A method and apparatus for reducing concentration of carbon monoxide and a catalyst for selective oxidation of carbon monoxide

 

(57) Abstract:

This invention is used to selectively reduce the concentration of carbon monoxide. For this purpose, the device, method and catalyst. The device includes a source of hydrogen-enriched gas, a source of oxidizing gas. The reaction of selective oxidation of carbon monoxide is carried out in the presence of a catalyst. As the primary component, the catalyst contains ruthenium and optionally contains alkali or alkaline earth metal. Alkali or alkaline earth metal is used as a simple mass of metal or alloy with ruthenium, or as a primary component, it contains ruthenium and optionally contains Nickel, or as a primary component, it contains ruthenium and additionally zinc. The invention allows to expand the range of effective temperatures, in which the activity of the selective oxidation reaction of carbon monoxide remains fairly high. 9 C. and 8 C.p. f-crystals, 5 Il.

The invention relates to the creation of a method and apparatus for reducing concentration of carbon monoxide (carbon monoxide), as well as catalyst for selective oxidation of carbon monoxide. More concrete carbon which is contained in rich hydrogen gas (gas with high hydrogen content), and also used for this catalyst for selective oxidation of carbon monoxide.

The known device to reduce the concentration of carbon monoxide contained in the rich hydrogen gas, in which the used catalyst of ruthenium mounted on the substrate, such as alumina. Such devices are described, for example, in the publication of JAPANESE PATENT LAID-OPEN GAZETTE 8-133701, 8-133702, and 8-217406). When the flow of hydrogen-enriched gas and oxygen quantity in any of such devices is the catalyst of ruthenium accelerates the reaction of selective oxidation of carbon monoxide, by means of which the oxidation of carbon monoxide and not the oxidation of hydrogen, resulting in a reduced concentration of carbon monoxide in rich hydrogen gas.

In such a device to reduce the concentration of carbon monoxide using a fuel cell system, such as fuel cells with polymer electrolyte or a phosphate fuel cells. In these fuel cells run the following electrochemical reaction:

H2-->2H++2E-(1)

2H+ response, which flows in the anode of the fuel elements. Equation (2) shows the reaction that occurs at the cathode of the fuel elements. Equation (3) shows the reaction that occurs in the volume of the fuel elements. From the above expressions it is easy to understand that for a normal course of reactions in fuel cells require a supply containing hydrogen gaseous fuel to the anode and the flow of oxygen-containing oxidizing gas (gas-oxidant) to the cathodes. Carbon monoxide, which is present in the input gas is absorbed by the platinum catalyst provided in the fuel elements, and it reduces its catalytic activity. The air, which is usually used as the oxidizing gas does not contain this level of carbon monoxide, which reduces the catalytic activity. On the other hand, the gaseous fuel usually contains small as carbon monoxide, which can interfere with what is happening on the anodes of the dissociation of hydrogen and lower quality characteristics of the fuel elements.

The presence of carbon monoxide in the gaseous fuel is attributed to the fact that this fuel is produced by the reforming of hydrocarbons. Specified in aetsa gaseous hydrogen of high purity, but is rich in hydrogen gas obtained by reforming of hydrocarbons. The fuel cell system, in which the gaseous fuel use gas reformer, usually is composed of a block of reforming fuel, in which the reforming of hydrocarbons with obtaining a hydrogen-enriched fuel gas, which is fed to the anodes of the fuel elements. The following is an example of reactions reformer to obtain hydrogen-enriched gas which is a reforming of methanol:

CH3HE-->CO+2H2(4)

CO+H2O-->2+H2(5)

CH3HE+H2O-->2+3H2(6)

When carrying out the reaction of steam reforming of methanol occurs at the same time, the dissociation of methanol in accordance with equation (4) and the reforming of carbon monoxide in accordance with equation (5). In General, the reaction in accordance with equation (6) allows to get rich in hydrogen gas, which contains carbon dioxide (carbon dioxide). With the full completion of these reactions in their final stage carbon monoxide no. However, in the real unit of the reforming fuel is almost impossible to move fully to the right reaction in souterhead as a by-product.

The reaction of steam reforming is usually carried out in the presence of a known catalyst of the reforming process, such as the catalyst Cu-Zn. However, in the presence of such a catalyst reformer simultaneously with the reaction of the steam reforming reaction is the reverse of the shift in accordance with the above equation (7), which generates traces of carbon monoxide in the gas reformer:

CO2+H2-->+H2O (7)

In accordance with the reaction of the reverse shift displayed by the expression (7), to receive carbon monoxide from hydrogen and carbon dioxide, which is produced by the process of steam reforming reaction. The reaction is reversed shear is relatively weak in comparison with the reaction of the steam reforming process. However, in cases when you want an extremely low concentration of carbon monoxide, for example, when the gas reformer is used as fuel gas for fuel cell obtained by the reaction of the reverse shift carbon monoxide has an important influence, and it should not be neglected.

Device to reduce the concentration of carbon monoxide is used to reduce the concentration of carbon monoxide in the gaseous fuel, earlier feeding gaseous Topley the oxidation of carbon monoxide instead of the oxidation of hydrogen, which, as mentioned above, is contained in the gas reformer. The oxidation reaction of carbon monoxide proceeds in accordance with the following equation (8). Allowable concentration of carbon monoxide in the input to the fuel elements of the gaseous fuel does not exceed a few percent for the case of phosphate fuel cells and does not exceed a few ppm (m-1) for the case of fuel cells with polymer electrolyte. When entering the gas reformer in the device to reduce the concentration of carbon monoxide, which contains the catalyst of ruthenium reaction of selective oxidation of carbon monoxide in accordance with equation (8). Due to this reduced concentration of carbon monoxide contained in the gas reformer, and is provided with a supply of gaseous fuel having a substantially reduced concentration of carbon monoxide to the fuel elements.

CO+(1/2)O2-->CO2(8)

The effective temperature range of the catalyst of ruthenium, which sufficiently accelerates the reaction of selective oxidation of carbon monoxide, is approximately 140 to 200oC. a Device to reduce the concentration of monex does not reduce sufficiently the concentration of carbon monoxide, which is contained in the gaseous fuel supplied to the fuel elements. So, for example, by lowering the temperature of the device to reduce the concentration of carbon monoxide below the range of effective operating temperature activity of the catalyst decreases and does not allow sufficiently to accelerate the oxidation of carbon monoxide, resulting in insufficient reduction of the concentration of carbon monoxide. On the other hand, when the temperature of the device to reduce the concentration of carbon monoxide above the effective range of working temperatures the oxidation of hydrogen, which is present in the gaseous fuel. This prevents selective oxidation of traces of carbon monoxide present in the gaseous fuel. For sufficiently reducing the concentration of carbon monoxide is required to regulate the internal temperature of the device to reduce the concentration of carbon monoxide in accordance with the volume of gas reformer, which is subjected to selective oxidation of carbon monoxide, which allows for the selective oxidation of carbon monoxide in the above-mentioned range of effective temperatures.

In the case when exists, is(i.e. the amount of gas reformer, supplied to the device to reduce the concentration of carbon monoxide) is difficult to maintain the internal temperature of the device to reduce the concentration of carbon monoxide in the range of effective temperatures. For example, in the case when as a power source for vehicles use fuel cells that receive gaseous fuel with a low concentration of carbon monoxide, an abrupt change of load. The change in the load leads to a significant change in the volume to be processed gas fed to the device to reduce the concentration of carbon monoxide, however, is difficult to regulate the internal temperature of the device to reduce the concentration of carbon monoxide. The sharp increase in load leads to a sharp increase in the volume of subject processing gas fed into the device to reduce the concentration of carbon monoxide, which can lead to a sharp increase in the internal temperature. Similarly, the sharp drop in the load leads to a significant reduction subject to the processing gas fed into the device to reduce the concentration of carbon monoxide, which can lead to a sharp decrease in the internal temperature is t a range of desirable temperatures resulting from changes in load, experiencing the previously mentioned problems hindering effective to reduce the concentration of carbon monoxide in the gas reformer. Therefore, it is desirable that the catalyst for preferential oxidation of carbon monoxide had a wide range of effective temperatures and remained active selective oxidation of carbon monoxide at a sufficient level, provided a relatively wide changes in load of the fuel elements.

The operating temperature of the fuel elements, which serves the gaseous fuel from the device to reduce the concentration of carbon monoxide is approximately 80 to 100oIn the case of fuel cells with polymer electrolyte. In that case, when the temperature of the gaseous fuel supplied from the device to reduce the concentration of carbon monoxide exceeds the operating temperature of the fuel elements, then direct the flow of gaseous fuel from the device to reduce the concentration of carbon monoxide in the fuel elements adversely increases the internal temperature of the fuel cell to an undesirable level. In that case, when the temperature of the oxidation reaction occurring in the device to reduce the concentration of co in Otopeni accelerates the reaction), exceeds the operating temperature range of the fuel elements, you should use a heat exchanger installed in the path of flow of gaseous fuel from the device to reduce the concentration of carbon monoxide to the fuel elements. The heat exchanger allows to considerably reduce the temperature of the gaseous fuel previously entered in fuel cells. However, the heat exchanger complicates the pipeline system and undesirable increases the size of the system as a whole.

Earlier it was mentioned that in order to accelerate the reaction of selective oxidation of carbon monoxide is desirable to use a catalyst with a wide range of effective temperatures, which allows for adequate acceleration of the reaction of selective oxidation of carbon monoxide in the event of a possible change in load. Especially, it is preferable to have a lower bound of the range of effective temperatures, which is located as close as possible to the operating temperature of the fuel elements. However, in the case of commonly used ruthenium catalyst from the lower boundary of the range of effective temperatures, which significantly reduces the concentration of carbon monoxide is about 140oSince, as already womenlooking carbon at the operating temperature of the fuel elements, which is about 100oC.

The present invention is to expand the range of effective temperatures, in which the activity of the reaction of selective oxidation of carbon monoxide remains fairly high, especially setting the lower range of effective temperatures close as possible to the operating temperature of the fuel elements. This task is implemented in the proposed method of reducing concentration of carbon monoxide in the proposed device to reduce the concentration of carbon monoxide, made with the use of a new catalyst for selective oxidation of carbon monoxide.

In accordance with the present invention, it is proposed the first device to reduce the concentration of carbon monoxide, which allows the oxidation of carbon monoxide contained in the rich hydrogen gas, and to reduce the concentration of carbon monoxide. The first device to reduce the concentration of carbon monoxide includes a source of hydrogen-enriched gas, which ensures the supply of hydrogen-enriched gas; a source of oxidizing gas, which ensures the supply of oxygen-containing of anglerad, which contains a catalyst for selective oxidation of carbon monoxide and which receives a rich hydrogen gas from a source rich in hydrogen gas and oxidizing gas from the oxidizing source gas. In the specified block is selective oxidation contained in rich hydrogen gas of carbon monoxide by the reaction of selective oxidation of carbon monoxide, and a catalyst for selective oxidation of carbon monoxide, which accelerates the reaction of selective oxidation of carbon monoxide, contains as a primary component ruthenium. In the first device to reduce the concentration of carbon monoxide catalyst for selective oxidation of carbon monoxide additionally contains a simple mass (the simple body) of an alkali metal, which together with the ruthenium extends the range of effective temperatures, which accelerates the reaction of selective oxidation of carbon monoxide.

At the entrance of the specified first device to reduce the concentration of carbon monoxide is fed a rich pipeline gas from a source rich in hydrogen gas and oxidizing gas from the oxidizing source gas and is selective oxidation contained in mogulette which the concentration of carbon monoxide is reduced. The reaction of selective oxidation of carbon monoxide takes place in the presence of a catalyst for selective oxidation of carbon monoxide, which, in addition to use as a primary component of ruthenium simple weight of an alkali metal, which together with the ruthenium extends the range of effective temperatures, which accelerates the reaction of selective oxidation of carbon monoxide.

In accordance with the present invention it is also proposed corresponding to the first method of oxidation of carbon monoxide contained in the rich hydrogen gas, and due to this, reduce the concentration of carbon monoxide. The first method of reducing concentration of carbon monoxide includes the following operations: mixing of hydrogen-enriched gas from the oxygen-containing oxidizing gas used for oxidation of carbon monoxide; and the oxidation of carbon monoxide contained in the rich hydrogen gas mixed with an oxidizing gas, due to the reaction of selective oxidation of carbon monoxide using a catalyst for selective oxidation of carbon monoxide, which contains as a primary component ruthenium and accelerates the reaction of the electoral metal, which extends the range of effective temperatures, which accelerates the reaction of selective oxidation of carbon monoxide.

In accordance with the present invention it is also proposed corresponding to the first catalyst for selective oxidation of carbon monoxide, which accelerates the reaction of selective oxidation of carbon monoxide contained in the rich hydrogen gas. The first catalyst for selective oxidation of carbon monoxide contains as a primary component ruthenium deposited on an appropriate substrate, and further comprises a simple mass of an alkali metal, which together with the ruthenium extends the range of effective temperatures, which accelerates the reaction of selective oxidation of carbon monoxide.

Proposed first device to reduce the concentration of carbon monoxide, the first method of reducing concentration of carbon monoxide and the first catalyst for selective oxidation of carbon monoxide allow you to extend the range of effective temperatures, which accelerates the reaction of selective oxidation of carbon monoxide. Compared with previously known devices, in which the used catalyst is about to reduce the concentration of carbon monoxide in rich hydrogen gas over a wide temperature range. The proposed solution allows to simplify the process of maintaining the temperature of the catalyst for selective oxidation of carbon monoxide in the effective temperature range, in which essentially decreases the concentration contained in the rich hydrogen gas of carbon monoxide. The proposed solution is particularly preferred in the case when changes substantially be processed, the loading device to reduce the concentration of carbon monoxide (i.e., the number of hydrogen-enriched gas supplied to the device to reduce the concentration of carbon monoxide), for example, when a rich hydrogen gas concentration of carbon monoxide, reduced with the help of the device to reduce the concentration of carbon monoxide comes in the form of gaseous fuels for fuel cells connected to a variable load. The change in the volume of hydrogen-enriched gas which is the object of reducing the concentration of carbon monoxide, changes calorimetric indicator reaction of selective oxidation of carbon monoxide and, therefore, changes the temperature of the catalyst for selective oxidation of carbon monoxide. However, even in oslojnyaetsya concentration of carbon monoxide, allows you to maintain a stable condition sufficient to reduce the concentration of carbon monoxide.

The effects of the joint action of the alkali metal and ruthenium can be explained as follows. Alkaline metal when placed together with the ruthenium allows you to shift the S electrons of the alkali metal in the region of the conductivity of ruthenium. This facilitates the dissociation of absorbed ruthenium oxygen or absorption of ruthenium monoxide, resulting in improved activity of accelerating the reaction of selective oxidation of carbon monoxide.

In accordance with the present invention it is proposed to use as the alkali metal of the first catalyst for selective oxidation of carbon monoxide used in the first device to reduce the concentration of carbon monoxide in the first method of reducing concentration of carbon monoxide, lithium or potassium.

In accordance with the present invention in the first device to reduce the concentration of carbon monoxide in the first method of reducing concentration of carbon monoxide in the first catalyst for selective oxidation of carbon monoxide, the effective temperature range, in to the of Imperator. Such a construction is desirable way simplifies or even eliminates the process of reducing the temperature of the hydrogen-enriched gas having a reduced concentration of carbon monoxide, earlier filing hydrogen-enriched gas having a reduced concentration of carbon monoxide as a gaseous fuel, for example, in fuel cells with polymer electrolyte.

In accordance with the present invention offers a second device to reduce the concentration of carbon monoxide, which allows the oxidation of carbon monoxide contained in the rich hydrogen gas, and to reduce the concentration of carbon monoxide.

A second device to reduce the concentration of carbon monoxide includes a source of hydrogen-enriched gas, which ensures the supply of hydrogen-enriched gas; a source of oxidizing gas, which ensures the supply of oxygen-containing oxidizing gas used for oxidation of carbon monoxide; and the block selective oxidation of carbon monoxide, which contains a catalyst for selective oxidation of carbon monoxide and which receives a rich hydrogen gas from the source bagatogaluzeva contained in rich hydrogen gas of carbon monoxide by the reaction of selective oxidation of carbon monoxide, moreover, the catalyst for selective oxidation of carbon monoxide, which accelerates the reaction of selective oxidation of carbon monoxide, contains as a primary component ruthenium. In the second device to reduce the concentration of carbon monoxide catalyst for selective oxidation of carbon monoxide additionally contains a simple weight alkaline earth metal, which together with the ruthenium extends the range of effective temperatures, which accelerates the reaction of selective oxidation of carbon monoxide.

At the entrance of the specified second device to reduce the concentration of carbon monoxide comes rich in hydrogen gas from a source rich in hydrogen gas and oxidizing gas from the oxidizing source gas and is selective oxidation contained in rich hydrogen gas of carbon monoxide through the reaction of selective oxidation of carbon monoxide, resulting in the concentration of carbon monoxide is reduced. The reaction of selective oxidation of carbon monoxide takes place in the presence of a catalyst for selective oxidation of carbon monoxide, which, in addition to use as a primary component of ruthenium, simple motor accelerates the reaction of selective oxidation of carbon monoxide.

In accordance with the present invention it is also proposed corresponding to the second method of oxidation of carbon monoxide contained in the rich hydrogen gas, and due to this, reduce the concentration of carbon monoxide. The second method of reducing concentration of carbon monoxide includes the following operations: mixing of hydrogen-enriched gas from the oxygen-containing oxidizing gas used for oxidation of carbon monoxide; and the oxidation of carbon monoxide contained in the rich hydrogen gas mixed with an oxidizing gas, due to the reaction of selective oxidation of carbon monoxide using a catalyst for selective oxidation of carbon monoxide, which contains as a primary component ruthenium and accelerates the reaction of selective oxidation of carbon monoxide, with the specified catalyst additionally contains a simple weight alkaline earth metal, which extends the range of effective temperatures, which accelerates the reaction of selective oxidation of carbon monoxide.

In accordance with the present invention it is also proposed corresponding second catalyst for selective oxidation of co ug is Odom gas. The second catalyst for selective oxidation of carbon monoxide contains as a primary component ruthenium deposited on an appropriate substrate, and further comprises a simple weight alkaline earth metal, which together with the ruthenium extends the range of effective temperatures, which accelerates the reaction of selective oxidation of carbon monoxide.

The proposed second device to reduce the concentration of carbon monoxide, a second method of reducing concentration of carbon monoxide and a second catalyst for selective oxidation of carbon monoxide allow us to expand the range of effective temperatures, which accelerates the reaction of selective oxidation of carbon monoxide. Compared with previously known devices that use a catalyst of ruthenium proposed in accordance with the present invention, the technical solution allows to considerably reduce the concentration of carbon monoxide in rich hydrogen gas over a wide temperature range. The proposed second technical solution similar to the first technical solution, allows you to simplify the process of maintaining the temperature of the catalyst for izbica reduce the concentration of carbon monoxide, over a wide temperature range, in which sufficiently reduces the concentration of carbon monoxide, allows to maintain a stable condition sufficient to reduce the concentration of carbon monoxide.

In accordance with the present invention it is proposed to use barium as the alkaline earth metal of the second catalyst for selective oxidation of carbon monoxide used in the second device to reduce the concentration of carbon monoxide or the second method of reducing concentration of carbon monoxide.

In accordance with the present invention, the second device to reduce the concentration of carbon monoxide in the second method of reducing concentration of carbon monoxide in the second catalyst for selective oxidation of carbon monoxide, the effective temperature range, in which accelerates the reaction of selective oxidation of carbon monoxide, especially expanded in the region of low temperatures. Such a construction is desirable way simplifies or even eliminates the process of reducing the temperature of the hydrogen-enriched gas having a reduced concentration of carbon monoxide, earlier filing hydrogen-enriched gas, the ima is the elements with polymer electrolyte.

As mentioned here earlier, the first catalyst for selective oxidation of carbon monoxide used in the first device to reduce the concentration of carbon monoxide or in the first method of reducing concentration of carbon monoxide in accordance with the present invention, in addition to ruthenium contains simple weight of an alkali metal. The second catalyst for selective oxidation of carbon monoxide used in the second device to reduce the concentration of carbon monoxide or the second method of reducing concentration of carbon monoxide in accordance with the present invention, in addition to ruthenium contains a lot of alkaline earth metal. Simple weight alkali or alkaline earth metal has a high absorption capacity for oxygen in the atmosphere of hydrogen, and therefore provides greater acceleration of the reaction of selective oxidation of carbon monoxide compared with the compound of the alkali or alkaline earth metal. Sharing simple weight alkali or alkaline earth metal ruthenium additionally improves the qualitative characteristics of the catalyst for selective oxidation.

In accordance with the present from which to produce the oxidation of carbon monoxide, contained in rich hydrogen gas, and to reduce the concentration of carbon monoxide. The third device to reduce the concentration of carbon monoxide comprises: a source of hydrogen-enriched gas, which ensures the supply of hydrogen-enriched gas; a source of oxidizing gas, which ensures the supply of oxygen-containing oxidizing gas used for oxidation of carbon monoxide; and the block selective oxidation of carbon monoxide, which contains a catalyst for selective oxidation of carbon monoxide and which receives a rich hydrogen gas from a source rich in hydrogen gas and oxidizing gas from the oxidizing source gas. In the specified block is selective oxidation contained in rich hydrogen gas of carbon monoxide by the reaction of selective oxidation of carbon monoxide, and a catalyst for selective oxidation of carbon monoxide, which accelerates the reaction of selective oxidation of carbon monoxide, contains as a primary component ruthenium. In the third device to reduce the concentration of carbon monoxide catalyst for selective oxidation of carbon monoxide advanced soode lighting designer comes rich in hydrogen gas from a source rich in hydrogen gas and oxidizing gas from the oxidizing source gas, and is selective oxidation contained in rich hydrogen gas of carbon monoxide through the reaction of selective oxidation of carbon monoxide, resulting in the concentration of carbon monoxide is reduced. The reaction of selective oxidation of carbon monoxide takes place in the presence of a catalyst for selective oxidation of carbon monoxide containing Nickel in addition to use as a primary component to ruthenium.

In accordance with the present invention it is also proposed corresponding to the third method of oxidation of carbon monoxide contained in the rich hydrogen gas, and due to this, reduce the concentration of carbon monoxide. The third method of reducing concentration of carbon monoxide includes the following operations: mixing of hydrogen-enriched gas from the oxygen-containing oxidizing gas used for oxidation of carbon monoxide; and reducing the concentration of carbon monoxide contained in the rich hydrogen gas mixed with an oxidizing gas, due to the reaction of selective oxidation of carbon monoxide using a catalyst for selective oxidation of carbon monoxide, which contains in whom the specified catalyst further comprises Nickel.

In accordance with the present invention it is also proposed corresponding to the third catalyst for selective oxidation of carbon monoxide, which accelerates the reaction of selective oxidation of carbon monoxide contained in the rich hydrogen gas. The third catalyst for selective oxidation of carbon monoxide contains as a primary component ruthenium deposited on an appropriate substrate, and optionally may contain Nickel.

Proposed third device to reduce the concentration of carbon monoxide, a third method of reducing concentration of carbon monoxide and a third catalyst for selective oxidation of carbon monoxide allow us to expand the range of effective temperatures, which accelerates the reaction of selective oxidation of carbon monoxide. Compared with previously known devices that use a catalyst of ruthenium proposed in accordance with the present invention, the technical solution allows to considerably reduce the concentration of carbon monoxide in rich hydrogen gas over a wide temperature range. Proposed third technical solution, similarly to the first and second technical which I of carbon monoxide. Even when the volume of hydrogen-enriched gas which is the object of reducing the concentration of carbon monoxide, over a wide temperature range, in which sufficiently reduces the concentration of carbon monoxide, allows to maintain a stable condition sufficient to reduce the concentration of carbon monoxide. Effective temperature range, in which accelerates the reaction of selective oxidation of carbon monoxide, especially expanded in the region of low temperatures. Such a construction is desirable way simplifies or even eliminates the process of reducing the temperature of the hydrogen-enriched gas having a reduced concentration of carbon monoxide, earlier filing hydrogen-enriched gas having a reduced concentration of carbon monoxide as a gaseous fuel, for example, in fuel cells with polymer electrolyte.

In accordance with the present invention it is also proposed fourth device to reduce the concentration of carbon monoxide, which allows the oxidation of carbon monoxide contained in the rich hydrogen gas, and to reduce the concentration of carbon monoxide. The fourth device to reduce Konz is the hydrogen-enriched gas; a source of oxidizing gas, which ensures the supply of oxygen-containing oxidizing gas used for oxidation of carbon monoxide; and the block selective oxidation of carbon monoxide, which contains a catalyst for selective oxidation of carbon monoxide and which receives a rich hydrogen gas from a source rich in hydrogen gas and oxidizing gas from the oxidizing source gas. In the specified block is selective oxidation contained in rich hydrogen gas of carbon monoxide by the reaction of selective oxidation of carbon monoxide, and a catalyst for selective oxidation of carbon monoxide, which contains as a primary component, ruthenium, accelerates the reaction of selective oxidation of carbon monoxide. In the fourth device to reduce the concentration of carbon monoxide catalyst for selective oxidation of carbon monoxide additionally contains zinc.

At the entrance of the specified fourth device to reduce the concentration of carbon monoxide comes rich in hydrogen gas from a source rich in hydrogen gas and oxidizing gas from the oxidizing source gas and is selective oxidation of PIDs carbon resulting in the concentration of carbon monoxide is reduced. The reaction of selective oxidation of carbon monoxide takes place in the presence of a catalyst for selective oxidation of carbon monoxide containing zinc in addition to use as a primary component to ruthenium.

In accordance with the present invention it is also proposed corresponding to the fourth mode of oxidation of carbon monoxide contained in the rich hydrogen gas, and due to this, reduce the concentration of carbon monoxide. The fourth method of reducing concentration of carbon monoxide includes the following operations mixing of the hydrogen-enriched gas from the oxygen-containing oxidizing gas used for oxidation of carbon monoxide; and reducing the concentration of carbon monoxide contained in the rich hydrogen gas mixed with an oxidizing gas, due to the reaction of selective oxidation of carbon monoxide using a catalyst for selective oxidation of carbon monoxide, which contains as a primary component ruthenium and accelerates the reaction of selective oxidation of carbon monoxide, with the specified catalyst additionally contains C isator for selective oxidation of carbon monoxide, which accelerates the reaction of selective oxidation of carbon monoxide contained in the rich hydrogen gas. The fourth catalyst for selective oxidation of carbon monoxide contains as a primary component ruthenium deposited on an appropriate substrate, and further comprises zinc.

The proposed fourth device to reduce the concentration of carbon monoxide, the fourth method of reducing concentration of carbon monoxide and fourth catalyst for selective oxidation of carbon monoxide allow us to expand the range of effective temperatures, which accelerates the reaction of selective oxidation of carbon monoxide. Compared with previously known devices that use a catalyst of ruthenium proposed in accordance with the present invention, the technical solution allows to considerably reduce the concentration of carbon monoxide contained in the rich hydrogen gas, in a wider temperature range. The proposed fourth technical solution, similar to the first, second and third solutions, you can simplify the process of maintaining the temperature of the catalyst for selective oxidation of the ation of carbon monoxide, over a wide temperature range, in which sufficiently reduces the concentration of carbon monoxide, allows to maintain a stable condition sufficient to reduce the concentration of carbon monoxide. Effective temperature range, in which accelerates the reaction of selective oxidation of carbon monoxide, especially expanded in the region of low temperatures. Such a construction is desirable way simplifies or even eliminates the process of reducing the temperature of the hydrogen-enriched gas having a reduced concentration of carbon monoxide, earlier filing hydrogen-enriched gas having a reduced concentration of carbon monoxide as a gaseous fuel, for example, in fuel cells with polymer electrolyte.

In accordance with the present invention it is also proposed fifth device to reduce the concentration of carbon monoxide, which allows the oxidation of carbon monoxide contained in the rich hydrogen gas, and to reduce the concentration of carbon monoxide. The fifth device to reduce the concentration of carbon monoxide includes a source of hydrogen-enriched gas, which ensures the supply of the rich in the gas, used for oxidation of carbon monoxide; and the block selective oxidation of carbon monoxide, which contains a catalyst for selective oxidation of carbon monoxide and which receives a rich hydrogen gas from a source rich in hydrogen gas and oxidizing gas from the oxidizing source gas. In the specified block is selective oxidation contained in rich hydrogen gas of carbon monoxide by the reaction of selective oxidation of carbon monoxide, and a catalyst for selective oxidation of carbon monoxide, which accelerates the reaction of selective oxidation of carbon monoxide, contains as a primary component ruthenium. In the fifth device to reduce the concentration of carbon monoxide catalyst for selective oxidation of carbon monoxide additionally contains an alkaline metal, which together with the ruthenium extends the range of effective temperatures, which accelerates the reaction of selective oxidation of carbon monoxide, with the specified alkali metal obtained by recovering alkali metal salt.

In accordance with the present invention it is also proposed corresponding to the fifth catalyst for houses is kind, contained in rich hydrogen gas. The fifth catalyst for selective oxidation of carbon monoxide contains as a primary component ruthenium deposited on an appropriate substrate, and further comprises an alkaline metal, which together with the ruthenium extends the range of effective temperatures, which accelerates the reaction of selective oxidation of carbon monoxide, with the specified alkali metal obtained by recovery of salts of alkaline metal, while in the specified fifth catalyst for selective oxidation of carbon monoxide alkali metal is obtained by recovery of the alkali metal salt to obtain a simple mass of the alkali metal. The presence of an alkali metal as a simple mass provides the previously discussed effects relating to the first device to reduce the concentration of carbon monoxide and a first catalyst for selective oxidation of carbon monoxide.

In accordance with the present invention it is also proposed sixth device to reduce the concentration of carbon monoxide, which allows the oxidation of carbon monoxide contained in the rich hydrogen gas, and to reduce the oxygen is the source of hydrogen-enriched gas, which ensures the supply of hydrogen-enriched gas; a source of oxidizing gas, which ensures the supply of oxygen-containing oxidizing gas used for oxidation of carbon monoxide; and the block selective oxidation of carbon monoxide, which contains a catalyst for selective oxidation of carbon monoxide and which receives a rich hydrogen gas from a source rich in hydrogen gas and oxidizing gas from the oxidizing source gas. In the specified block is selective oxidation contained in rich hydrogen gas of carbon monoxide by the reaction of selective oxidation of carbon monoxide, and a catalyst for selective oxidation of carbon monoxide, which accelerates the reaction of selective oxidation of carbon monoxide, contains as a primary component ruthenium. In the sixth device to reduce the concentration of carbon monoxide catalyst for selective oxidation of carbon monoxide additionally contains an alkaline earth metal, which together with the ruthenium extends the range of effective temperatures, which accelerates the reaction of selective oxidation of carbon monoxide, and specified deliciosamente invention it is also proposed corresponding to the sixth catalyst for selective oxidation of carbon monoxide, which accelerates the reaction of selective oxidation of carbon monoxide contained in the rich hydrogen gas. The sixth catalyst for selective oxidation of carbon monoxide contains as a primary component ruthenium deposited on an appropriate substrate, and further comprises alkaline earth metal, which together with the ruthenium extends the range of effective temperatures, which accelerates the reaction of selective oxidation of carbon monoxide, with the specified alkaline earth metal obtained by recovering salts of alkaline earth metal, while in the specified sixth catalyst for selective oxidation of carbon monoxide alkaline earth metal is obtained by recovery of the salts of alkaline earth metal to obtain a simple mass alkaline earth metal. The presence of alkaline earth metal in the form of a simple mass provides the previously discussed effects relating to the second device to reduce the concentration of carbon monoxide and the second catalyst for selective oxidation of carbon monoxide.

In accordance with the present invention it is also proposed corresponding seventh catalyst for the election of ociosa rich in hydrogen gas. Seventh catalyst for selective oxidation of carbon monoxide contains as a primary component ruthenium deposited on an appropriate substrate, and further comprises an alkaline metal, which together with the ruthenium extends the range of effective temperatures, which accelerates the reaction of selective oxidation of carbon monoxide, with the specified alkali metal and ruthenium is applied in the form of alloy on an appropriate substrate.

In accordance with the present invention it is also proposed corresponding eighth catalyst for selective oxidation of carbon monoxide, which accelerates the reaction of selective oxidation of carbon monoxide contained in the rich hydrogen gas. Eighth catalyst for selective oxidation of carbon monoxide contains as a primary component ruthenium deposited on an appropriate substrate, and further comprises alkaline earth metal, which together with the ruthenium extends the range of effective temperatures, which accelerates the reaction of selective oxidation of carbon monoxide, with the specified alkaline earth metal and ruthenium is applied in the form of alloy on an appropriate substrate.

In the seventh catalyst for selective oxidation of carbon monoxide alkali metal may be lithium or potassium.

In the eighth catalyst for selective oxidation of carbon monoxide alkaline earth metal may be barium.

These and other features of the present invention will be more apparent from the subsequent detailed description, given with reference to the accompanying drawings.

In Fig.1 shows a block diagram of a method of manufacturing a catalyst of ruthenium with the addition of lithium.

In Fig.2 schematically shows the structure of the fuel cell system 10.

In Fig.3 schematically shows the sectional structure of the element 28, the supplied fuel cells 20.

In Fig.4 schematically pok the characteristics, at different temperatures, various catalysts for selective oxidation of carbon monoxide in accordance with the present invention, each of which contains ruthenium and the second element, and a known catalyst of ruthenium.

In Fig.1 shows a block diagram of a method of manufacturing a catalyst of ruthenium with the addition of lithium, which mainly corresponds to the present invention. In Fig. 2 schematically shows the structure of the fuel cell system 10 included in the device to reduce the concentration of carbon monoxide in which the used catalyst of ruthenium with the addition of lithium. Used in this embodiment, the catalyst for selective oxidation of carbon monoxide obtained by applying a certain (specified) amount of ruthenium and a small amount of lithium on tablets of aluminum oxide. In the following description, such a catalyst for selective oxidation of carbon monoxide is called a catalyst of ruthenium with the addition of lithium. In this embodiment, in the fuel cell system 10 included in the device to reduce the concentration of carbon monoxide, the used catalyst of ruthenium with the addition of lithium, which has excellent activity about which emperature. Even in the case when you change the load connected to the fuel elements, such a construction provides a sufficient decrease in the concentration of carbon monoxide contained in the rich hydrogen gas. The following describes the first method of manufacturing the catalyst of ruthenium with the addition of lithium in accordance with the flowchart shown in Fig.1, and then describes the structure of the fuel cell system 10 and the reaction of reducing concentration of carbon monoxide contained in the rich hydrogen gas, which flows in the fuel cell system 10 shown in Fig.2.

As shown in Fig.1, a method of manufacturing a catalyst of ruthenium with the addition of lithium involves first obtaining a porous pellets of aluminum oxide, formed with an average diameter of about 3 mm, which are soaked in distilled water (operation S100). The method involves a separate operation feeding an aqueous solution of lithium acetate drop in distilled water with her tablets of aluminum oxide, with stirring, to produce absorption of lithium salts tablets aluminum oxide (operation S110). Then the method involves drying pellets of aluminum oxide with the absorbed salt of litury for approximately 1 hour (operation S130). The result is a tablet aluminum oxide coated with lithium. The method in accordance with this embodiment of the present invention allows the application of lithium density of 0.005 mole of lithium per liter of volume pills alumina. The method then provides the processing for the additional deposition of ruthenium on tablets of aluminum oxide, which is similar to the operation of the deposition of lithium.

Tablets coated with lithium soaked in distilled water (operation S140). The method involves a separate operation feeding an aqueous solution of ruthenium chloride drop by drop in distilled water with her pills alumina coated with lithium, with stirring, to produce absorption of salts of ruthenium tablets aluminum oxide (operation S150). Then the method involves drying pellets of aluminum oxide coated with lithium and with the absorbed salt of ruthenium, to remove water (operation S160), and heating the pellets of aluminum oxide in restoring the pipeline environment 500oWith hold the temperature for approximately 2 hours (operation S170). This operation allows you to recover ruthenium on tablets and completes the process of obtaining produce the STU being 0.036 mol of ruthenium per liter of volume pills alumina.

In the described method of manufacturing a catalyst of ruthenium with the addition of lithium to lithium deposition on tablets of aluminum oxide using lithium acetate, but with the same success can be used any suitable lithium salt, for example, selected from the group comprising lithium chloride, lithium acetate, lithium sulfide, or any combination of these salts. Similarly, in the described method of manufacturing a catalyst of ruthenium with the addition of lithium for the deposition of ruthenium on tablets of aluminum oxide using ruthenium chloride, but with the same success can be used any suitable salt of ruthenium, for example, selected from the group comprising ruthenium nitrate, ruthenium iodide, harutunian acid, chlorbutanol ammonium hydrochloride ruthenium and routenet potassium, as well as any combination of these salts.

The structure of the fuel cell system 10 shown in Fig.2. The fuel cell system 10 includes a tank for methanol 12, a water tank 14, block reformer fuel 30 and the set of fuel cells 20.

The flow of methanol from the tank 12 and the water from the tank 14 to the block of the reforming fuel 30 is conducted through the pipe system. Block reformer fuel 30 allows to obtain containing hydrogen gas Ringa fuel 30, and oxygen-containing oxidizing gas, a fuel cell 20 generates an electromotive force through electrochemical processes occurring in them reactions.

Fuel cells 20 are fuel cells with polymer electrolyte, which have a multilayer structure obtained by the installation of a large number of individual elements on each other. In Fig.3 schematically shows a cross-section of a single element 28, the supplied fuel cells 20. Single elements 28 include electrolytic membrane 21, the anode 22, a cathode 23 and two separator 24 and 25.

The anode 22 and the cathode 23 are of the gas diffusion electrodes, which have a sandwich structure and go from edge to edge of the electrolyte membrane 21. The separators 24 and 25 go from edge to edge of sandwich structures and connected appropriately with the anode 22 and cathode 23 to form a flow path of gaseous fuel and oxidizing gas. The flow path of gaseous fuel 24P is provided in the anode 22 and the separator 24, while the path of flow of the oxidizing gas 25R is provided in the cathode 23 and the separator 25.

Electrolytic membrane 21 is a conductive protons ion exchange mastergamer platinum alloy, acting as a catalyst. The anode 22 and the cathode 23 are made of carbon fiber obtained from yarns of carbon fibers or carbon paper or felt, obtained from carbon fibers. The separators 24 and 25 are made of gas-tight electrically conductive material, for example of gas-tight solid carbon formed by pressing, and have ribs specific shape formed on their surface. These ribs are in contact with surfaces of the anode 22 and cathode 23 and respectively form the flow path of gaseous fuel 24P and the path of flow of the oxidizing gas 25R. Although described here separators 24 and 25 are shown as independent elements, in fact, between any adjacent unit elements 28 in the bundle of the fuel elements 20 has only one separator having ribs formed on its both sides.

Kit fuel cell 20 is formed by individual elements 28, having the above construction, and many (in this example, 100) single elements 28 are mounted relative to each other so that a separator is located between every two adjacent blocks of the electrode-membrane, each of which is ornago plate of dense carbon or copper, going from edge to edge together the fuel elements.

In Fig. 1 shows only the supply of gaseous fuel to the anodes of the fuel elements 20, while not shown is also provided a system of compressed oxidizing gas to the cathodes of fuel cells 20. In addition, the fuel cell 20 are connected also not shown, the exhaust fuel and oxidizing gas, resulting from electrochemical reactions at the respective electrodes.

Block reformer fuel 30 (Fig.2) includes installation reformer 32, block 34 selective oxidation of CO sensor carbon monoxide 40, the blower 38 and the controller 70. Upon receipt of methanol and water installation reformer 32 produces rich in hydrogen gas reformer. Block 34 of selective CO oxidation produces oxidation contained in the gas reforming of carbon monoxide, which decreases the concentration contained in the gas reforming of carbon monoxide, thus receive gaseous fuel having a reduced concentration of carbon monoxide below the specified level. Sensor carbon monoxide 40 is installed in the connection pipe 36, through which the gas resperine concentration of carbon monoxide in the gas reformer. Blower 38 delivers the oxygen-containing oxidizing gas (in this embodiment, the air in the connecting pipe 36 through the inlet pipe 39, which is connected downstream of the sensor monoxide 40. The controller 70 controls the operating state of the respective component unit of the reforming fuel 30, which are further described in more detail.

When the flow of methanol from the tank 12 and the water from the tank 14 installing the reformer 32 produces gas reformer containing hydrogen and carbon dioxide by steam reforming reactions proceeding in accordance with the previously described equations (4)-(6). As mentioned earlier, it is almost impossible the complete reaction of the reforming of carbon monoxide in accordance with equation (5), so the gas reformer contains some amount of carbon monoxide as a by-product. Concentration contained in the gas reforming of carbon monoxide depends on the type of catalyst used in the installation of the reformer 32, the operating temperature installation reformer 32 and flows of methanol and water supplied to the reformer 32 on a unit volume of catalyst. In this option, the installation reformer 32 used Cu-Zn ratestogo process co-deposition, molded into tablets with a diameter of about 3 mm Installation reformer 32 is filled with tablets Cu-Zn catalyst. Coming methanol and water is turned into steam by the evaporator (not shown), which is installed upstream of the inlet installation reformer 32, with her as the fuel enters the gaseous mixture of methanol and water. Flowing into the plant reformer 32 raw fuel gas comes into contact with the Cu-Zn catalyst and undergoes reforming reactions occurring in the Cu-Zn catalyst. As progress in reforming reactions produce hydrogen and carbon dioxide, and rich in hydrogen gas reformer enters the connecting pipe 36.

Flowing in the installation reformer 32 reaction of the reforming process are generally endothermic (reaction in accordance with the expression (6)). To obtain the heat necessary for the occurrence of a specified reaction in the plant reformer 32 includes a combustion unit (not shown) to which the fuel is methanol from the tank 12. The quantity supplied to the combustion unit of methanol is adjusted, so that the working temperature installation reformer 32 is maintained in the range from 220 to 300oC. Installation the of ethanol and water to the reformer 32.

Block 34 of selective CO oxidation in the gas flow reformer from installation reformer 32 and the supply oxidizing gas produces oxidation, predominantly in the hydrogen contained in the gas reforming of carbon monoxide, so you get a gaseous fuel having a reduced concentration of carbon monoxide. Block 34 of selective CO oxidation works as a unit decrease in the concentration of carbon monoxide in the reformer unit fuel 30. The block structure 34 of selective CO oxidation is schematically shown in Fig. 4. This block 34 is filled as described here previously, the catalyst of ruthenium with the addition of lithium, namely, tablets of aluminum oxide coated with the lithium and ruthenium, which are used as catalyst for selective oxidation of carbon monoxide.

When the gas reformer from installation reformer 32 through the connecting pipe 36 to the block 34 selective oxidation of CO in it begins to leak, the reaction of selective oxidation of carbon monoxide, when the gas reformer passes along the surface of the catalyst of ruthenium with the addition of lithium; this reduces the concentration contained in the gas reforming of carbon monoxide. Gas reformer is the quality of gaseous fuel to the fuel cell 20. The concentration of carbon monoxide contained in the resulting gaseous fuel obtained by reducing the concentration of carbon monoxide in the block 34 of selective CO oxidation depends on the operating temperature of the block 34 selective oxidation WITH, from the initial concentration of carbon monoxide in the gas reformer received at block 34 of selective CO oxidation, and gas flow rate of reforming received at block 34 selective oxidation of CO, per unit volume of catalyst.

Sensor carbon monoxide 40 has, as mentioned earlier, in the connection pipe 36 and is designed to measure the concentration of carbon monoxide in the gas reformer, which goes to the block 34 of selective CO oxidation through the connecting pipe 36. Sensor carbon monoxide 40 is connected to the controller 70 and outputs to the controller 70 information regarding the concentration of carbon monoxide in the gas reformer.

The blower 38, as previously mentioned, delivers air that is used for oxidation of carbon monoxide in the block 34 of selective CO oxidation. The blower 38 is connected to the controller 70 and receives the control signals from the controller 70 to supply ZAT sensor carbon monoxide 40 information regarding the concentration of carbon monoxide in the gas reformer, supplied to the block 34 selective CO oxidation, the Controller 70 sends a control signal to the blower 38 on the basis of the aforementioned information, the blower 38 serves to block 34 selective oxidation WITH the specified amount of air, depending on the concentration of carbon monoxide in the gas reformer supplied to the block 34 of selective CO oxidation.

The controller 70 is made in the form of a logic circuit with a microprocessor, and more specifically, the controller 70 includes a Central processing unit (CPU) 72, which performs various operations according to preset control programs, a persistent storage device (ROM) 74, which stores control programs and control data required to perform the various operations using the CPU 72, and a storage device with random access (RAM) 76, which produces an entry in the CPU 72 and reads from various data required for performing various operations using the CPU 72, and, in addition, the port I / o 78, to which the output signals from the sensor monoxide 40 and from which the signals of the control installation reformer 32, block 34 of selective CO oxidation on Waseda described the structure of the fuel cell system 10 unit 34 of selective CO oxidation contains a catalyst of ruthenium with the addition of lithium, which works as a catalyst for selective oxidation of carbon monoxide, as mentioned earlier. Such a system can significantly reduce the concentration of carbon monoxide contained in the gas reformer, coming from the installation reformer 32, and feeding the processed gas as fuel gas to the fuel cell 20. Were studied qualitative characteristics of the catalyst of ruthenium with the addition of lithium, which in this case was used as catalyst for selective oxidation of carbon monoxide. In Fig.5 shows characteristics reduce the concentration of carbon monoxide in rich hydrogen gas at different temperatures for a known catalyst of ruthenium, which is usually used for selective oxidation of carbon monoxide, and a catalyst of ruthenium with the addition of lithium under this option.

Used to compare the catalyst of ruthenium was made when performing processing operations from S140 to S170 flowchart shown in Fig. 1, and on tablets of aluminum oxide was applied only ruthenium. The amount of ruthenium done on tablets of aluminum oxide (moles of ruthenium per unit volume of the catalyst for selective oxidation of carbon monoxide have been studied as follows. In a reactor with a volume of about 10 cm3introduced the catalyst and then the standard gas, which had a typical composition of the gas reformer supplied from installation reformer 32 to block 34 of selective CO oxidation fuel cell system 10. Used exemplary gas, which was obtained by bubbling fluidised bed wetting with water at a temperature of 60oWith gas from a cylinder, a composition of N275%, CO224,5%, WITH 0.5% in the dry state. This process of humidification allows you to set the humidity exemplary gas is mainly equal to the humidity of the gas reformer, which is obtained by the reaction of steam reforming of methanol at a molar ratio of water to methanol [H2ON]/[CH3IT]=2. Moist exemplary gas mixed with air was used as oxidant monoxide, and introduced into the reactor filled with catalyst. The mixed number with an exemplary gas air was used as oxidant monoxide, regulated in such a way as to obtain a molar ratio of oxygen to carbon monoxide in the exemplary gas [O2/[CO] = 3. Moistened and mixed with air exemplary gas was introduced into the filled catalyst reactor with what ATOR of ruthenium with the addition of lithium under this option and, for comparison, a catalyst of ruthenium. In reactors proceeded reaction of selective oxidation of carbon monoxide, due to which the output of the corresponding reactor was getting gas reformer with a low concentration of carbon monoxide. The concentration of carbon monoxide in the resulting gas reformer was measured using a gas chromatograph. Test to check the quality characteristics of each catalyst, lowering the concentration of carbon monoxide, conducted at temperatures of 100, 40 and 200oC.

As shown in Fig.5, the catalyst of ruthenium with the addition of lithium under this option sufficiently reduced concentration of carbon monoxide in rich hydrogen gas at a temperature of 100, 140 and 200oC. Known used for comparing the catalyst of ruthenium reduces the concentration of carbon monoxide to levels comparable with the catalyst of ruthenium with the addition of lithium, at a temperature of 140 and 200oC. However, when the temperature of the catalyst 100oWith the catalyst of ruthenium has significantly worst characteristics reduce the concentration of carbon monoxide in comparison with the catalyst of ruthenium with the addition of lithium. So obrazach temperature, which significantly reduces the concentration of carbon monoxide in the direction of lower temperatures and allows to sufficiently reduce the concentration of carbon monoxide in rich hydrogen gas at temperatures in the broad range from 100 to 200oC.

The use of the catalyst of ruthenium with the addition of lithium facilitates the process of regulating the internal temperature of the block 34 selective CO oxidation, filled with such a catalyst, and simplifies the structure of the overall fuel cell system 10. Block 34 of selective CO oxidation has a wider range of effective temperatures, extended in the direction of lower temperatures, which sufficiently reduces the concentration of carbon monoxide in rich hydrogen gas. Even in the case when the temperature in the immediate vicinity of the outlet unit 34 of selective CO oxidation is reduced to a lower level than in previously known devices, the system in accordance with this variant allows to sufficiently reduce the concentration of carbon monoxide in rich hydrogen gas. This allows you to set the temperature of the gaseous fuel obtained from the output of the block 34 izbirat the t or even eliminates the block reducing the temperature of the gaseous fuel output unit 34 selective CO oxidation, before admission of fuel to the fuel cell 20.

The catalyst of ruthenium with the addition of lithium in accordance with this variant has sufficient activity even at high temperatures of up to approximately 200oWith similarly well-known catalyst of ruthenium. Thus, the gas reformer output setup reformer 32 can be directly submitted to the block 34 selective oxidation WITH, for the reaction of selective oxidation of carbon monoxide. The reforming reaction usually occurs in the setting of reformer 32, filled with Cu-Zn catalyst, at temperatures in the range from 250 to 300oC. the temperature of the gas reformer fed with output setup reformer 32 to the block 34 selective oxidation of CO, approximately 200oC. Thus, the gas reformer output setup reformer 32 may be directly introduced into the reaction of selective oxidation of carbon monoxide. The reaction of selective oxidation of carbon monoxide is exothermic, so primarily it is necessary to lower the internal temperature of the unit 34 selective oxidation WITH, for example, by circulating cooling water in order to have an average temperature katalizatore approximately 100oC. This simplifies the piping system between the installation of the reformer 32, block 34 selective oxidation of CO and fuel cells 20.

The catalyst of ruthenium with the addition of lithium in accordance with this variant has a wider range of effective temperatures, which sufficiently reduces the concentration contained in the rich hydrogen-air carbon monoxide, as compared with the known catalyst of ruthenium. This allows you to expand the permissible temperature range of the catalyst in block 34 of selective CO oxidation and therefore simplifies the temperature control unit 34 of selective CO oxidation. Extended temperature range of the catalyst in block 34 of selective CO oxidation allows to stably produce a reduced concentration of carbon monoxide, even if changes substantially connected to the fuel cell load. The change in the load leads to a change in the amount of gas reformer supplied to the block 34 selective CO oxidation, and changes calorimetric indicator proceeding in this block the reaction of selective oxidation of carbon monoxide, which leads to a change of the internal temperature of the block 34, the elector shall onanie (output) the internal temperature of the block 34 of selective CO oxidation in the range of effective temperatures, in which sufficiently reduces the concentration contained in the rich hydrogen-air carbon monoxide, and provides continuous production of gaseous fuel having a relatively low concentration of carbon monoxide.

The previously described variant makes it possible to obtain the effect due to the use of the catalyst of ruthenium with the addition of lithium, in which ruthenium and lithium deposited on the tablets of aluminum oxide. This catalyst compared with the known catalyst of ruthenium allows you to expand in the direction of lower temperature range of effective temperatures where sufficient activity to accelerate the reaction of selective oxidation of carbon monoxide. Are discussed further catalysts which, in addition to ruthenium is used for the second element different from the lithium, and which provide effects equivalent to the one discussed above for the catalyst of ruthenium with the addition of lithium.

As different from the lithium second element, which is like a litany improves the activity of the catalyst of ruthenium in accelerating the reaction of selective oxidation of carbon monoxide, can be used alkali metal is potassium, alkaline earth E. the second element potassium, referred to as the catalyst of ruthenium with the addition of potassium.

The catalyst of ruthenium different from the second element lithium is produced by the same method that was used for the manufacture of the catalyst of ruthenium with the addition of lithium, in accordance with the flowchart of Fig.1. In the case of the catalyst of ruthenium with the addition of potassium operation S110 use aqueous potassium acetate solution instead of an aqueous solution of lithium acetate, so that the potassium salt was absorbed by the pellets of aluminum oxide. In the case of the catalyst of ruthenium with the addition of barium operation S110 use an aqueous solution of barium acetate, so that the barium salt was absorbed by the pellets of aluminum oxide. In the case of the catalyst of ruthenium with the addition of Nickel in operation S110 use an aqueous solution of Nickel nitrate, so that salt of Nickel was absorbed by the pellets of aluminum oxide. In the case of the catalyst of ruthenium with the addition of zinc during operation S110 use an aqueous solution of zinc nitrate, so that salt of zinc was absorbed by the pellets of aluminum oxide. Similarly, the catalyst of ruthenium with the addition of lithium, in any of these catalysts the second element is applied on the tablets of aluminum oxide with plotnostei per liter of volume pills alumina.

In Fig.5 shows characteristics reduce the concentration of carbon monoxide in rich hydrogen gas at different temperatures for the catalyst of ruthenium with additive different from the lithium second element, and described here earlier catalyst of ruthenium with the addition of lithium. The tests were carried out under the same conditions as the test catalyst of ruthenium with the addition of lithium. As shown in Fig.5, similar to the catalyst of ruthenium with the addition of lithium, the catalyst of ruthenium with additive different from the second element lithium sufficiently reduces the concentration of carbon monoxide in rich hydrogen gas at temperatures of 100, 140 and 200oC. Similarly, the catalyst of ruthenium with the addition of lithium, the catalyst of ruthenium with additive different from the second lithium element can extend in the direction of lower temperature range of effective temperatures, which significantly reduces the concentration of carbon monoxide, and allows to sufficiently reduce the concentration of carbon monoxide in rich hydrogen gas at temperatures in the broad range from 100 to 200oC.

The use of any catalyst of ruthenium with the addition of different ora has the structure similar to the structure of the fuel cell system 10 facilitates the process of regulating the internal temperature of the block selective oxidation of CO and simplifies the structure of the overall fuel cell system. When using any of the above mentioned catalysts extends in the direction of lower temperature range of effective temperatures, which significantly reduces the concentration of carbon monoxide in rich hydrogen gas. This build allows you to set the temperature of the gaseous fuel in the immediate vicinity of the exit of the block selective oxidation of CO, at a lower level than in previously known devices, so that the temperature of the gaseous fuel flowing from the block selective CO oxidation, becomes closer to the operating temperature of the fuel elements. Thus, such a solution is desirable way to simplify or even eliminate the block reducing the temperature of the gaseous fuel output unit of selective CO oxidation, prior to receipt of fuel on the fuel elements.

The catalyst of ruthenium with additive different from the lithium second element has sufficient activity even at high temperatures of up to approximately 200ooC and the temperature of the catalyst in the immediate vicinity of the outlet roughly 100oC. This simplifies the piping system between the installation of the reformer, the block selective oxidation of CO and fuel cells.

Similarly, the catalyst of ruthenium with the addition of lithium, the catalyst of ruthenium with additive different from the lithium second element has a wider range of effective temperatures, which sufficiently reduces the concentration contained in the rich hydrogen gas of carbon monoxide compared with the known catalyst of ruthenium. This allows you to expand the permissible temperature range of the catalyst in the block selective CO oxidation and therefore simplifies the temperature control unit of selective CO oxidation. As described herein previously, the extended temperature range of the catalyst in the block selective CO oxidation enables stable to make it lower concentrations of co-plerophoria use potassium acetate, the barium acetate, Nickel nitrate and zinc nitrate for the manufacture accordingly catalyst of ruthenium with the addition of potassium catalyst of ruthenium with the addition of the barium catalyst of ruthenium with the addition of Nickel and the catalyst of ruthenium with the addition of zinc. However, these examples are not restrictive and can be used and other compounds selected appropriately from nitrates, acetates, chlorides and sulphides. The material for the deposition of ruthenium on the substrate is not limited to the case of ruthenium chloride and for the manufacture of the catalyst of ruthenium with the addition of lithium can be used and other compounds of ruthenium.

The applicant of the present invention have already proposed a catalyst alloy, platinum-ruthenium in ruthenium has a second element and allows you to accelerate the reaction of selective oxidation of carbon monoxide (JAPANESE PATENT LAID-OPEN GAZETTE No. 9-30802). The proposed catalyst alloy, platinum-ruthenium also significantly improves the acceleration of the reaction of selective oxidation of carbon monoxide compared with previously known catalyst of ruthenium (without the second element). However, the catalyst of ruthenium with the addition of lithium or any other specified here above the second cell battery (included) is in the reaction of selective oxidation of carbon monoxide can leak reaction reverse shift which can prevent a significant decline in the concentration of carbon monoxide in the gas reformer. Similarly, the known catalyst of ruthenium, the catalyst of ruthenium with the addition of lithium or any other specified here above the second element has an activity of accelerating ketanazii (conversion to methane), which turns into methane obtained in the course of the reaction the reverse shift carbon monoxide, thereby substantially decreasing the concentration of carbon monoxide in the gas reformer. Meanace proceeds in accordance with the expression:

CO+3H2-->CH4+H2(9)

The catalyst of ruthenium has activity accelerate ketanazii of carbon monoxide in accordance with the expression (9). The addition of lithium or any other above the second element does not lead to a significant reduction in the activity of accelerating ketanazii. Since the reaction is reversed shear is endothermic, the effects of acceleration of ketanazii in accordance with the expression (9) is particularly evident in the high temperatures of the catalyst used in the block selective CO oxidation. Despite the fact that the catalyst alloy, platinum-ruthenium, and has activity to accelerate ketanazii, under the et reaction reverse shift which prevents further reduction due to ketanazii concentration of carbon monoxide in the gas reformer. The catalyst of ruthenium with the addition of lithium or any other specified here above the second element has an activity of accelerating ketanazii, allowing you to absorb the carbon monoxide obtained by the reaction of the backward shift, and more effectively reduce the concentration of carbon monoxide in the gas reformer than the catalyst alloy, platinum-ruthenium. Used in accordance with the present invention, lithium or other second elements are not as expensive as platinum, so the manufacturing cost of the catalyst for selective oxidation of carbon monoxide is reduced compared to the cost of manufacture of the catalyst alloy, platinum-ruthenium.

In the above-described variants produced drawing on tablets of aluminum oxide lithium or other second elements, servants addition to ruthenium, the density of 0.005 mole per liter, and ruthenium density being 0.036 mole per liter. However, these density deposition of the second element and ruthenium are not restrictive and may be modified accordingly molar ratio of the second element to the ruthenium, which in prion ruthenium, which is present in the form of particles on the carrier, which reduces the open area of the surface of ruthenium. This is undesirable affects qualitative characteristics of the preferential oxidation unit containing such a catalyst, namely, it reduces the amount of decrease in the concentration of carbon monoxide in rich hydrogen gas. The molar ratio of the second element to the ruthenium can also be set higher values of 0.14, while ensuring the preferential oxidation unit sufficient to reduce the concentration of carbon monoxide in rich hydrogen gas. On the other hand, an excessively low content of the second element may result in insufficient improvement activity to accelerate the reaction of selective oxidation of carbon monoxide. The molar ratio of the second element to the ruthenium may be installed below a value of 0.14, assuming uniform deposition of the second element in the vicinity of the particles of ruthenium. The molar ratio of the second element to the ruthenium can be set by a corresponding change in the manufacturing process of the catalyst, the weight ratio of aqueous solution of salt of the second element to the tablets of aluminum oxide and due to changes in weight ratio of aqueous solution of salt of Lenia, in accordance with which at first put on tablets of aluminum oxide of a second element, and then the ruthenium. However, if the second element will not cover the surface of the ruthenium and reduce the area of open surface of ruthenium with the creation mentioned here earlier problems, it can be applied on tablets of aluminum oxide after application of ruthenium. Alternatively, the ruthenium and the second element can be applied simultaneously on tablets of aluminum oxide.

Ruthenium and the second element can be fused during the manufacturing process of the catalyst for selective oxidation of carbon monoxide. The creation of an alloy of ruthenium and the second element allows you to place them closer to each other microscopically, so you can expect additional strengthening of the interaction between the ruthenium and the second element acting as a catalyst for selective oxidation of carbon monoxide.

The catalyst of ruthenium with the addition of the second element may be manufactured using any suitable manufacturing method, not necessarily coincident with the described here, while ensuring sufficient activity of the obtained catalyst. In accordance with one modified method after the closure) of the second element on tablets of aluminum oxide. Can be used with any method of manufacture, provided that the resulting catalyst, the second element is in the immediate vicinity of ruthenium and provides improved activity of accelerating the reaction of selective oxidation of carbon monoxide.

Instead of tablets of aluminum oxide as a substrate can be used honeycomb structure (honeycomb). In this case produce the grinding of the catalyst obtained in accordance with the method described here (that is, the catalyst obtained by the deposition of ruthenium and the second element on tablets of aluminum oxide) and applying it to a metal honeycomb structure. In another embodiment, a honeycomb structure is covered with aluminum oxide, and then put the ruthenium and the second element of a cellular structure with a coating of aluminum oxide according to the method similar to that described here previously. The result is a honeycomb structure coated with a catalyst.

In the described embodiments use aluminum oxide as the substrate metal catalyst having an activity of accelerating the reaction of selective oxidation of carbon monoxide. However, it can also be used any other suitable substrate, if not the karenia reaction of selective oxidation of carbon monoxide.

Despite what has been described the preferred embodiment of the invention, it is clear that it specialists in this field can be amended and supplemented, which do not extend, however, beyond the scope of the following claims.

Device to reduce the concentration of carbon monoxide, the method of reducing concentration of carbon monoxide and a catalyst to reduce the concentration of carbon monoxide can be used in the systems of supply of gaseous fuel, for example, hydrogen-enriched gas to the fuel cells, which can be used, for example, as a power source in electric vehicles.

1. Device to reduce the concentration of carbon monoxide contained in the rich hydrogen gas by oxidation, comprising a source of hydrogen-enriched gas, which ensures the supply of hydrogen-enriched gas; a source of oxidizing gas, which ensures the supply of oxygen-containing oxidizing gas used for oxidation of carbon monoxide, and the block selective oxidation of carbon monoxide, which contains a catalyst for selective oxidation of carbon monoxide and which receives the rich in the specified block is selective oxidation contained in rich hydrogen gas of carbon monoxide by the reaction of selective oxidation of carbon monoxide, when this catalyst for selective oxidation of carbon monoxide, which accelerates the reaction of selective oxidation of carbon monoxide, contains as a primary component, ruthenium and optionally contains alkali or alkaline earth metal, which together with ruthenium expand the range of effective temperatures, which accelerates the reaction of selective oxidation of carbon monoxide and alkali or alkaline earth metal is used as a simple mass of metal or alloy with ruthenium.

2. Device to reduce the concentration of carbon monoxide under item 1, characterized in that the alkali or alkaline earth metal obtained by reduction of salts of alkaline or alkaline earth metal.

3. Device to reduce the concentration of carbon monoxide under item 1, characterized in that the alkali metal is lithium or potassium.

4. Device to reduce the concentration of carbon monoxide under item 1, characterized in that the alkaline earth metal is barium.

5. Device to reduce the concentration of carbon monoxide by oxidation contained in the hydrogen rich gas of carbon monoxide, comprising istochnaja, which ensures the supply of oxygen-containing oxidizing gas used for oxidation of carbon monoxide; and the block selective oxidation of carbon monoxide, which contains a catalyst for selective oxidation of carbon monoxide and which receives a rich hydrogen gas from a source rich in hydrogen gas and oxidizing gas from the oxidizing source gas, and in the specified block is selective oxidation contained in rich hydrogen gas of carbon monoxide by the reaction of selective oxidation of carbon monoxide, the catalyst for selective oxidation of carbon monoxide, which accelerates the reaction of selective oxidation of carbon monoxide, contains as a primary component further comprises ruthenium and Nickel.

6. Device to reduce the concentration of carbon monoxide by oxidation contained in rich hydrogen gas, carbon monoxide, comprising a source of hydrogen-enriched gas, which ensures the supply of hydrogen-enriched gas, a source of oxidizing gas, which ensures the supply of oxygen-containing oxidizing gas used for oxidation of co is th oxidation of carbon monoxide and which receives a rich hydrogen gas from a source rich in hydrogen gas and oxidizing gas from the oxidizing source gas, moreover, in the specified block is selective oxidation contained in rich hydrogen gas of carbon monoxide by the reaction of selective oxidation of carbon monoxide, the catalyst for selective oxidation of carbon monoxide, which accelerates the reaction of selective oxidation of carbon monoxide, contains as a primary component further comprises ruthenium and zinc.

7. The method of reducing concentration of carbon monoxide contained in the rich hydrogen gas by oxidation, comprising mixing hydrogen-enriched gas from the oxygen-containing oxidizing gas used for oxidation of carbon monoxide, and the oxidation of carbon monoxide contained in the rich hydrogen gas mixed with an oxidizing gas, due to the reaction of selective oxidation of carbon monoxide using a catalyst for selective oxidation of carbon monoxide, which accelerates the reaction of selective oxidation of carbon monoxide, and contains as a primary component, ruthenium, and additionally contains an alkaline or alkaline-earth metal, which together with ruthenium expand the range of effective temperatures, in which on oxidation of carbon monoxide, moreover, alkali or alkaline earth metal is used as a simple mass of metal or alloy with ruthenium.

8. The method according to p. 7, characterized in that the alkali metal is lithium or potassium.

9. The method according to p. 7, characterized in that the alkaline earth metal is barium.

10. The method of reducing concentration of carbon monoxide contained in the rich hydrogen gas by oxidation, comprising mixing hydrogen-enriched gas from the oxygen-containing oxidizing gas used for oxidation of carbon monoxide; and reducing the concentration of carbon monoxide contained in the rich hydrogen gas mixed with an oxidizing gas, due to the reaction of selective oxidation of carbon monoxide using a catalyst for selective oxidation of carbon monoxide, which accelerates the reaction of selective oxidation of carbon monoxide and contains as a primary component further comprises ruthenium and Nickel.

11. The method of reducing concentration of carbon monoxide contained in the rich hydrogen gas by oxidation, comprising mixing hydrogen-enriched gas from the oxygen-containing omissus is found in rich hydrogen gas, mixed with an oxidizing gas, due to the reaction of selective oxidation of carbon monoxide using a catalyst for selective oxidation of carbon monoxide, which accelerates the reaction of selective oxidation of carbon monoxide and contains as a primary component further comprises ruthenium and zinc.

12. Catalyst for selective oxidation of carbon monoxide contained in the rich hydrogen gas containing as a primary component ruthenium deposited on an appropriate substrate, and optionally containing alkali or alkaline earth metal, which together with ruthenium expand the range of effective temperatures, which accelerates the reaction of selective oxidation of carbon monoxide and alkali or alkaline earth metal is used as a simple mass of metal or alloy with ruthenium.

13. The catalyst according to p. 12, characterized in that the alkali metal is lithium or potassium.

14. The catalyst according to p. 12, characterized in that the alkaline earth metal is barium.

15. The catalyst according to p. 12, characterized in that the alkali or alkaline earth metal obtained by reduction of the sid carbon contained in rich hydrogen gas containing as a primary component ruthenium deposited on an appropriate substrate, and optionally containing Nickel.

17. Catalyst for selective oxidation of carbon monoxide contained in the rich hydrogen gas containing as a primary component ruthenium deposited on an appropriate substrate, and optionally containing zinc.

 

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