54) dissolved in Tano Sangyo Co., Ltd. 99/5 CO 75 to which ZS 5 (Zeo C 3 2) O was added, and 3 was sprinkled into the hot-water bath pot. In the evening, further 2 C at 35 C and 5 S ZS 5 were obtained.

1 C ne prepared in the same way 6 Mix 5 S ZS 52 obtained in the above order with

5 S ZS 5 (8) was obtained. Table 4 shows the results of the values obtained.

078 27 (C Ne a ZS 5 (

2))

99 g a () 6 2 32 (

3 3

73) dissolved in Tano Sangyo Co., Ltd. 99/5 CO 5 ot ZS 5 (Zeo C 3 2) O was added here, and the Tano was spattered into the 3 C pot. Line 5 at 5 C gave a ZS 5.

(1) C Ne a ZS 5 (2) was obtained by mixing a ZS 55 obtained in the same order as above. Table 4 shows the results of the values obtained.

0079 28 (C Ne a ZS 5 (

2))

Lanterns made by company 99

2) Dissolved in Tano Sangyo Co., Ltd. 99 ・ 5 CO 5 ot ZS 5 (Zeo C 3 2) O added to 3 C Tano was spattered into the pot and it was overnight at 4 C. Then, it was run at 3 C at 2 C and a ZS 5 was obtained.

1 C-Need prepared in the same manner A ZS 55 obtained in the above order was mixed with to obtain (2) of C-nezide and a ZS 5. Table 4 shows the results of the values obtained.

0800 29 (C 5a ZS 5 (

2))

1 Prepared in the same way C Implementation 24 A mixture of 5a ZS 55 prepared in the same way with C

We obtained (2) of the new one and a ZS 5. Table 4 shows the results of the values obtained.

008 3 (C 5a ZS 5 (

2 solutions))

Lanterns made by company 99

59) Dissolved in the water ZS 5 (Zeo C 3 2 O) 2 impregnated in 2C 3

a ZS 5 was prepared.

1 C Neuride Prepared in the Same Way 5 a ZS 55 obtained in the above order was mixed with to obtain (2 solutions) of C neon and a ZS 5. Table 4 shows the results of the values obtained.

008 3 (C 5C ZS 5 (

2))

1 C-Needs prepared in the same way.Implementation 25 C.

The nitride and (2) of 5 Ce ZS 5 were obtained. The results of the results are shown in Table 4.

0083 32 (C Net 5 S ZS 5 (

2))

1 C-Needs Prepared in the Same Way Execution 26 5 S ZS 55 prepared in the same way was mixed with to obtain (2) of C-needed and 5 S ZS 5. Table 4 shows the results of the results.

084 33 (C 5a ZS 5 (

))

1 C-Needs prepared in the same manner as Example 24 5 a ZS 5 prepared in the same manner as above was mixed with to obtain () of C-n-oxide and 5 a ZS 5. Table 5 shows the results of the results.

0085 34 (C Neonide 5 Ce ZS 5 (

))

1 C-Needs Prepared in the Same Way Example 25 C-Neutide and 5 Ce ZS 5 () were obtained by mixing 5 Ce ZS 5 O prepared in the same manner with. Table 5 shows the results of the results.

086 35 (C 5S ZS 5 (

))

1 C Nemonide Prepared in the Same Way Execution 26 5 S ZS 5 O prepared in the same manner as above was mixed with to obtain () of C nitride and 5 S ZS 5. Table 5 shows the results of the results.

0087 36 (C-Noise ZS 5 ())

1 Mix C C and ZS 5 (Z eos C 3 2) O The chemical and ZS 5 () were obtained. Table 5 shows the results of the values obtained.

0088 4 (C Z ZS 5 (8))

(8) of C Z and ZS 5 was obtained by mixing commercially available C Z (C 3) 6 and ZS 5 (Zeo C 3 2) 29. Table 5 shows the results of the values obtained.

0089 4

0090 5

0091 In addition, the results of activity values in the implementation and implementation 3 [Table 5 and Table 5 above are also shown. did. Compared with CZ and ZS5 in C-ZS5, 24 to 26, Comparison 4 and Implementation 3, compared with CZ and ZS5, the (Methite) rate was improved, the King rate was low, and the addition of rare earth elements further increased King It is confirmed that it is suppressed. In addition, from implementation 27 to 32 implementation 33 to 35 implementation 36, C

It is confirmed that the ringing is suppressed by adding rare earth element of ZS5.

Utilization of the above, clear, containing copper, and containing metal oleite, containing conventional copper, containing metal and metal It is highly steamy and has less catalyst than the conventional Olite. In addition, it contains metal oleite that contains copper and has a structure, and further contains anana, group 8, and rare earth elements, so that it is possible to further control the odor of hydrogen oxyhydride. it can.

As a result, various modifications can be made to oxygen for light, and hydrogen synthesis gas can be determined for a long period of time and efficiently manufactured. In addition, an excellent fuel cell system having a fuel cell using hydrogen produced by the above-described excellent fuel can be constructed.

Claims

Solicitation

Elemental metal containing copper and containing metal oleite.

2 The ratio of metal oleite containing copper and having a metal structure is as follows.

3 The metal object including copper and having a structure is a C-type spi or an element described in 2.

4 Olite is ZS 5

5. The element according to any one of [1] to [4], comprising copper, a metal having a structure, oleite and anna.

6 Olite contains 8 and / or earth elements.

7 8 Genus is at least one genus selected from P Pd R and

The raw material described in 6.

8 The element according to 6, wherein the genus 8 is at least one genus selected from e and Co.

Obtained based on the description in 9 to 8

Primitive.

Oxygen is at least one kind selected from Methyte Methite. Production of a hydrogen synthesis gas characterized in that oxygen is steamed for use as described in the deviation of element described in ~ 6.

Production of hydrogen syngas characterized by self-oxygenation as described in the deviation from 2 to.

Production of hydrogen synthesis gas characterized by partial oxygen as described in the deviation from 3 to. Production of hydrogen synthesis gas characterized in that the oxygenated hydrogen is carbon dioxide as described in any of 4 to 4.

A fuel cell system, comprising: a fuel cell using hydrogen produced by the method described in any one of 5 to 5 above.