CN100344526C - Carbon monoxide removing device, filter, and method for removing carbon monoxide by using them - Google Patents

Carbon monoxide removing device, filter, and method for removing carbon monoxide by using them Download PDF

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CN100344526C
CN100344526C CNB2005100696201A CN200510069620A CN100344526C CN 100344526 C CN100344526 C CN 100344526C CN B2005100696201 A CNB2005100696201 A CN B2005100696201A CN 200510069620 A CN200510069620 A CN 200510069620A CN 100344526 C CN100344526 C CN 100344526C
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carbon monoxide
monoxide removal
iron
catalyzer
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CN1689963A (en
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越后满秋
田畑健
山崎修
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Osaka Gas Co Ltd
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Osaka Gas Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

In operating the carbon monoxide removal reactor or the fuel reforming system, there is provided a technique for removing carbon monoxide in a stable manner for an extended period of time. In a method of removing carbon monoxide including an introducing step of introducing a reactant gas including mixture gas and an oxidizer added thereto to a carbon monoxide removal reactor forming in its casing a catalyst layer comprising a carbon monoxide removal catalyst for removing carbon monoxide contained in the mixture gas and an removing step of removing the carbon monoxide by causing the oxidizer to react with the mixture gas on the carbon monoxide removal catalyst, in said introducing step, the reactant gas of 100 DEG C. or lower is introduced to the carbon monoxide removal reactor.

Description

Carbon monoxide removal device, strainer and carbon monoxide removal method
Technical field
The present invention relates to comprise and import operation and remove the carbon monoxide removal method of operation and the operation method that adopts the fuel reforming system of this carbon monoxide removal method, importing operation is that the reactant gases that will add oxygenant in mixed gas imports in the carbon monoxide removal device, wherein above-mentioned mixed gas be similar to the modification gas that alcohols upgrading (water vapour upgrading, partial combustion upgrading etc.) such as hydrocarbon polymer such as Sweet natural gas, raw gasline, kerosene or methyl alcohol is obtained such, contain hydrogen (H as main component 2), contain the gas of carbon monoxide (CO) as impurity; The carbon monoxide removal device forms the catalyst layer that is made of the carbon monoxide removal catalyzer of removing the carbon monoxide in the mixed gas in its basket; Removing operation is to make above-mentioned oxygenant and above-mentioned mixed gas reaction remove the operation of carbon monoxide by above-mentioned carbon monoxide removal catalyzer.
And, the present invention relates to have the carbon monoxide removal device of the basket that can hold above-mentioned carbon monoxide removal catalyzer, and relate to fuel reforming system with this carbon monoxide removal device.
And, the present invention relates to constitute be loaded in the basket in the catalysing area that above-mentioned carbon monoxide removal catalyzer is constituted and make above-mentioned mixed gas by above-mentioned catalysing area the carbon monoxide removal device and can will import to above-mentioned mixed gas in this carbon monoxide removal device as pretreated technology.
Background technology
In the past, be original fuel with fossil oils such as Sweet natural gases, making in the fuel reforming system of the modification gas (gas (moisture-free basis) that contains the hydrogen more than the 40 volume %) that contains hydrogen and carbon monoxide, above-mentioned original fuel is carried out desulfurization, water vapour upgrading (according to circumstances carrying out the combination of partial combustion upgrading or water vapour upgrading and partial combustion upgrading) in the devulcanizer that is provided with continuously, modifier (fuel modifying device), obtaining with hydrogen is that main component contains carbon monoxide, carbonic acid gas (CO 2), moisture (H 2O) etc. modification gas.And with above-mentioned alcohols, for example methyl alcohol is the methyl alcohol modifier of armoring pure modifying catalyst in the fuel reforming system of original fuel has, and obtaining with hydrogen from methyl alcohol is the modification gas that main component contains carbon monoxide, carbonic acid gas, moisture etc.
Here, making confession in the fuel reforming system of the modification gas of phosphoric acid type fuel cell, people have known because the existence of carbon monoxide, the electrode catalyst of fuel cell produces poisoning of catalyst, so with above-mentioned be that the modification gas of main component imports in the CO (carbon monoxide converter) converter with hydrogen, utilize the transformationreation of carbon monoxide, change above-mentioned carbon monoxide into carbonic acid gas, the concentration that obtains to make the carbon monoxide in the gas is the modification gas of prescribed value following (for example 0.5%).
But, making confession in the fuel reforming system of the modification gas of polymer electrolyte fuel cell, because polymer electrolyte fuel cell is worked under about 80 ℃ low temperature, even so carbon monoxide of trace, electrode catalyst also produces poisoning of catalyst, so need further to reduce above-mentioned carbon monoxide, be provided with the carbon monoxide removal device that holds the carbon monoxide removal catalyzer of removing carbon monoxide in the downstream of above-mentioned CO (carbon monoxide converter) converter, add to oxygenants such as air in the above-mentioned modification gas that above-mentioned CO (carbon monoxide converter) converter is handled and import in the carbon monoxide removal device, in the presence of this carbon monoxide removal catalyzer, carbon monoxide is oxidized to carbonic acid gas, acquisition is reduced to carbon monoxide concentration the modification gas of (for example, 100ppm is following) below the normality.And, in order to ensure the superior performance and the weather resistance of polymer electrolyte fuel cell, obtain carbon monoxide concentration is reduced to modification gas below the 10ppm.
Above-mentioned carbon monoxide removal device is provided with the accommodation section that holds the catalyst layer that is made of the carbon monoxide removal catalyzer on basket, wherein, the carbon monoxide removal catalyzer carries ruthenium (Ru), rhodium (Rh), platinum (Pt), palladium (Pd) etc. on carriers such as aluminum oxide, from gas inflow entrance the gas (reactant gases) that has added oxygenants such as air above-mentioned modification gas is imported in the above-mentioned catalyst layer of above-mentioned accommodation section, and make it to contact with above-mentioned carbon monoxide removal catalyzer, like this, change the carbon monoxide in the above-mentioned modification gas into carbonic acid gas.And, the above-mentioned reactant gases that has reduced carbon monoxide concentration by above-mentioned catalyst layer is discharged from running through the gas stream outlet that is arranged on the above-mentioned basket.And, because when above-mentioned carbon monoxide removal catalyzer is 80～200 ℃ degree in the temperature of catalyst layer, optionally the reaction of oxidizing carbon monoxide becomes and carries out easily, so, on above-mentioned basket, set up thermoregulation mechanism (well heater, water cooler etc.), keep above-mentioned catalyst layer to form the said temperature territory.
In addition, in the past, consider all reasons such as weathering resistance, thermotolerance, intensity, processibility, cost, the stainless steel that mainly adopts iron-bearing materials is as the parts that constitute above-mentioned fuel reforming system.
Summary of the invention
But, the present application people finds, if in the temperature field that is suitable for above-mentioned carbon monoxide removal catalyst action, turn round above-mentioned carbon monoxide removal device for a long time, carbon monoxide concentration from the above-mentioned modification gas that above-mentioned carbon monoxide removal device is discharged raises gradually and reaches tens of ppm, as the fuel feed of above-mentioned polymer electrolyte fuel cell, carbon monoxide concentration is too high sometimes.The reason that this above-mentioned carbon monoxide removal catalyst performance worsens is the neodoxy of not distinguishing in the past.
Therefore, the objective of the invention is, provide a kind of when above-mentioned carbon monoxide removal device of operation or above-mentioned fuel reforming system in view of the foregoing, in long-time, stably remove the method for carbon monoxide and the operation method of above-mentioned fuel reforming system.
And, the objective of the invention is, a kind of carbon monoxide removal device and the fuel reforming system that can remove the carbon monoxide in the mixed gas that contains hydrogen and carbon monoxide in long-time is provided in view of the foregoing.
And, the objective of the invention is, a kind of carbon monoxide removal method that can remove carbon monoxide removal device and strainer and the employing carbon monoxide removal device and the strainer of the carbon monoxide concentration in the mixed gas that contains hydrogen and carbon monoxide in long-time is provided in view of the foregoing.
The first feature means that are used for reaching the carbon monoxide removal method of the present invention of this purpose are, has the importing operation that in the carbon monoxide removal device of the catalyst layer that the carbon monoxide removal catalyzer that forms the carbon monoxide in the mixed gas that is contained hydrogen and carbon monoxide by removal in its basket is constituted, imports the reactant gases that in above-mentioned mixed gas, has added oxygenant, with make above-mentioned oxygenant and above-mentioned mixed gas reaction by above-mentioned carbon monoxide removal catalyzer, thereby in the carbon monoxide removal method of the removal operation of removal carbon monoxide, in above-mentioned importing operation, the above-mentioned reactant gases below 100 ℃ is imported in the above-mentioned carbon monoxide removal device.
And, in the above-mentioned first feature means, in above-mentioned importing operation, be preferably the above-mentioned reactant gases below 80 ℃ is imported in the above-mentioned carbon monoxide removal device.
Perhaps, in the above-mentioned first feature means, the dew point of above-mentioned reactant gases is preferably below 60 ℃ in flow process pressure.
And the dew point of above-mentioned reactant gases is preferably below 40 ℃ in flow process pressure.
And, the second feature means that are used for reaching the carbon monoxide removal method of the present invention of this purpose are, has the importing operation that in the carbon monoxide removal device of the catalyst layer that the carbon monoxide removal catalyzer that forms the carbon monoxide in the mixed gas that is contained hydrogen and carbon monoxide by removal in its basket is constituted, imports the reactant gases that in above-mentioned mixed gas, has added oxygenant, with make oxygenant and above-mentioned mixed gas reaction by above-mentioned carbon monoxide removal catalyzer, thereby in the carbon monoxide removal method of the removal operation of removal carbon monoxide, in above-mentioned removal operation, the top temperature of above-mentioned catalyst layer is remained on more than 130 ℃, below 180 ℃.
And in the above-mentioned second feature means, the top temperature of above-mentioned catalyst layer is preferably more than 150 ℃, below 180 ℃.
And the 3rd feature means that are used for reaching the carbon monoxide removal method of the present invention of this purpose are, has the importing operation that in the carbon monoxide removal device of the catalyst layer that the carbon monoxide removal catalyzer that forms the carbon monoxide in the mixed gas that is contained hydrogen and carbon monoxide by removal in its basket is constituted, imports the reactant gases that in above-mentioned mixed gas, has added oxygenant, with make oxygenant and above-mentioned mixed gas reaction by above-mentioned carbon monoxide removal catalyzer, thereby in the carbon monoxide removal method of the removal operation of removal carbon monoxide, in above-mentioned importing operation, above-mentioned reactant gases below 100 ℃ is imported in the above-mentioned carbon monoxide removal device, in above-mentioned removal operation, the top temperature of above-mentioned catalyst layer is remained on more than 130 ℃, below 180 ℃.
And in above-mentioned feature means, above-mentioned mixed gas is to be preferably hydrocarbon or alcohols upgrading and the modification gas that obtains.
Perhaps in above-mentioned feature means, above-mentioned carbon monoxide removal catalyzer is to be preferably the catalyzer that contains ruthenium.
Perhaps, the first feature means of operation method that are used for reaching the fuel reforming system of the present invention of this purpose are, in the operation method of following fuel reforming system, promptly this method will be held the modifier of modifying catalyst, the CO (carbon monoxide converter) converter of holding carbon monoxide transformation catalyst is connected to gas with said sequence with pipe arrangement with the carbon monoxide removal device that holds the carbon monoxide removal catalyzer of removing the carbon monoxide in the reactant gases and can flows, wherein will to contain the above-mentioned original fuel upgrading in the gas of original fuel and water vapour be the mixed gas that contains hydrogen and carbon monoxide to modifying catalyst, carbon monoxide transformation catalyst carries out conversion with the carbon monoxide in the above-mentioned mixed gas, and reactant gases is to the gas that has added oxygenant from the above-mentioned mixed gas that above-mentioned CO (carbon monoxide converter) converter is discharged; And be provided with the heat exchanger that heat-transfer medium circulates, wherein heat-transfer medium can carry out heat exchange with respect to the above-mentioned mixed gas or the above-mentioned reactant gases that circulate in the pipe arrangement that connects above-mentioned CO (carbon monoxide converter) converter and above-mentioned carbon monoxide removal device; The heat exchange of above-mentioned mixed gas that utilization is circulated in above-mentioned pipe arrangement or above-mentioned reactant gases and the above-mentioned heat-transfer medium that circulates in above-mentioned heat exchanger will remain on below 100 ℃ than the position that is provided with above-mentioned heat exchanger by the above-mentioned reactant gases that circulates in the pipe arrangement of downstream one side and import in the above-mentioned carbon monoxide removal device.
First feature that is used for reaching of the present invention a kind of carbon monoxide removal device of this purpose constitutes and is, has basket, this basket is provided with the catalyzer accommodation section that holds the carbon monoxide removal catalyzer of removing the carbon monoxide in the mixed gas that contains hydrogen and carbon monoxide, with the mixed gas circulation path that is used for above-mentioned mixed gas importing, the above-mentioned catalyzer of discharge accommodation section, wherein, constitute local or whole inner-wall surfaces of the above-mentioned mixed gas circulation path of above-mentioned catalyzer accommodation section and upstream one side thereof with nonferrous material.
In above-mentioned feature constituted, above-mentioned nonferrous material was preferably the copper based material.
Perhaps, in above-mentioned feature constituted, above-mentioned nonferrous material was preferably pottery or glass.
Perhaps, in above-mentioned feature constitutes, be preferably with local or whole inner-wall surfaces from the above-mentioned mixed gas circulation path of be covered by at least a above coating material of selecting the group that aluminum oxide, silicon-dioxide, titanium dioxide were constituted above-mentioned catalyzer accommodation section and upstream one side thereof.
Perhaps, in above-mentioned feature constituted, above-mentioned nonferrous material was preferably synthetic resins.
Perhaps, in above-mentioned feature constitutes, be preferably with above-mentioned synthetic resins be covered above-mentioned mixed gas circulation path local of above-mentioned catalyzer accommodation section and upstream one side thereof or whole inner-wall surfaces.
And, in above-mentioned feature constitutes, be provided with the iron capture mechanism that captures at least a above material that is selected from iron and iron cpd by upstream one side than the zone that holds above-mentioned carbon monoxide removal catalyzer.
And, first feature that is used for reaching the fuel reforming system of the present invention of this purpose constitutes and is, be that to have by upgrading reaction be to contain the fuel modifying device of mixed gas of hydrogen and carbon monoxide and the fuel reforming system of above-mentioned above-mentioned carbon monoxide removal device with hydrocarbon polymer or alcohols upgrading to order, position, be formed in mobile in the system with nonferrous material and contain the gas flowing path that mixed gas was contacted local of hydrogen and carbon monoxide or whole inner-wall surfaces from above-mentioned fuel modifying device to above-mentioned carbon monoxide removal device.
And, second feature that is used for reaching the carbon monoxide removal device of the present invention of this purpose constitutes and is, in constituting the catalysing area that the carbon monoxide removal catalyzer that will be contained the carbon monoxide in the mixed gas of hydrogen and carbon monoxide by removal constitutes, be loaded in the basket, and make above-mentioned mixed gas by in the carbon monoxide removal device of above-mentioned catalysing area, be provided with in the upstream of above-mentioned catalysing area one side and possess the collection unit that iron captures mechanism, wherein iron capture mechanism traps from by select the group that iron and iron cpd constituted at least a more than material.
In above-mentioned feature constitutes, in being preferably, above-mentioned trap portion is loaded in the above-mentioned basket.
And, in above-mentioned feature constitutes, above-mentioned iron capture mechanism be preferably possess can capture from by select the group that iron and iron cpd constituted at least a more than the porous plastid of material.
And in above-mentioned feature constituted, above-mentioned porous plastid was that to be preferably with the aluminum oxide be the porous plastid of main raw.
And in above-mentioned feature constituted, also can have can be with the thermoregulation mechanism of above-mentioned trap portion insulation under 80 ℃～200 ℃.
And, first feature that is used for reaching the strainer of the present invention of this purpose constitutes and is, be to be used for subtend to possess and carry out pretreated strainer with containing the above-mentioned mixed gas that imports in the carbon monoxide removal device of carbon monoxide removal catalyzer of the carbon monoxide removal in the mixed gas of hydrogen and carbon monoxide, and be provided with and possess the trap portion that iron captures mechanism, wherein iron capture mechanism can capture from by select the group that iron and iron cpd constituted at least a more than material.
And, the 4th feature means that are used for reaching the carbon monoxide removal method of the present invention of this purpose are, thereby the carbon monoxide in making the mixed gas that contains hydrogen and carbon monoxide contacts with the carbon monoxide removal catalyzer in the carbon monoxide removal method of removing carbon monoxide, will from by select in the group that iron and iron cpd constituted of sneaking into the above-mentioned mixed gas at least a more than material remove in advance after, above-mentioned mixed gas is contacted with above-mentioned carbon monoxide removal catalyzer.
And the action effect of these square law devices is as follows.
The operation method of carbon monoxide removal method that is proposed among the present invention and the fuel reforming system that adopts this method is based on following neodoxy, that is, the carbon monoxide removal catalyzer that is contained in this carbon monoxide removal device produces poison (iron catalyst poisoning) because of iron or iron cpd.
And, carbon monoxide removal device, fuel reforming system and the strainer that is proposed among the present invention is also based on following above-mentioned opinion, that is, above-mentioned carbon monoxide removal catalyzer produces poisoning because of iron that material contained or the iron cpd that constitutes above-mentioned fuel reforming system.
The contriver has carried out research with keen determination to the reason of the reduction gradually (deterioration reason) of the carbon monoxide removal rate of illustrating above-mentioned carbon monoxide removal device, the result resolves the condition of surface of the catalyzer of above-mentioned deterioration by utilizing electron probe microanalysis (EPMA) (EPMA), and confirming on its surface has iron atom to exist with certain state.And the inventor also confirms does not simultaneously almost have iron atom to exist on the surface of the catalyzer that does not worsen, and thinks that the deterioration of above-mentioned iron or iron cpd or above-mentioned iron and both existence of iron cpd and above-mentioned catalyzer has very dark relation.
So, further the origin of existing iron or iron cpd is inquired in the catalyzer to above-mentioned deterioration, the result learns, the parts that constitute above-mentioned fuel reforming system (for example, the reactor of stainless steel or pipe arrangement, heat exchanger etc.) iron or the iron cpd that are contained sneak in the above-mentioned modification gas, attached on the interior above-mentioned catalyzer that is loaded in the above-mentioned carbon monoxide removal device and blocked active site, thereby the active danger of reduction is arranged.
So far, people do not expect when using the carbon monoxide removal device under common condition, the carbon monoxide removal catalyzer has been subjected to the iron catalyst poisoning, but try iron or iron cpd is sneaked in the above-mentioned modification gas, the carbon monoxide removal catalyzer may produce iron poisoning reason are investigated, as one of possibility, inferring has following such operation.
At first, the modification gas that reduces carbon monoxide concentration by above-mentioned CO (carbon monoxide converter) converter (for example, consist of as representational: hydrogen 65%, carbonic acid gas 19%, carbon monoxide 0.5%, water vapour 15.5%) be with the temperature of temperature out (the about 200 ℃) same degree of above-mentioned CO (carbon monoxide converter) converter under, discharge from above-mentioned CO (carbon monoxide converter) converter, but because the operating temperature of follow-up above-mentioned carbon monoxide removal device is than this temperature low (80～200 ℃), so before in importing to above-mentioned carbon monoxide removal device, at the reactor or the pipe arrangement that connect above-mentioned CO (carbon monoxide converter) converter and above-mentioned carbon monoxide removal device, dispel the heat in the heat exchangers etc., its temperature descends.Because the concentration height of hydrogen, and, constitute in the stainless material of above-mentioned pipe arrangement or heat exchanger etc. and have iron, nickel, so above-mentioned modification gas utilizes iron to combine with carbon monoxide and takes iron carbonyl (Fe (CO) 5) thereby such form forms easy free condition.Therefore think that iron moves with above-mentioned modification gas, flow in the above-mentioned carbon monoxide removal device, by attached to producing poisoning of catalyst on the above-mentioned carbon monoxide removal catalyzer.
And the water etc. of dewfall also might be relevant with the flow process that above-mentioned iron catalyst is poisoned at the oxygenant that adds between above-mentioned CO (carbon monoxide converter) converter and the above-mentioned carbon monoxide removal device or between above-mentioned CO (carbon monoxide converter) converter and above-mentioned carbon monoxide removal device in order to remove carbon monoxide.
Here, even above-mentioned basket is made of stainless steel, but because the carbon monoxide concentration of above-mentioned catalysing area periphery reduces because of catalyst reaction, so think and compare with the inflow from the upstream region of above-mentioned carbon monoxide removal device, the generation of above-mentioned iron carbonyl is few.
So, the inventor has carried out research with keen determination to the method for removing carbon monoxide from the above-mentioned mixed gas that has adopted above-mentioned carbon monoxide removal catalyzer, found that above-mentioned carbon monoxide removal catalyzer is difficult for producing because of iron the carbon monoxide removal method of poisoning of catalyst, thereby finished the present invention.
And, the inventor expects spilling to the above-mentioned modification gas of supplying with above-mentioned carbon monoxide removal device from the parts that constitute above-mentioned fuel reforming system by suppressing iron and iron cpd, thereby prevent the poisoning of catalyst of above-mentioned carbon monoxide removal catalyzer, and having carried out research with keen determination, the result has finished the present invention.
And, the inventor expects by remove the material more than select at least a from by the group that iron and iron cpd constituted in the above-mentioned modification gas from supply to above-mentioned carbon monoxide removal device after, make it to contact with above-mentioned catalyzer, thereby prevent the poisoning of above-mentioned catalyzer, and having carried out research with keen determination, the result has finished the present invention.
Here, has the importing operation that in the carbon monoxide removal device of the catalyst layer that the carbon monoxide removal catalyzer that forms the carbon monoxide in the mixed gas that is contained hydrogen and carbon monoxide by removal in its basket is constituted, imports the reactant gases that in above-mentioned mixed gas, has added oxygenant, with make above-mentioned oxygenant and above-mentioned mixed gas reaction by above-mentioned carbon monoxide removal catalyzer, thereby in the carbon monoxide removal method of the removal operation of removal carbon monoxide, if in above-mentioned importing operation, above-mentioned reactant gases below 100 ℃ is imported in the above-mentioned carbon monoxide removal device, then becoming is not easy to cause combining of the ferrous components that constitutes above-mentioned pipe arrangement etc. and carbon monoxide, thus the generation of inhibition iron carbonyl.And, even generate above-mentioned iron carbonyl, because its boiling point is 103 ℃, so think and remain on below 100 ℃ by temperature with above-mentioned reactant gases, suppress gasification, thereby can suppress its inflow to the above-mentioned carbon monoxide removal device that is positioned at above-mentioned pipe arrangement downstream.
In addition, if make above-mentioned reactant gases cooling,, thereby can adopt easy cooling way then with media such as air or water more than 0 ℃.
And, in the above-mentioned first feature means, in above-mentioned importing operation, if making the temperature that imports to the above-mentioned reactant gases in the above-mentioned carbon monoxide removal device is below 80 ℃, then the formation speed of above-mentioned iron carbonyl can be suppressed fully low, and the easily control that also becomes of the top temperature of above-mentioned catalyst layer, so preferred.
And, if contain a large amount of moisture in the reactant gases in importing to above-mentioned carbon monoxide removal device, when then the temperature of the above-mentioned reactant gases in will importing to above-mentioned carbon monoxide removal device inlet drops to below 100 ℃, moisture condenses and dewfall in above-mentioned pipe arrangement and in the above-mentioned carbon monoxide removal device, thereby above-mentioned pipe arrangement is interior and the sectional area or the volume random variation of the path of the above-mentioned reactant gases that above-mentioned carbon monoxide removal device is interior, supply to the also possible random fluctuation of above-mentioned flow rate of reactive gas of above-mentioned carbon monoxide removal device, the above-mentioned carbon monoxide removal catalyzer that perhaps is contained in the above-mentioned carbon monoxide removal device might be wetting by condensed water, reduces active.So, when the temperature of the above-mentioned reactant gases in will importing to above-mentioned carbon monoxide removal device inlet descends, if condensing in advance separation before dew point in the above-mentioned reactant gases being become importing to the water vapour that is contained in the above-mentioned reactant gases in the above-mentioned carbon monoxide removal device below 60 ℃ in flow process pressure, then since above-mentioned carbon monoxide removal catalyzer become be difficult for wetting, so activity is not easy to descend, and can with in the above-mentioned pipe arrangement and the amplitude of fluctuation of the above-mentioned flow rate of reactive gas in the carbon monoxide removal device suppress very for a short time.And, when load change etc., S/C in the above-mentioned modifier (mol ratio of the carbon that steam and above-mentioned original fuel contained) change, water vapour quantitative change in above-mentioned reactant gases for a long time, also can import to the amount of the water vapour of the above-mentioned reactant gases in above-mentioned pipe arrangement and the carbon monoxide removal device by adjustment, stably remove carbon monoxide.
And, if the dew point of above-mentioned reactant gases is below 40 ℃ in flow process pressure, then can fully suppress the moisture dewfall in the above-mentioned reactant gases, and, the temperature range (particularly temperature range at low temperatures) of utilizing above-mentioned carbon monoxide removal catalyzer the carbon monoxide removal catalyzer in the above-mentioned reactant gases can be removed to below the 10ppm becomes big, even because cryogenic above-mentioned reactant gases is imported in the above-mentioned carbon monoxide removal device, also begin the carbon monoxide removal reaction easily, so preferred.
And people have known that above-mentioned iron carbonyl at high temperature decomposes or polymerization.So think, has the importing operation that in the carbon monoxide removal device of the catalyst layer that the carbon monoxide removal catalyzer that forms the carbon monoxide in the mixed gas that is contained hydrogen and carbon monoxide by removal in its basket is constituted, imports the reactant gases that in above-mentioned mixed gas, has added oxygenant, with make oxygenant and above-mentioned mixed gas reaction by above-mentioned carbon monoxide removal catalyzer, thereby in the carbon monoxide removal method of the removal operation of removal carbon monoxide, remain on more than 130 ℃ by top temperature the above-mentioned catalyst layer in the above-mentioned removal operation, even when iron carbonyl flows in the above-mentioned carbon monoxide removal device, also can perhaps can attachment point substantially be reduced by decomposing the attachment state of control to above-mentioned carbon monoxide removal catalyzer.
In addition, if the temperature of above-mentioned catalyst layer is too high, be easy to generate the methanation reaction of carbonic acid gas, the hydrogen that is contained in the not only above-mentioned mixed gas is consumed yield and descends, and because reaction heat, it is difficult that temperature controlling becomes, so the top temperature that is preferably above-mentioned catalyst layer remains on below 180 ℃.
Here, the top temperature that makes above-mentioned catalyst layer is more than 150 ℃, below 180 ℃, can further realize the long lifetime (with reference to embodiment) of above-mentioned carbon monoxide removal catalyzer.
And, has the importing operation that in the carbon monoxide removal device of the catalyst layer that the carbon monoxide removal catalyzer that forms the carbon monoxide in the mixed gas that is contained hydrogen and carbon monoxide by removal in its basket is constituted, imports the reactant gases that in above-mentioned mixed gas, has added oxygenant, with make oxygenant and above-mentioned mixed gas reaction by above-mentioned carbon monoxide removal catalyzer, thereby in the carbon monoxide removal method of the removal operation of removal carbon monoxide, the temperature that makes the above-mentioned reactant gases in the above-mentioned importing operation is to import to below 100 ℃ to suppress above-mentioned iron carbonyl in the above-mentioned carbon monoxide removal device and flow in the above-mentioned catalyst layer, and in above-mentioned removal operation, the top temperature of above-mentioned catalyst layer is remained on more than 130 ℃, 180 ℃ are suppressed above-mentioned iron carbonyl adhering to above-mentioned carbon monoxide removal catalyzer to get off, by the composite effect of the two, the poisoning of catalyst of above-mentioned carbon monoxide removal catalyzer is further suppressed, and can remove above-mentioned carbon monoxide in the above-mentioned reactant gases with very high ratio.
And, when above-mentioned mixed gas is hydrocarbon or alcohols are carried out upgrading and during the modification gas that obtains, if utilize aforesaid method to remove carbon monoxide, then can to remove carbon monoxide in long-time, so preferably.
And, because the present application people finds, above-mentioned carbon monoxide removal catalyzer is when containing the catalyzer of ruthenium, the influence of the active low and lost of life that above-mentioned iron catalyst poisoning is caused etc. is bigger, so, above-mentioned carbon monoxide removal catalyzer is when containing the catalyzer of ruthenium, is effective if be suitable for present method.
Here, when moving following fuel reforming system, promptly, this system will hold the modifier of modifying catalyst, the CO (carbon monoxide converter) converter of holding carbon monoxide transformation catalyst is connected to gas with said sequence with pipe arrangement with the carbon monoxide removal device that holds the carbon monoxide removal catalyzer of removing the carbon monoxide in the reactant gases and can flows, wherein will to contain the above-mentioned original fuel upgrading in the gas of original fuel and water vapour be the mixed gas that contains hydrogen and carbon monoxide to modifying catalyst, carbon monoxide transformation catalyst carries out conversion to the carbon monoxide in the above-mentioned mixed gas, and reactant gases is to the gas that has added oxygenant from the above-mentioned mixed gas that above-mentioned CO (carbon monoxide converter) converter is discharged; And be provided with the heat exchanger that heat-transfer medium circulates, wherein heat-transfer medium can carry out heat exchange with respect to the above-mentioned mixed gas or the above-mentioned reactant gases that circulate in the pipe arrangement that connects above-mentioned CO (carbon monoxide converter) converter and above-mentioned carbon monoxide removal device; By as described in claim 10, the heat exchange of above-mentioned mixed gas that utilization is circulated in above-mentioned pipe arrangement or above-mentioned reactant gases and the above-mentioned heat-transfer medium that in above-mentioned heat exchanger, circulates, to remain on below 100 ℃ by the above-mentioned reactant gases that circulates in the pipe arrangement of downstream one side than the position that is provided with above-mentioned heat exchanger, thereby in above-mentioned pipe arrangement, can suppress to produce above-mentioned iron carbonyl.Therefore, import in the above-mentioned carbon monoxide removal device by the reactant gases that will adjust temperature like this, can suppress above-mentioned iron carbonyl flows in the above-mentioned catalyst layer, and the iron catalyst that can alleviate above-mentioned carbon monoxide removal catalyzer is poisoned, thereby the carbon monoxide removal activity of above-mentioned carbon monoxide removal catalyzer is remained on higher level.
And, as other form of implementation of the present invention, be provided with the catalyzer accommodation section that holds the carbon monoxide removal catalyzer of removing the carbon monoxide in the mixed gas contain hydrogen and carbon monoxide and be used for above-mentioned mixed gas is imported having, discharge in the carbon monoxide removal device of basket of mixed gas circulation path of above-mentioned catalyzer accommodation section, if constitute local or whole inner-wall surfaces of the above-mentioned mixed gas circulation path of above-mentioned catalyzer accommodation section and upstream one side thereof with nonferrous material, then iron and iron cpd are separated out disappearance to the dissolving of above-mentioned mixed gas (fuel gas), so can prevent contacting of above-mentioned carbon monoxide removal catalyzer and iron and iron cpd.So, owing to can prevent above-mentioned carbon monoxide removal catalyzer by iron and the caused poisoning of catalyst of iron cpd, so above-mentioned carbon monoxide removal activity of such catalysts can be maintained higher level.Therefore, can prolong above-mentioned carbon monoxide removal life of catalyst, meanwhile can save the time of the operation of Maintenance and Repair, the above-mentioned carbon monoxide removal catalyzer of exchange.
In addition, the position that is contacted with above-mentioned mixed gas about above-mentioned carbon monoxide removal device, constitute its part, be preferably and constitute in fact that they are whole with above-mentioned nonferrous material although require, but about other position, because with irrelevant, so also can constitute by iron-bearing materials to above-mentioned mixed gas supply iron.If constitute like this, then have the advantages that iron-bearing materials had (intensity etc.) such as stainless steel, and can prevent the iron catalyst poisoning of above-mentioned carbon monoxide removal catalyzer.
In above-mentioned feature constituted, if above-mentioned nonferrous material is copper based materials such as phosphorized copper, brass, then erosion resistance, heat conductivity, weathering resistance were good, so preferred.And, because phosphorized copper, copper bond are good, even so only constitute above-mentioned carbon monoxide removal device with copper based materials such as phosphorized copper, brass since with the engaging easily and form firm joint of the parts of downstream provided thereon one side, so the weather resistance height.
And, if constitute above-mentioned nonferrous material, then owing to thermotolerance and excellent corrosion resistance, so preferred with glass such as pottery or quartz and vulval vycols.And it is also preferred because of same reason to cover enamel.And,, meanwhile can save the time of Maintenance and Repair, exchanging operation so can prolong above-mentioned carbon monoxide removal life of catalyst owing to can suppress the iron catalyst poisoning of carbon monoxide removal catalyzer.
Here, for fear of contacting of above-mentioned mixed gas and above-mentioned iron and iron cpd, be preferably with from by select the group that aluminum oxide, silicon-dioxide, titanium dioxide were constituted as above-mentioned pottery at least a more than coating material be covered above-mentioned mixed gas circulation path local of above-mentioned catalyzer accommodation section and upstream one side thereof or whole inner-wall surfaces.If like this, the above-mentioned coating material of coating etc. on the inner face of the carbon monoxide removal device that constitutes by the such iron-bearing materials of stainless steel that can be former, with simple enforcement, keep the strong point of above-mentioned iron-bearing materials, and economy ground suppresses the iron catalyst poisoning of above-mentioned carbon monoxide removal catalyzer.
And, if utilize synthetic resins (for example, in the operating temperature of above-mentioned carbon monoxide removal device, the teflon resin of character shape invarianceization, polyether-ether-ketone (PEEK) resin etc.) constitute above-mentioned nonferrous material, low price and excellent processability, thus preferred, and owing to can suppress the iron catalyst poisoning of above-mentioned carbon monoxide removal catalyzer, so can prolong above-mentioned carbon monoxide removal life of catalyst, meanwhile can save the time of Maintenance and Repair, exchanging operation.
Here, for fear of contacting of above-mentioned mixed gas and above-mentioned iron and iron cpd, be preferably with above-mentioned synthetic resins be covered above-mentioned mixed gas circulation path local of above-mentioned catalyzer accommodation section and upstream one side thereof or whole inner-wall surfaces.If like this; form protective membrane of above-mentioned synthetic resins etc. on the inner face of the carbon monoxide removal device that constitutes by the such iron-bearing materials of stainless steel that can be former; with simple enforcement; the strong point that keeps above-mentioned iron-bearing materials, and economy ground suppresses the iron catalyst poisoning of above-mentioned carbon monoxide removal catalyzer.
And, leaning on upstream one side than the zone that holds above-mentioned carbon monoxide removal catalyzer, when the face that contacts with gas is provided with raw-material parts of iron content such as exposing stainless steel etc., in above-mentioned feature constitutes, in the iron capture mechanism that is provided with at least a above material that capture selects than the zone that holds above-mentioned carbon monoxide removal catalyzer by upstream one side from the group that is made of iron and iron cpd.Capture mechanism with this iron, can capture the iron and the iron cpd that splash in from the gas that leans on upstream one effluent than the zone that holds above-mentioned carbon monoxide removal catalyzer.With this, can further reduce above-mentioned carbon monoxide removal catalyzer and the chance that iron that splashes or iron cpd contact, suppress the iron catalyst of above-mentioned carbon monoxide removal catalyzer and poison.Therefore, can prolong above-mentioned carbon monoxide removal life of catalyst, meanwhile can save the time of Maintenance and Repair, exchanging operation.
And, if having by upgrading reaction in proper order with the nonferrous material formation is the fuel reforming system that contains the fuel modifying device of mixed gas of hydrogen and carbon monoxide and above-mentioned carbon monoxide removal device with hydrocarbon polymer or alcohols upgrading, position from above-mentioned fuel modifying device to above-mentioned carbon monoxide removal device, local or whole inner-wall surfaces of the gas flowing path that mixed gas contacted of mobile hydrogen and carbon monoxide in system, even then this field becomes and is easy to generate the temperature province that dissolved ferric iron is separated out, owing to there is not the supply source of iron, separate out to the dissolving of above-mentioned carbon monoxide removal device so no longer produce iron and iron cpd, thereby can suppress iron and the iron cpd inflow in zone downstream thus.If like this, can further suppress iron and iron cpd to the adhering to of above-mentioned carbon monoxide removal catalyzer, thereby the iron catalyst of above-mentioned carbon monoxide removal catalyzer is poisoned and is further suppressed.Therefore, can prolong above-mentioned carbon monoxide removal life of catalyst, meanwhile can save the time of Maintenance and Repair, exchanging operation.
Other form of implementation as the application, in constituting the catalysing area that the carbon monoxide removal catalyzer that will be contained the carbon monoxide in the mixed gas of hydrogen and carbon monoxide by removal constitutes, be loaded in the basket, and make above-mentioned mixed gas by in the carbon monoxide removal device of above-mentioned catalysing area, one side possesses trap portion in the upstream of above-mentioned catalysing area, capture mechanism by the iron that the material more than at least a that capture selects is set at this from by the group that iron and iron cpd constituted, above-mentioned mixed gas is at first by above-mentioned trap portion, at this moment, contact by capturing mechanism with above-mentioned iron, from by select the group that iron and iron cpd constituted at least a more than material be caught in above-mentioned iron and capture in the mechanism, removed from by select the group that iron and iron cpd constituted at least a more than the mixed gas of material arrived above-mentioned catalysing area.So, be difficult for producing poisoning of catalyst owing to the above-mentioned carbon monoxide removal catalyzer that is positioned at above-mentioned catalysing area becomes, so can in long-time, its activity be maintained higher level.Therefore, can provide a kind of carbon monoxide removal device that can reduce the concentration of the carbon monoxide in the mixed gas that contains hydrogen and carbon monoxide for a long time.
Here, change if consider the influence that has form Yin Wendu or coexisting substances of iron, for positively suppressing the generation that above-mentioned iron catalyst is poisoned, it is the mechanism of catching iron and iron cpd that above-mentioned iron captures that mechanism is preferably.Perhaps, use form according to it, particularly when clear and definite iron and and iron cpd in the iron compound of particular types when promoting that iron catalyst is poisoned, also can use the above-mentioned iron of the iron compound of catching this particular types to capture mechanism.
Particularly, because the stainless steels that use in other device, reaction tubes and pipe arrangement beyond constituting above-mentioned fuel reforming system, the heat exchanger etc. more, if so consider the convenience that it connects etc., although the present invention forms above-mentioned carbon monoxide removal device with stainless steel, but can prevent that carbon monoxide removal device involved in the present invention is useful on this aspect of the caused poisoning of catalyst of iron or iron cpd.
In above-mentioned feature constitutes, if will be loaded in the above-mentioned trap portion in the above-mentioned basket, because it is short with the distance of above-mentioned catalysing area, even so for example use the basket that might the free starting material be constituted by iron or iron cpd, owing to be difficult for causing iron or iron cpd dissociating between above-mentioned trap portion and above-mentioned catalysing area, so preventing that aspect the poisoning of catalyst of above-mentioned catalyzer be preferred.
And, if above-mentioned iron capture mechanism possess can capture from by select the group that iron and iron cpd constituted at least a more than the porous plastid of material, then per unit volume from by select the group that iron and iron cpd constituted at least a more than the collection efficiency height of material, so can make the compact constructionization of above-mentioned trap portion.
And, if above-mentioned porous plastid is to be the porous plastid of main raw with the aluminum oxide, then to from by the group that iron and iron cpd constituted, select at least a more than the high adsorption capacity of material, capture easily from by at least a above material of selecting the group that iron and iron cpd constituted, so preferably.
And, can be if having with the thermoregulation mechanism of above-mentioned trap portion insulation under 80 ℃～200 ℃, thereby above-mentioned trap portion is remained 80 ℃～200 ℃, then the temperature out of the use temperature of above-mentioned trap portion and the above-mentioned CO (carbon monoxide converter) converter of being located at its leading portion and the temperature of being located at the above-mentioned carbon monoxide removal catalyzer of its back segment become identical temperature province, so temperature control easily, and is preferred.
In the carbon monoxide removal device before the carbon monoxide removal catalyzer that possesses the carbon monoxide of removing in the mixed gas that contains hydrogen and carbon monoxide, if will carry out pretreated strainer to above-mentioned mixed gas as being used for, be provided with possess can capture from by select the group that iron and iron cpd constituted at least a more than the iron of the material strainer that captures the trap portion of mechanism be mounted thereon trip one side, then capture from by the group that iron and iron cpd constituted that produces by one side place, upstream than above-mentioned strainer, select at least a more than material, thereby can prevent above-mentioned catalyzer with from by select the group that iron and iron cpd constituted at least a more than the contacting of material, so can prevent the poisoning of catalyst of above-mentioned catalyzer thus.So, because becoming, the above-mentioned carbon monoxide removal catalyzer in the above-mentioned carbon monoxide removal device is difficult for producing poisoning of catalyst, so can in long-time, its activity be maintained higher level, thereby can reduce the concentration of the carbon monoxide in the mixed gas that contains hydrogen and carbon monoxide for a long time.
And, by above-mentioned strainer being set independently, can directly utilize former carbon monoxide removal device, and can also carry out the Maintenance and Repair that above-mentioned iron captures mechanism independently with the Maintenance and Repair of above-mentioned carbon monoxide removal device with above-mentioned carbon monoxide removal device.
Here, change if consider the influence that has form Yin Wendu or coexisting substances of iron, for positively suppressing the generation that above-mentioned iron catalyst is poisoned, it is the mechanism of catching iron and iron cpd that above-mentioned iron captures that mechanism is preferably.Perhaps, use form according to it, particularly when clear and definite iron and and iron cpd in the iron compound of particular types when promoting that iron catalyst is poisoned, also can use the above-mentioned iron of the iron compound of catching this particular types to capture mechanism.
And, thereby the carbon monoxide in making the mixed gas that contains hydrogen and carbon monoxide contacts with the carbon monoxide removal catalyzer in the carbon monoxide removal method of removing carbon monoxide, if will from by select in the group that iron and iron cpd constituted of sneaking into the above-mentioned mixed gas at least a more than material remove in advance, then as mentioned above, can with the reason material that causes above-mentioned carbon monoxide removal catalyzer to produce poisoning of catalyst with removal before above-mentioned carbon monoxide removal catalyzer contact.Therefore, if make removed from by select the group that iron and iron cpd constituted at least a more than the mixed gas of material contact with above-mentioned carbon monoxide removal catalyzer, then the iron catalyst poisoning is suppressed, and can in long-time its activity be maintained higher level.Therefore, utilize the reaction with above-mentioned carbon monoxide removal catalyzer, can reduce the concentration of the carbon monoxide in the mixed gas that contains hydrogen and carbon monoxide for a long time.
Here, change if consider the influence that has form Yin Wendu or coexisting substances of iron, for positively suppressing the generation that above-mentioned iron catalyst is poisoned, be preferably from make the mixed gas that contact with the carbon monoxide removal catalyzer and remove except that de-iron and iron cpd.
Description of drawings
Fig. 1 is the block diagram that expression can be implemented fuel reforming system of the present invention;
Fig. 2 is the curve that expression imports to the temperature and the active correlationship of carbon monoxide oxidation removal of the gas in the carbon monoxide removal device;
Fig. 3 is the catalyst layer top temperature of expression carbon monoxide removal device and the curve of the active correlationship of carbon monoxide oxidation removal;
Fig. 4 is the block diagram of expression other form of implementation of the present invention;
Fig. 5 is the block diagram of expression another embodiment of the present invention;
Fig. 6 is the sectional view that is used to implement reaction tubes of the present invention;
Fig. 7 is the curve of expression effect of the present invention;
Concrete form of implementation
Below based on description of drawings form of implementation of the present invention.
Fig. 1 represents to implement the fuel reforming system of carbon monoxide removal method involved in the present invention.This fuel reforming system is to be original fuel with Sweet natural gas (domestic gas), manufacturing is the system of the modification gas of main component for the hydrogen in polymer electrolyte fuel cell, and it is 1 that the original fuel of supplying with above-mentioned original fuel is supplied with, hold the devulcanizer 2 of desulfurization catalyst, the modifier 4 that holds modifying catalyst, the carbon monoxide removal device 6 that holds the CO (carbon monoxide converter) converter 5 of carbon monoxide transformation catalyst and hold above-mentioned carbon monoxide removal catalyzer connect by pipe arrangement.The modification gas (fuel gas) of upgrading is supplied to polymer electrolyte fuel cell 7 by these devices.
Being stored in that above-mentioned original fuel supplies with is Sweet natural gas in 1 during by above-mentioned devulcanizer 2, contacts with above-mentioned desulfurization catalyst and removes sulfur component.With after the water vapour of being supplied with by water vapour producer 3 mixes, be transported in the above-mentioned modifier 4 then, here contact with above-mentioned modifying catalyst, the methane in the above-mentioned Sweet natural gas is that main component is a hydrogen by upgrading, is the carbon monoxide as by product then.Although the modification gas of Huo Deing is rich in hydrogen like this, owing to contain the carbon monoxide of the secondary resultant of conduct of tens %, so can not directly supply with above-mentioned polymer electrolyte fuel cell 7.So, in above-mentioned CO (carbon monoxide converter) converter 5, the such carbon monoxide transformation catalyst of modification gas and copper-zinc system catalyst is contacted, be carbonic acid gas with carbon monodixe conversion, carbon monoxide concentration is reduced to 0.5～1%.
And, after carbon monoxide concentration being reduced to 0.5～1% above-mentioned modification gas and the air of being supplied with by oxygenant feeder 9 (oxygen is as the oxygenant effect) mixing, be directed in the above-mentioned carbon monoxide removal device 6 by above-mentioned pipe arrangement as reactant gases.
This carbon monoxide removal device 6 is that structure is to form the catalyst layer that is made of the carbon monoxide removal catalyzer in its basket, and makes the device of above-mentioned reactant gases by above-mentioned catalyst layer.Above-mentioned carbon monoxide removal catalyzer adopts and carry for example material of precious metals such as ruthenium, platinum, rhodium, palladium on carrier such as aluminum oxide.
When carbon monoxide concentration is reduced to 0.5～1% above-mentioned modification gas when flowing in the basket of above-mentioned carbon monoxide removal device 6 with above-mentioned oxygenant, the then above-mentioned catalyst layer contact that forms of place therewith.Accommodating above-mentioned carbon monoxide removal catalyzer in the above-mentioned catalyst layer, here by the catalyzed reaction of above-mentioned carbon monoxide removal catalyzer, mainly is that the reaction of carbon monoxide and oxygen is oxidized, forms carbonic acid gas.Like this, the carbon monoxide concentration in the above-mentioned modification gas is removed, and finally is supplied to above-mentioned polymer electrolyte fuel cell 7.
Because above-mentioned carbon monoxide removal device 6 is used for the thermoregulation mechanism 8 of above-mentioned basket temperature regulation in this scope so have so that above-mentioned catalyst layer forms about 80～180 ℃ mode moves.This thermoregulation mechanism 8 has the water cooler that is used for heating the well heater of above-mentioned basket or is used for cooling off thermal source and above-mentioned basket.
And be attached on the above-mentioned carbon monoxide removal catalyst surface and reduce active and suppress the side reactions such as methanation of carbon monoxide in order to suppress to flow into iron containing compounds such as iron carbonyl in the above-mentioned catalyst layer or metallic iron, with aforementioned temperature regulating mechanism 8 top temperature of above-mentioned catalyst layer is adjusted into 130 ℃～180 ℃, is preferably 150 ℃～180 ℃.
And, connect on the part or all of outside wall surface of pipe arrangement of above-mentioned CO (carbon monoxide converter) converter 5 and above-mentioned carbon monoxide removal device 6 and extended heat exchanger 81, the heat-transfer medium (for example, air or water etc.) that wall that can be by above-mentioned pipe arrangement and above-mentioned mixed gas or above-mentioned reactant gases carry out heat exchange circulates in above-mentioned heat exchanger.The position that above-mentioned heat exchanger 81 is set can be than adding the forward stage of above-mentioned oxygenant in above-mentioned mixed gas as shown in Figure 1 both, also can be to add the position of above-mentioned oxygenant as above-mentioned reactant gases circulation in above-mentioned mixed gas.Owing to utilize above-mentioned heat-transfer medium of mobile and above-mentioned mixed gas of mobile or above-mentioned reactant gases generation heat exchange in above-mentioned pipe arrangement in above-mentioned heat exchanger 81, above-mentioned mixed gas or above-mentioned reactant gases are cooled, so measure above-mentioned mixed gas or the above-mentioned flow rate of reactive gas that flow in the above-mentioned pipe arrangement in advance, thereby temperature etc. are suitably adjusted the flow of above-mentioned heat-transfer medium etc., or make above-mentioned heat-transfer medium circulation with the flow etc. of regulation, to in pipe arrangement, be adjusted into below 100 ℃ by the mobile gas temperature with this, consider that load change etc. is preferably and adjust to below 80 ℃, wherein pipe arrangement than the position that above-mentioned heat exchanger 81 is set by downstream one side.In addition, based on the factors such as temperature that environment and employed above-mentioned thermal medium are set of above-mentioned carbon monoxide removal device 6, determine the temperature (lower limit) of above-mentioned reactant gases.
As mentioned above, or the temperature of above-mentioned catalyst layer is adjusted into more than 130 ℃, below 180 ℃, or will be adjusted into below 100 ℃ with the temperature of the contacted above-mentioned pipe arrangement in upstream of above-mentioned carbon monoxide removal device, though poison by any one iron catalyst that promptly can significantly suppress above-mentioned carbon monoxide removal catalyzer at least of implementing such scheme, and the long lifetime and active improvement of realizing above-mentioned carbon monoxide removal catalyzer, but can obtain composite effect by implementing two schemes, but also can further realize the long lifetime of carbon monoxide removal catalyzer and improve active.
And, if on above-mentioned pipe arrangement, drain trap is set, make the steam coagulation in the above-mentioned reactant gases that imports in the above-mentioned carbon monoxide removal device 6, the dew point that makes above-mentioned reactant gases is below 60 ℃ in flow process pressure, is preferably below 40 ℃, can prevent dewfall in above-mentioned pipe arrangement or above-mentioned carbon monoxide removal device.
Carbon monoxide removal method involved in the present invention can be preferably 500～50,000/ hour, more preferably 1,00～30,000/ hour space velocity (GHSV) is used above-mentioned carbon monoxide removal catalyzer.
Embodiment
Below, describe to the test of the effect that is used for verifying above-mentioned carbon monoxide removal method involved in the present invention.
With diameter is that the spherical gamma-aluminium oxide carrier of 2～4mm is immersed in the ruthenium trichloride aqueous solution, and makes it to carry ruthenium by pickling process.After being dried, be immersed in the aqueous sodium carbonate, thereby make the immobilization on above-mentioned carrier of above-mentioned ruthenium, and washing, drying, precursor obtained.This precursor is immersed in the hydrazine solution ruthenium of the above-mentioned preceding surface of reduction, washes once again, make it at 105 ℃ of dry down Ru/ aluminium oxide catalysts (A) that obtain.The concentration of the ruthenium in the Ru/ aluminium oxide catalyst that is obtained is 0.98 weight %, and average micro-pore diameter is 7.4nm.
In addition, in following embodiment 1,2, be filled into the Ru/ aluminium oxide catalyst that is obtained in the reaction tubes after, in the gas flow that is mixed with hydrogen and nitrogen that contains 5 volume % hydrogen, keep down 1.5 hours (pre-treatment) in 220 ℃.This pre-treatment is the processing that is used for improving the initial activity of above-mentioned Ru/ aluminium oxide catalyst in low temperature.
(embodiment 1)
To be filled into inside as Ru/ aluminium oxide catalyst (A) 8cc of carbon monoxide removal catalyzer, to have external diameter be that the telescopic internal diameter that the insertion thermocouple of 6mm is used is in the stainless steel reaction tubes (basket) of 21.2mm, after forming catalyst layer, implement above-mentioned pre-treatment, make two microreactors (carbon monoxide removal device).The reaction analog gas that imports to basket inside from the inlet of this carbon monoxide removal device is released to outside the basket from above-mentioned outlet by above-mentioned catalyst layer.And this carbon monoxide removal device constitutes, thereby by utilizing the temperature of well heater from the above-mentioned reaction tubes of the above-mentioned reaction tubes may command of indirect heating.
Be connected with the pipe arrangement of stainless steel in the upstream of above-mentioned carbon monoxide removal device one side, above-mentioned reaction analog gas is supplied with to above-mentioned carbon monoxide removal device from this pipe arrangement.
As above-mentioned reaction analog gas, adopt the mol ratio ([O be equivalent in the exit gas of above-mentioned CO (carbon monoxide converter) converter mixing air and make oxygen/carbon monoxide 2]/[CO]) be the gas (, adding water vapour so that the water vapor concentration of wet gas is the reaction analog gas of 5% (being equivalent to 33 ℃ of dew points) in the mixed gas that divides with the 1000Nml/ of hydrogen balance) of 1.5 composition to carbon monoxide 0.5%, methane 0.5%, carbonic acid gas 20.9%, oxygen 0.75%, nitrogen 3.0%.In addition, Ci Shi space velocity (GHSV) is 7,500/ hours (moisture-free basis).
The above-mentioned reaction analog gas that is heated to 80 ℃ is supplied with above-mentioned each pipe arrangement with the above-mentioned reaction analog gas that is heated to 140 ℃, the intravital top temperature of above-mentioned basket of the above-mentioned carbon monoxide removal device that will be connected with each aforementioned pipe arrangement is adjusted into 90 ℃, carries out the removal of carbon monoxide.In addition, the top temperature of above-mentioned catalyst layer becomes 110 ℃.At this moment, above-mentioned reaction analog gas (exit gas) is gathered in outlet (spout) at above-mentioned basket ageingly, with the carbon monoxide concentration (moisture-free basis) in the above-mentioned exit gas of gas chromatograph measurement device that is equipped with thermal conductivity detector (TCD) and hydrogen flame ionization activity detector (FID).This measuring result is shown in Fig. 2.In addition, the detection lower limit of the carbon monoxide that carries out of above-mentioned gas chromatograph device is 1ppm.
140 ℃ gas is being supplied with in the carbon monoxide removal device of above-mentioned pipe arrangement, soon, the carbon monoxide concentration of above-mentioned exit gas begins to rise after the operation beginning, after 100 hours, surpasses 10ppm from the operation beginning.And 80 ℃ gas is supplied with the carbon monoxide concentration of above-mentioned exit gas of the carbon monoxide removal device of above-mentioned pipe arrangement, low during than another carbon monoxide removal device operation beginning, even begin through about 100 hours from operation, the carbon monoxide concentration in the above-mentioned exit gas also has only about 2ppm.
Here, the above-mentioned carbon monoxide removal catalyzer that activity is descended takes out from above-mentioned reaction tubes, utilize the atom in the above-mentioned carbon monoxide removal catalyst surface of above-mentioned EPMA (electron probe microanalyzer) research to distribute, verified the existence that iron is arranged on its surface.And in having kept highly active carbon monoxide removal catalyst surface, promptly using the atom on EPMA research surface to distribute, iron is also detecting below the boundary.
Therefore, think to remain on below 100 ℃ that the inhibition ferrous components flows in the above-mentioned carbon monoxide removal device, thereby can keep the greater activity of above-mentioned carbon monoxide removal catalyzer by the temperature that will import to the above-mentioned reactant gases in the above-mentioned carbon monoxide removal device.
(embodiment 2)
Make 3 except the diameter of filling 8cc to the leading portion of catalyst layer is the spherical gama-alumina (alumina balls) of 2～4mm, the carbon monoxide removal device that all the other are identical with the carbon monoxide removal device structure of above-mentioned the foregoing description 1, to form identical gas heating to 140 ℃ with the reactant gases that adopts among the embodiment 1, supply with above-mentioned each pipe arrangement.The basket temperature of these 3 kinds of carbon monoxide removal devices is remained 100,120,140 ℃ respectively, and the carbon monoxide concentration (moisture-free basis) in the above-mentioned exit gas the when top temperature of above-mentioned catalyst layer is become 120,140,160 ℃ is shown in Fig. 3.
As shown in Figure 3, be heated to 140 ℃ of temperature province of the above-mentioned iron carbonyl of easy generation at the reaction analog gas of the exit gas that will simulate above-mentioned CO (carbon monoxide converter) converter, and make it by in the above-mentioned carbon monoxide removal device in the above-mentioned pipe arrangement, the top temperature of above-mentioned catalyst layer is near the carbon monoxide removal device 120 ℃ because respectively in continuous operation beginning after hundreds of hours, the carbon monoxide removal ability drop is so distinguished and be unsuitable for long-time running.
And it is 120,140 ℃ in the temperature that makes above-mentioned basket, promptly, the top temperature that makes above-mentioned catalyst layer is near 140～160 ℃ the carbon monoxide removal device, even surpass 1000 hours, also can continue to keep the carbon monoxide concentration of above-mentioned exit gas is the following higher carbon monoxide removal ability of 4ppm.Particularly, in the temperature that makes above-mentioned basket is 140 ℃, promptly, the top temperature that makes above-mentioned catalyst layer is near 160 ℃ the carbon monoxide removal device, even surpass 2500 hours, also can continue to keep the carbon monoxide concentration of above-mentioned exit gas is the following higher carbon monoxide removal ability of 4ppm.In the temperature that makes above-mentioned basket is 160 ℃, that is, the top temperature that makes above-mentioned catalyst layer is to have obtained such result too near 180 ℃ the carbon monoxide removal device.
Here, from above-mentioned reaction tubes taking-up catalyzer separately, the atom that utilizes above-mentioned EPMA to study in the surface of above-mentioned carbon monoxide removal catalyzer distributes, and the result has verified at three kinds of catalyzer and has been filled on the local surfaces of the alumina balls in the leading portion has iron to exist.Therefore, even learn 140 ℃ the temperature that the temperature in iron cpd of carbon monoxide removal device flows into easily,, above-mentioned carbon monoxide removal life of catalyst is prolonged by changing the top temperature of above-mentioned catalyst layer.
Therefore, think and remain 130～180 ℃ by top temperature with the above-mentioned catalyst layer of above-mentioned carbon monoxide removal device, control the attachment state of iron, thereby keep above-mentioned carbon monoxide removal activity of such catalysts for a long time to above-mentioned carbon monoxide removal catalyst surface.
Below, further other embodiment of the present invention is described based on accompanying drawing.
Fig. 4 represents to have the fuel reforming system of carbon monoxide removal device of the present invention.This fuel reforming system is to be original fuel with Sweet natural gas (domestic gas), manufacturing is the system of the modification gas of main component for the hydrogen in polymer electrolyte fuel cell, the original fuel of supplying with above-mentioned original fuel supply be 1, the devulcanizer 2 of interior dress desulfurization catalyst, the modifier (fuel modifying device) 4 of interior dress modifying catalyst, the CO (carbon monoxide converter) converter 5 of interior dress carbon monoxide transformation catalyst and carbon monoxide removal device 6 involved in the present invention connect by pipe arrangement respectively according to above-mentioned record order.The modification gas of upgrading is supplied to polymer electrolyte fuel cell 7 by these devices.
Supply with when being 1 Sweet natural gas of supplying with by above-mentioned original fuel, contact with above-mentioned desulfurization catalyst and remove sulfur component by above-mentioned devulcanizer 2.With after the water vapour of being supplied with by water vapour producer 3 mixes, be transported in the above-mentioned modifier 4 then, here contact with above-mentioned modifying catalyst, the hydrocarbon polymers such as methane in the above-mentioned Sweet natural gas are hydrogen, carbon monoxide, carbonic acid gas by upgrading.Although the modification gas of Huo Deing is main component with hydrogen like this, owing to contain the carbon monoxide of the secondary resultant of conduct of tens %, if directly supply with, the electrode of then above-mentioned polymer electrolyte fuel cell 7 produces poisoning of catalyst.So, about 200 ℃, move above-mentioned CO (carbon monoxide converter) converter 5 down, above-mentioned modification gas is contacted with above-mentioned carbon monoxide transformation catalyst, be carbonic acid gas with carbon monodixe conversion, carbon monoxide concentration is reduced to 0.5～1%.
And, after carbon monoxide concentration being reduced to 0.5～1% above-mentioned modification gas and the air of being supplied with by oxygenant feeder 9 (oxygen is as the oxygenant effect) mixing, be directed in the carbon monoxide removal device 6 involved in the present invention by above-mentioned pipe arrangement as reactant gases.
This carbon monoxide removal device 6 is by utilizing nonferrous material to constitute local or whole inner-wall surface of the above-mentioned modification gas circulation path of above-mentioned catalyzer accommodation section and upstream one side thereof, prevent iron and iron cpd intravital the spilling of above-mentioned basket, and prevent the carbon monoxide removal device of the iron catalyst poisoning of above-mentioned carbon monoxide removal catalyzer.In order to reach these purposes, for example, both can be by glass such as copper based material, pottery, silica glass such as phosphorized copper brass, the character shape is difficult to change in the operating temperature of above-mentioned carbon monoxide removal device 6 synthetic resins formations such as (teflon resin, PEEK resins), perhaps also can cover with stainless steel etc. by above-mentioned nonferrous material be the inner-wall surface of the above-mentioned basket of mother metal.And, there is no need to cover whole above-mentioned basket by above-mentioned nonferrous material, even only cover (plating) inner wall surface that above-mentioned mixed gas, above-mentioned reactant gases contacted, also can prevent spilling of iron and iron cpd by above-mentioned nonferrous material.
(for example in basket, be filled with above-mentioned carbon monoxide removal catalyzer, on carriers such as alumina balls, carry the material of precious metals such as ruthenium, platinum, rhodium, palladium), above-mentioned reactant gases contacts above-mentioned carbon monoxide removal catalyzer, and carbon monoxide is become carbonic acid gas by the oxygen oxidation.Carbon monoxide concentration is cut to the following above-mentioned modification gas of 10ppm and supplies with above-mentioned polymer electrolyte fuel cell 7 like this, the most at last.
And, because above-mentioned carbon monoxide removal device moves above-mentioned catalyzer down at about 80～200 ℃ usually, be used for the thermoregulation mechanism 8 of above-mentioned basket temperature regulation in this scope so have.This thermoregulation mechanism 8 has the water cooler that is used for heating the well heater of above-mentioned basket or is used for cooling off thermal source and above-mentioned basket.
And, if operating to, above-mentioned carbon monoxide removal device make above-mentioned catalyst layer become 180 ℃, then suppress the carrying out of side reaction, thereby can suppress to consume the hydrogen in the above-mentioned reactant gases.
And carbon monoxide removal device involved in the present invention and the fuel reforming system with this carbon monoxide removal device are not limited to the method for oxidation removal carbon monoxide, also can be used for the carbon monoxide methanation removal method that carbon monoxide is removed in methanation.At this moment, in the above-mentioned carbon monoxide removal device that holds above-mentioned catalyzer, do not import oxygenant, under the temperature about 200 ℃, move.By like this, carbon monoxide and H-H reaction generate methane, can remove carbon monoxide.
Embodiment
Below the test of the performance that is used for verifying above-mentioned carbon monoxide removal device involved in the present invention is described.
With diameter is that the spherical gamma-aluminium oxide carrier of 2～4mm is immersed in the ruthenium trichloride aqueous solution, makes it to carry ruthenium by pickling process.After being dried, be immersed in the aqueous sodium carbonate, and make the immobilization on above-mentioned carrier of above-mentioned ruthenium, and washing, drying, precursor obtained.This precursor is immersed in the hydrazine solution ruthenium of the above-mentioned preceding surface of reduction, washes once again, make it dry down and obtain Ru/ aluminium oxide catalyst (B) at 105 ℃.The concentration of the ruthenium in the Ru/ aluminium oxide catalyst that is obtained is 0.5 weight %, and average largest diameter is 7.1nm.
(embodiment 3)
To be filled into as Ru/ aluminium oxide catalyst (B) 8cc of carbon monoxide removal catalyzer in the reaction tubes (basket) of quartzy system, form the catalysing area that has formed catalyst layer on it, make the carbon monoxide removal device.The reaction analog gas that imports to basket inside from the inlet of this carbon monoxide removal device is released to outside the basket from above-mentioned outlet by above-mentioned catalysing area.And this carbon monoxide removal device constitutes, and has the thermoregulation mechanism of well heater, thereby and by utilizing the temperature of well heater from the above-mentioned reaction tubes of the above-mentioned reaction tubes may command of indirect heating.In addition, be used for supplying with the quartz system vapor lamp of water vapour when the leading portion of above-mentioned reaction tubes is provided with modulation reaction analog gas described later, this vapor lamp is connected by teflon resin system pipe arrangement with above-mentioned reaction tubes.
Import sensitization gas (hydrogen 6%, nitrogen 94%) to this carbon monoxide removal device with the flow that 1000Nml/ divides on one side, by said temperature regulating mechanism make reaction tube temperature intensification reach 220 ℃ on one side, and keep carrying out in 1.5 hours pre-treatment down at 220 ℃.This pre-treatment is when above-mentioned reaction analog gas carries out following formal processing at low temperatures, is used for initial activity is maintained the necessary processing of higher level.
Afterwards, after making the temperature decline of above-mentioned reaction tubes, making space velocity (GHSV) is 7, in above-mentioned reaction tubes, imported the reaction analog gas in 500/ hour (moisture-free basis), and the temperature of controlling above-mentioned reaction tubes to make the top temperature of above-mentioned catalyst layer be 151 ℃, carry out the removal reaction (the formal processing) of carbon monoxide.As above-mentioned reaction analog gas, adopt to be equivalent in the exit gas of above-mentioned CO (carbon monoxide converter) converter mixing air and to make oxygen (O 2) with respect to the mol ratio of carbon monoxide (CO) gas (to carbon monoxide 0.5%, methane 0.5%, carbonic acid gas 20.9%, oxygen 0.8%, nitrogen 3.1%, all the other are for adding water vapour so that the water vapor concentration in the wet gas is 20% gas in the mixed gas of hydrogen (1000Nml/ branch)) of 1.6 composition.
In addition, the temperature that makes above-mentioned vapor lamp and above-mentioned pipe arrangement is 120 ℃, so that the temperature of the inlet gas of above-mentioned reaction tubes is 120 ℃.
(comparative example 2)
Employing has except the above-mentioned pipe arrangement of making above-mentioned reaction tubes, above-mentioned vapor lamp, the above-mentioned reaction tubes of connection and above-mentioned vapor lamp with the SUS316 steel, the carbon monoxide removal device of the structure that all the other are identical with the foregoing description 3 utilizes the selective oxidation reaction of carrying out carbon monoxide with embodiment 3 identical operations.
(result)
In the related carbon monoxide removal device of embodiment 3, at the beginning of the operation beginning, the carbon monoxide concentration in the exit gas (moisture-free basis) is suppressed in below the 10ppm, and in service continuously at 96 hours continues to keep this level.
And in the related carbon monoxide removal device of above-mentioned comparative example 2, during the operation beginning, the carbon monoxide concentration in the exit gas (moisture-free basis) be below the 10ppm, but rising gradually later on, after 95 hours, carbon monoxide concentration reaches below the 14ppm.
And, finish back (after moving about 100 hours) in the selective oxidation of carbon monoxide reaction and take out the foregoing description 3 employed carbon monoxide removal catalyzer, the result who utilizes EPMA to carry out surface analysis is that the concentration that exists of iron atom on the surface of above-mentioned carbon monoxide removal catalyzer is detecting below the boundary.And utilize EPMA to be to the result that employed Ru/ aluminium oxide catalyst in the comparative example 2 carries out surface analysis, and on this measurement point, detecting iron atom, the surface local that has obtained above-mentioned carbon monoxide removal catalyzer is by the result of iron or iron cpd covering.
Verified in above-mentioned carbon monoxide removal activity of such catalysts by these results and to have reduced and aforementioned iron and iron cpd have correlationship between the adhering to of above-mentioned carbon monoxide removal catalyst surface, carbon monoxide removal device utilization involved in the present invention is made of and the local of the contacted zone of above-mentioned carbon monoxide removal catalyzer of above-mentioned basket or whole inner-wall surfaces nonferrous material, and, above-mentioned carbon monoxide removal activity of such catalysts can be maintained higher level by iron and iron cpd are not contacted with above-mentioned carbon monoxide removal catalyzer.
Below, based on accompanying drawing another form of implementation of the present invention is described.
Fig. 5 represents to have the fuel reforming system of carbon monoxide removal device involved in the present invention.This fuel reforming system is to be original fuel with Sweet natural gas (domestic gas), manufacturing is the system of the modification gas of main component for the hydrogen in polymer electrolyte fuel cell, the original fuel of supplying with above-mentioned original fuel supply be 1, the devulcanizer 2 of interior dress desulfurization catalyst, the modifier 4 of interior dress modifying catalyst, the CO (carbon monoxide converter) converter 5 of interior dress carbon monoxide transformation catalyst and carbon monoxide removal device 6 involved in the present invention connect by pipe arrangement respectively according to above-mentioned record order.The modification gas of upgrading is supplied to polymer electrolyte fuel cell 7 by these devices.
Supply with when being 1 Sweet natural gas that imports by above-mentioned original fuel, contact with above-mentioned desulfurization catalyst and remove sulfur component by above-mentioned devulcanizer 2.With after the water vapour of being supplied with by water vapour producer 3 mixes, be transported in the above-mentioned modifier 4 then, here contact with above-mentioned modifying catalyst, the hydrocarbon polymers such as methane in the above-mentioned Sweet natural gas are hydrogen, carbon monoxide, carbonic acid gas by upgrading.Although the modification gas of Huo Deing is main component with hydrogen like this, owing to contain the carbon monoxide of the secondary resultant of conduct of tens %, if directly supply with, the electrode of then above-mentioned polymer electrolyte fuel cell 7 produces poisoning of catalyst.So, about 200 ℃, move above-mentioned CO (carbon monoxide converter) converter 5 down, above-mentioned modification gas is contacted with above-mentioned carbon monoxide transformation catalyst, be carbonic acid gas with carbon monodixe conversion, carbon monoxide concentration is reduced to 0.5～1%.
And, after carbon monoxide concentration being reduced to 0.5～1% above-mentioned modification gas and the air of being supplied with by oxygenant feeder 9 (oxygen is as the oxygenant effect) mixing, be directed in the carbon monoxide removal device 6 involved in the present invention as reactant gases.
This carbon monoxide removal device 6 constitutes, in basket, be provided with trap portion 6a and by above-mentioned carbon monoxide removal catalyzer (for example in its downstream one side, on carriers such as alumina balls, carry the material of precious metals such as ruthenium, platinum, rhodium, palladium) the catalysing area 6b that constitutes, wherein, trap portion 6a be provided with collection from by select the group that iron and iron cpd constituted at least a more than material the iron collecting mechanism (for example, porous plastids such as aluminum oxide), the reactant gases by above-mentioned trap portion 6a arrives above-mentioned catalysing area 6b.
Carbon monoxide concentration being reduced to 0.5～1% above-mentioned reactant gases at first flows among the above-mentioned trap portion 6a, here, from by select the group that iron and iron cpd constituted at least a more than material captured mechanism traps by above-mentioned iron, from concentration reduction by at least a above material of selecting the group that iron and iron cpd constituted.Then, from by select the group that iron and iron cpd constituted at least a more than the above-mentioned reactant gases that reduced of the concentration of material flow among the above-mentioned catalysing area 6b, by contacting with above-mentioned catalyzer, carbon monoxide is become carbonic acid gas by the oxygen oxidation.Like this, the carbon monoxide concentration in the final above-mentioned reactant gases (modification gas) is cut to below the 10ppm, and is supplied to above-mentioned polymer electrolyte fuel cell 7.
And, because above-mentioned carbon monoxide removal device moves above-mentioned catalyzer down at about 80～200 ℃ usually, be used for the thermoregulation mechanism 8 of above-mentioned basket temperature regulation in this scope so have.This thermoregulation mechanism 8 has the water cooler that is used for heating the well heater of above-mentioned basket and is used for cooling off above-mentioned basket.And, when above-mentioned iron captures mechanism when being aluminum oxide, since higher 80～200 ℃ of following iron trapping ability, utilize this thermoregulation mechanism 8 that temperature regulation is become identical with catalyzer so be preferably.
And, if operating to, above-mentioned carbon monoxide removal device make above-mentioned catalyst layer become 180 ℃, then suppress the carrying out of side reaction, thereby can suppress to consume the hydrogen in the above-mentioned reactant gases.
And, in order to prevent spilling of iron and iron cpd, in this form of implementation, also can constitute the inner-wall surface of above-mentioned at least catalysing area of the above-mentioned basket of above-mentioned carbon monoxide removal device 6 by nonferrous material except above-mentioned iron and iron cpd.And, by from above-mentioned modifier 4 to the position of above-mentioned carbon monoxide removal device 6, be formed in mobile in the above-mentioned fuel reforming system by nonferrous material and contain the gas flowing path that mixed gas contacted local of hydrogen and carbon monoxide or whole inner-wall surfaces, can prevent to spill iron and iron cpd from above-mentioned inner-wall surface.Flow into above-mentioned carbon monoxide removal device 6 from this field if can suppress iron and iron cpd, then can further suppress iron and iron cpd to the adhering to of above-mentioned carbon monoxide removal catalyzer, thereby suppress the poisoning of catalyst of above-mentioned carbon monoxide removal catalyzer significantly.Here, in order to suppress spilling of above-mentioned iron and iron cpd as much as possible, be preferably the whole inner-wall surface that constitutes the above-mentioned gas circulation path with above-mentioned nonferrous material, but consider the difficulty cost of execution operation etc., also can constitute local above-mentioned gas circulation path with above-mentioned nonferrous material in emphasis ground.
This structure, for example, can be at position from above-mentioned modifier 4 to above-mentioned carbon monoxide removal device 6, local or the whole inner-wall surface of the gas flow path that mixed gas was contacted that contains mobile hydrogen and carbon monoxide in system is carried out plating and obtain with nonferrous material, perhaps also can be in that constitute the parts that have this part with nonferrous material whole and obtain.More particularly, can connect pipe arrangement local of the CO (carbon monoxide converter) converter 5 that above-mentioned carbon monoxide removal device 6 and its leading portion had or whole inner-wall surfaces, perhaps constitute this pipe arrangement integral body with nonferrous material with the nonferrous material plating.
And, poison if prevent to comprise the iron catalyst of the above-mentioned carbon monoxide removal catalyzer in the fuel reforming system of known configurations of carbon monoxide removal device, at the leading portion of the inlet of above-mentioned carbon monoxide removal device strainer is set and gets final product, wherein this strainer be provided with possess can capture from by select the group that iron and iron cpd constituted at least a more than the trap portion of iron collecting mechanism of material.According to this structure, since from by at least a above material of selecting in the group that iron and iron cpd constituted that is contained the above-mentioned fuel gas by above-mentioned iron capture mechanism traps, can not flow out to its downstream, so can prevent from by select the group that iron and iron cpd constituted at least a more than material flow into before in the carbon monoxide removal device of structure, therefore can prevent the poisoning of catalyst of above-mentioned carbon monoxide removal catalyzer, its activity is maintained higher level.
And carbon monoxide removal device involved in the present invention and the fuel reforming system with this carbon monoxide removal device are not limited to the method for oxidation removal carbon monoxide, also can be used for the carbon monoxide methanation removal method that carbon monoxide is removed in methanation.At this moment, in the above-mentioned carbon monoxide removal device that holds above-mentioned catalyzer, do not import oxygenant, under the temperature about 200 ℃, move.By like this, carbon monoxide and H-H reaction generate methane, can remove carbon monoxide.
Embodiment
Below, describe to the test of the performance that is used for verifying above-mentioned carbon monoxide removal device involved in the present invention.
(embodiment 4)
As shown in Figure 6, to be filled into downstream (outlet) side that is provided with the SUS system reaction tubes 61 of the thermoregulation mechanism 62 that possesses well heater and water cooler in its periphery as Ru/ aluminium oxide catalyst (B) 8cc of carbon monoxide removal catalyzer, form catalysing area 6b, and, capture the alumina balls of mechanism what the upstream (inlet) of the above-mentioned catalysing area 6b of above-mentioned reaction tubes 61 side was filled 8cc as iron, form trap portion 6a, make 6 carbon monoxide removal devices.In addition, iron and many iron cpds are caught by above-mentioned alumina balls by absorption.
Import to the reaction analog gas of above-mentioned reaction tubes 61 inside by behind the above-mentioned trap portion 6a, from the inlet of this carbon monoxide removal device 6 by above-mentioned catalysing area 6b, outside above-mentioned outlet is released to above-mentioned reaction tubes 61.And the temperature in this carbon monoxide removal device 6 is by being provided with the measurement point 63a that measures the temperature of above-mentioned reaction analog gas in the inlet portion of above-mentioned carbon monoxide removal device 6, and thermocouple 63 monitoring of measurement point 63b of measuring the temperature of above-mentioned trap portion 6a and above-mentioned catalysing area 6b.In addition, these positions are variable.Said temperature regulating mechanism 62 constitutes and can cool off above-mentioned reaction tubes 61 according to this monitored results heating, thereby controls the temperature of above-mentioned reaction tubes 61.In addition, be used for supplying with the SUS system vapor lamp (omitting diagram) of water vapour when the leading portion of above-mentioned reaction tubes 61 is provided with modulation reaction analog gas described later, this vapor lamp is made pipe arrangement with above-mentioned reaction tubes by SUS and is connected.
Import sensitization gas (hydrogen 6%, nitrogen 94%) to this carbon monoxide removal device with the flow that 1000Nml/ divides on one side, by said temperature regulating mechanism make reaction tube temperature intensification reach 220 ℃ on one side, and keep carrying out in 1.5 hours pre-treatment down at 220 ℃.This pre-treatment is when above-mentioned reaction analog gas is carried out following formal processing under low temperature (120 ℃), is used for initial activity is maintained the necessary processing of higher level.
Afterwards, the temperature of above-mentioned reaction tubes is dropped to 120 ℃, also remains at that under 120 ℃, the temperature that makes above-mentioned inlet gas is that 120 ℃, space velocity (GHSV) are to import the reaction analog gas in 7500/ hour in above-mentioned reaction tubes (moisture-free basis), carries out the removal reaction (the formal processing) of carbon monoxide.As above-mentioned reaction analog gas, adopt to be equivalent in the exit gas of above-mentioned CO (carbon monoxide converter) converter mixing air and to make oxygen (O 2) with respect to the mol ratio of carbon monoxide (CO) gas (to carbon monoxide 0.5%, methane 0.5%, carbonic acid gas 20.9%, oxygen 0.8%, nitrogen 3.1%, all the other are for adding water vapour so that the water vapor concentration in the wet gas is 20% gas in the mixed gas of hydrogen (1000Nml/ branch)) of 1.6 composition.
In addition, the top temperature of Ci Shi above-mentioned catalyst layer is 147 ℃.
(comparative example 3)
Employing is except filling the alumina balls as iron capture mechanism, all the other have the carbon monoxide removal device identical with the foregoing description 4 structures, and by except using when the pre-treatment above-mentioned reaction analog gas to replace the above-mentioned sensitization gas, all the other and the foregoing description 4 identical operations are carried out the removal reaction of carbon monoxide.
The passing of the carbon monoxide concentration (moisture-free basis) in the modification gas (exit gas) that will be obtained by the carbon monoxide removal reaction of the foregoing description 4 and comparative example 3 is shown in Fig. 7.
In the related carbon monoxide removal device of embodiment 4, at the beginning of the operation beginning, the carbon monoxide concentration in the exit gas is suppressed in below the 10ppm, and the continuation continuous in service at 100 hours keeps this level.And in the related carbon monoxide removal device of above-mentioned comparative example, from operation beginning up to through 40 hours, the not enough 10ppm of the carbon monoxide concentration in the exit gas, but carbon monoxide increases gradually later on, reaches 40ppm during through 100 hours.
And, selective oxidation reaction at carbon monoxide finishes back (after moving 100 hours) taking-up the foregoing description 4 employed catalyzer, and utilizing EPMA to carry out surface analysis, the result is that the concentration that exists of iron atom on the surface of above-mentioned catalyzer is detecting below the boundary.And utilize EPMA to be to the result that employed Ru/ aluminium oxide catalyst in the comparative example 3 carries out surface analysis, on its measurement point, detect the iron atom of 16.7 weight %.
And, to take out when being used as above-mentioned iron in the foregoing description 4 and capturing the alumina balls of mechanism, there is tawny variable color part on the surface that is found in above-mentioned alumina balls.This part is carried out surface analysis with EPMA, learnt that iron atom exists.
Verified in above-mentioned activity of such catalysts by these results and to have reduced and aforementioned iron or iron cpd have correlationship between the adhering to of above-mentioned removal catalyst surface, carbon monoxide removal device involved in the present invention by be provided with above-mentioned trapping layer stop from by select the group that iron and iron cpd constituted at least a more than material flow into above-mentioned catalyst layer, above-mentioned activity of such catalysts can be maintained higher level.
In addition, in above-mentioned any form of implementation, when enforcement was of the present invention, desulfurization catalyst, modifying catalyst, carbon monoxide transformation catalyst used in the above-mentioned fuel reforming system can use known material and need not limit its kind.And, as above-mentioned method for modifying, be not limited to use the water vapour upgrading, also can adopt partial combustion process, thus the carbon monoxide that is used to remove thus and is produced.And carbon monoxide removal device involved in the present invention can be used in the carbon monoxide that is contained in the fuel gas that upgrading obtained such as removing methyl alcohol and raw gasline.

Claims (7)

1, a kind of carbon monoxide removal device constitutes in the catalysing area that the carbon monoxide removal catalyzer that will be contained the carbon monoxide in the mixed gas of hydrogen and carbon monoxide by removal constitutes and is loaded in the basket, and makes above-mentioned mixed gas by above-mentioned catalysing area,
Be provided with the trap portion that possesses iron capture mechanism in the upstream of above-mentioned catalysing area one side, wherein iron capture mechanism traps contains attached to the material that produces the iron of poisoning of catalyst on the above-mentioned carbon monoxide removal catalyzer.
2, carbon monoxide removal device as claimed in claim 1 is characterized in that, is loaded in the above-mentioned basket in the above-mentioned trap portion.
3, carbon monoxide removal device as claimed in claim 1 is characterized in that, above-mentioned iron captures mechanism and constitutes by capturing the porous plastid that contains attached to the material of the iron of generation poisoning of catalyst on the above-mentioned carbon monoxide removal catalyzer.
4, carbon monoxide removal device as claimed in claim 3 is characterized in that, above-mentioned porous plastid is to be the porous plastid of main raw with the aluminum oxide.
5, carbon monoxide removal device as claimed in claim 1 is characterized in that, having can be with the thermoregulation mechanism of above-mentioned trap portion insulation under 80 ℃～200 ℃.
6, a kind of strainer, be to be used for subtend to have and carry out pretreated strainer with containing the above-mentioned mixed gas that imports in the carbon monoxide removal device as claimed in claim 1 of carbon monoxide removal catalyzer of the carbon monoxide removal in the mixed gas of hydrogen and carbon monoxide
And be provided with the trap portion that possesses iron capture mechanism, wherein iron captures mechanism and can capture the material that contains attached to producing the iron of poisoning of catalyst on the above-mentioned carbon monoxide removal catalyzer.
7, a kind of carbon monoxide removal method, thus make the carbon monoxide in the mixed gas that contains hydrogen and carbon monoxide contact the removal carbon monoxide with the carbon monoxide removal catalyzer,
To above-mentioned mixed gas be contacted with above-mentioned carbon monoxide removal catalyzer from by after sneaking into containing the material that produces the iron of poisoning of catalyst attached to above-mentioned carbon monoxide removal catalyzer and remove in advance the above-mentioned mixed gas.
CNB2005100696201A 2001-03-28 2002-03-25 Carbon monoxide removing device, filter, and method for removing carbon monoxide by using them Expired - Lifetime CN100344526C (en)

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