KR101854941B1 - Highly active water gas shift catalyst, preparation process and use thereof - Google Patents

Abstract

The present invention relates to a highly active water gas shift catalyst and a process for producing the same, and also to a process for converting a gas mixture comprising at least carbon monoxide and water into hydrogen and carbon dioxide over a wide temperature range using the catalyst.

Description

HIGHLY ACTIVE WATER GAS SHIFT CATALYST, PREPARATION PROCESS AND USE THEREOF BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to a highly active aqueous gas catalyst and a process for preparing it and also to a process for converting a gas mixture comprising at least carbon monoxide and water into hydrogen and carbon dioxide over a wide temperature range using the catalyst.

In a fuel cell, electrical energy is obtained using a chemical reaction. Most fuel cells utilize the reaction of the reducing and oxidizing streams, usually hydrogen and oxygen. In order to be able to use the fuel in the fuel cell, this must be converted in advance to the hydrogen-rich stream.

The preliminary treatment of the fuel is performed in three stages:

The fuel is first reformed and dissociated into CO and H ₂ in this way. Followed by a water gas conversion step in which the produced CO is reacted with water in a temperature dependent equilibrium reaction to produce CO ₂ and H ₂ :

CO + H ₂ O? CO ₂ + H ₂

In this equilibrium, the further the H ₂ and CO ₂ side, the lower the temperature. Usually a CO refining step is followed.

The high concentration of CO (> 50 ppm) damages the anode of the fuel cell. Therefore, the CO content must be minimized prior to the actual cell. This is carried out in the water gas conversion step and also in the CO micro-purification step. The water gas conversion step usually occurs at two temperature steps. The reaction at a temperature within the range of 150 to 280 ° C is referred to as a low temperature conversion reaction (LTS). The LTS is usually carried out catalytically using a Cu / Zn oxide catalyst. Within the range of 280 to 550 캜, the reaction is referred to as a high temperature conversion reaction (HTS). This is traditionally performed on Fe / Cr catalysts. This reaction can also be promoted by Mo, Ni and further elements. Precious metals on cerium oxide have also been described numerous times as catalysts for this reaction.

Conversion the desired product increases the rate of H ₂ in the fuel stream, as well as to induce the removal of catalyst poisons (catalyst poison) CO. It is therefore important that the catalyst for HTS promotes the production of H ₂ from CO and H ₂ O but does not promote the elimination or depletion of the desired product H ₂ . These reactions include, among other things, methanation, which can be observed on noble metal catalysts at elevated temperatures, and even above 350 ° C. This involves the following two reaction pathways:

CO + 3 H _{2 -} > CH ₄ + H ₂ O

CO ₂ + 4 H ₂ → CH ₄ + 2 H ₂ O

All of the two reactions are then consume the desired product H ₂ and thus reduce the hydrogen yield.

Reactions and catalysts which provide a very high yield of hydrogen and exhibit a very low tendency to methanation are known from the prior art.

EP 1 571 125 A2 discloses a catalyst for separating carbon monoxide from hydrogen gas. This includes oxide support materials including zirconium dioxide, titanium dioxide, aluminum oxide, silicon dioxide, silicon dioxide-aluminum oxide, zeolites, and cerium oxide. Platinum is present as a catalytically active metal. Further, alkali metals such as lithium, sodium, potassium, rubidium or cesium can be present as additional inorganic compounds, thereby improving the activity of the catalyst for removing carbon monoxide by conversion to carbon dioxide in the water gas shift reaction. The catalytically active metal is present in the catalyst in an amount of 2% by weight, according to EP 1 571 125 A2.

WO 2005/072871 A1 discloses a catalyst for an aqueous gas conversion reaction comprising metallic particles and metal oxide particles. Suitable metal oxides are, for example, cerium oxide, titanium dioxide, iron oxide, manganese oxide or zinc oxide. Suitable metal particles are, for example, gold or platinum and are present in an amount of from 0.5 to 25% by weight, based on the oxide material.

US 2006/0002848 A1 discloses a catalyst having a support material composed of, for example, aluminum oxide, titanium dioxide, silicon dioxide, zirconium dioxide or a combination thereof. Further, metals selected from alkali or alkaline earth metals and also lead, bismuth, polonium, manganese, titanium-vanadium-chromium, manganese iron, nickel or cobalt may be present. Existing catalytically active metals are, for example, platinum, palladium, copper, rhodium, and the like.

EP 1 908 517 A1 discloses a catalyst for the conversion of H ₂ O / carbon monoxide to hydrogen and the use of this catalyst for increasing the hydrogen concentration in the stream used for fuel cell supply. The catalyst may be a promoter from a group of active phases and rare earths, such as lanthanum or cerium, containing active Group VIII elements on a support material comprising aluminum oxide, silicon dioxide, zirconium dioxide or mixtures thereof, ≪ / RTI >

 US 2005/0207958 A1 discloses a method for reducing the amount of carbon monoxide in a water gas shift reactor without the formation of methane. Catalysts with cerium oxide and zirconium oxide or support materials based on cerium oxide and lanthanum oxide are used for this purpose. As a promoter to avoid methanation, use is made of copper, manganese, iron compounds or a combination. Additional promoters may be alkaline or alkaline earth metals. The amount of platinum present in the catalyst is at least 1% by weight.

US 2005/0191224 A1 discloses a catalyst for separating carbon monoxide from hydrogen gas. The catalyst used for this purpose has a support composed of a metal oxide and has a platinum component and an alkali metal applied to the support. According to this document, zirconium dioxide, titanium dioxide, aluminum oxide, silicon dioxide, silicon dioxide-aluminum oxide, zeolite or cerium oxide, for example, are suitable as support materials.

It is therefore an object of the present invention to find an active catalyst which can be used over a wide temperature range and which scarcely forms methane. The catalyst should ideally have a low precious metal input.

The catalyst comprising the noble metal is prepared by impregnating the shaped support material with a noble metal component metal salt solution or by impregnating the support powder and subsequently molding it. It is therefore a further object of the present invention to provide a method of depositing a very small amount of noble metal component in a location where access to the reaction is difficult.

This object is achieved according to the present invention by providing on a support material at least one noble metal in an amount of 0.001 to 1.10% by weight, based on the total weight of the catalyst, of at least one alkali metal and / or alkaline earth metal and at least one of Fe, Cr, Cu, Zn And mixtures thereof. ≪ Desc / Clms Page number 2 >

The invention further comprises a process for preparing such a catalyst and also a process for converting a gas mixture comprising at least carbon monoxide and water into hydrogen and carbon dioxide using such a catalyst.

Embodiments of the invention can be ascertained in the claims, specification and examples. Needless to say, the above-mentioned features of the subject matter of the present invention and the features to be described hereinafter can be used in combination in each case described, as well as in other combinations not departing from the scope of the invention.

Surprisingly, it has been found that, on the support material, at least one noble metal in an amount of from 0.001 to 1.10% by weight, based on the total weight of the catalyst, of at least one alkali metal and / or alkaline earth metal and a mixture of Fe, Cr, Cu, When a supported noble metal catalyst having at least one dopant selected from the group is used, the water gas shift reaction can be successfully carried out in a wide temperature range and the undesirable methanation can be carried out at a high temperature, do. This is precisely the combination of features of the catalyst of the present invention which provide the mentioned advantages.

For example, conversion catalysts containing noble metals by the addition of sodium cause an increased tendency of methanation and an increase in the combined conversion activity. For example, the addition of iron leads to a reduced tendency of methanation and a decrease in the combined conversion activity. For this reason, the optimum should be found between the addition of iron and an alkali metal, for example, both iron and alkali metals provide satisfactory conversion activity and inhibit the tendency of methanation formation to a sufficient amount.

The catalysts of the present invention may comprise on the support material a mixture of at least one noble metal selected from the group consisting of Fe, Cr, Cu, Zn, and mixtures thereof in amounts specified in each case, at least one noble metal and at least one alkali metal and / or alkaline earth metal, And a dopant including the above elements.

The at least one noble metal is preferably selected from the group consisting of Au, Pt, Pd, Rh and Ru. It is particularly preferable to use Pt. A combination of Pt and one or more of the above-mentioned noble metals or a combination of one or more of the noble metals mentioned above except Pt is also advantageous.

The invention particularly preferably provides a catalyst according to the invention, wherein the noble metal is selected from the group consisting of Au, Pt, Pd, Rh, Ru and mixtures thereof. Very particular preference is given to using Pt as the noble metal; In particular, Pt is preferably present as the sole noble metal on the catalyst of the present invention.

The concentration of one or more noble metals according to the invention is advantageously in each case 0.001 to 1.10% by weight, preferably 0.01 to 1.00% by weight, particularly preferably 0.1 to 0.99% by weight, based on the total weight of the catalyst, 0.1 to 0.96% by weight. The specific combination of features of the catalyst of the present invention makes use of very small amounts of expensive precious metals and nevertheless makes it possible to achieve high catalytic activity.

According to the present invention, Li, Na, K, Rb, Cs, Mg, Ca and / or Sr are preferably used as at least one alkali metal and / or alkaline earth metal. Li, Na, K and Rb, especially Na and K are particularly preferred.

Accordingly, the present invention particularly preferably provides a catalyst of the present invention wherein the alkali metal and / or alkaline earth metal is selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr and mixtures thereof .

In a preferred embodiment, the concentration of one or more alkali metals and / or alkaline earth metals is in each case 1.0 to 4.0% by weight, particularly preferably 1.2 to 4.0% by weight, very particularly preferably 1.8 to 3.5% by weight, By weight, especially 2.0 to 3.2% by weight. In a further preferred embodiment, 1.2-3.5 wt.% Of K or Na is used, based on the total weight of the catalyst.

The present invention thus provides, in a preferred embodiment, a catalyst according to the invention in which at least one alkali metal and / or alkaline earth metal is present in an amount of from 1.0 to 4.0% by weight, based on the total catalyst.

As a further component, the catalyst of the present invention comprises at least one dopant selected from the group consisting of Fe, Cr, Cu, Zn and mixtures thereof. According to the invention, it is very particularly preferred to use iron as the dopant. In particular, iron is used exclusively as a dopant.

In the catalyst of the present invention, the at least one dopant, in particular iron, is in each case generally from 0.01 to 5% by weight, preferably from 0.05 to 2.5% by weight, particularly preferably from 0.1 to 1.5% by weight, based on the total weight of the catalyst Lt; / RTI >

In addition to one or more alkali metals and / or alkaline earth metals and one or more dopants, the catalyst of the present invention may comprise further dopants, such as rare earth metals and / or Group 13 elements of Group 15 to Group 15 elements. Such additional dopants may have a total concentration of up to 15% by weight.

Suitable support materials for the purposes of the present invention are all materials which can be used conventionally for these purposes in catalytic chemistry and which have a sufficiently high BET specific surface area.

The BET surface area should advantageously be at least 50 m ² / g.

It is preferred to use a support material comprising a combination of a lanthanide oxide and a transition metal, particularly preferably a Ce / Zr oxide. Here, the ratio of Ce oxide to Zr oxide should advantageously be 15-25: 85-75% by weight, based on the total weight of the support material in each case. In an advantageous embodiment, the Ce / Zr oxide support material contains additional oxides, such as Al ₂ O ₃ and / or La oxide, as dopants. For example, the preferred ratio of Al ₂ O ₃ to Ce / Zr oxide according to the invention is 5-20: 95-80, particularly preferably 8-12: 92-88, for example 10:90.

The amount of La oxide (La ₂ O ₃ ) is, for example, in each case 1 to 10% by weight, preferably 3 to 8% by weight, particularly preferably 4 to 6% by weight, based on the total weight of the support material .

Thus, the present invention particularly preferably provides a catalyst of the present invention wherein the support material comprises at least Ce and / or Zr. In a preferred embodiment, the present invention provides a catalyst of the present invention wherein the support material further comprises La and / or Al.

In a particularly preferred embodiment, the present invention relates to a process for the preparation of platinum complexes, wherein Pt is present as a noble metal and the alkali and / or alkaline earth metals are selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr and mixtures thereof, , And a support material comprising Ce and / or Zr is present. The present invention particularly preferably provides this catalyst according to the invention in which the support material further comprises La.

According to the present invention, the components are present or optionally present in the catalyst of the present invention, i.e. the abovementioned noble metals, alkali metals and / or alkaline earth metals, dopants and supporting materials may be present in elemental form and / have.

In a further preferred embodiment, the present invention relates to a process for the preparation of catalysts, which comprises, in each case based on the total weight of the catalyst, from 0.001 to 1.10% by weight, preferably from 0.01 to 1.00% by weight, By weight, for example from 0.1 to 0.96% by weight, of one or more alkali metals and / or alkaline earth metals, in particular from 1.2 to 4.0% by weight, preferably from 1.8 to 3.5% by weight, Is present in an amount of 2.0 to 3.2% by weight and at least one dopant, in particular Fe, is present in an amount of 0.05 to 2.5% by weight, particularly preferably 0.1 to 1.5% by weight, and the support material comprises at least Ce and / or Zr Based on the total weight of the catalyst.

Very particularly preferred embodiments of the present invention, including specific combinations of precious metals, alkali metals and / or alkaline earth metals, dopants and support materials, are disclosed in the following examples.

This precisely provides a catalyst according to the invention of noble metals, alkali metals and / or alkaline earth metals, dopants and supporting materials, in particular very high activity combined with very high efficiency when used in conversion reactions. It is a combination in a specified amount. The high reactivity of the catalysts of the present invention may be indicated, for example, by the fact that the above-mentioned conversion reactions are carried out to substantially complete the thermodynamically feasible conversion even at relatively low temperatures. In addition, a particularly high efficiency of the catalyst of the present invention is indicated by the fact that this catalyst exhibits only a small tendency towards methanation in the conversion reaction, i.e. only a very small proportion of the formed hydrogen is reacted by the formation of methane It can be done.

Needless to say, the above-mentioned features of the catalyst and the following features which will be described hereinafter are to be understood as being within the scope of the present invention, as well as other combinations and numerical ranges within the scope of the main claim Lt; / RTI >

The catalyst of the present invention can be prepared as individual components by impregnation of the support material. In a further advantageous manufacturing variant, the active ingredient is then at least partially kneaded and applied to the extruded powdery support material. It is also possible to combine manufacturing variants with each other and, for example, to apply only a portion of the active ingredient to the powdered support material, knead and extrude the latter, and then apply the remaining active ingredient or some remaining amount thereof .

The active ingredients are preferably used in the form of their salts or their oxides. Salts suitable for the purposes of the present invention are, for example, oxides, nitrates, hydroxides, acetates, acetylacetonates, carbonates, nitrosyl nitrates or halides such as fluorides, chlorides, bromides and iodides.

In an advantageous embodiment, this component is applied to the support material to ensure good availability of the noble metal. Catalysts with various promoters, for example, are not exclusive, but often in a plurality of impregnation steps, for example in succession, because the various metal salts can not usually be applied in parallel due to conditions such as pH, And two impregnation steps being carried out.

The introduction of the active ingredient by application to a support material can be carried out in a conventional manner, for example as a wash coat on a monolith.

If, in accordance with a further advantageous embodiment, the active substance is first applied at least in part onto a support material, preferably a powdered support material, and then kneaded and then extruded, the dough and extrusion of the support material and the active composition, Lt; RTI ID = 0.0 > conventional < / RTI > technique.

The present invention thus provides, in particular, a process for preparing the catalyst of the present invention, wherein one or more noble metals, at least one alkali metal and / or alkaline earth metal and at least one dopant are applied to the support material as a solution or dispersion,

At least one noble metal, at least one alkali metal and / or alkaline earth metal, and at least a portion of at least one dopant is applied as a solution or dispersion to the support material and the support material is mixed with the remainder of the components.

Contrary to the assumption that the relative activity will be lower for direct kneaded catalysts due to the uniform distribution of the active ingredient over the whole volume of the catalyst particles as compared to the catalyst having the same active composition but prepared by impregnation, Found.

The preparation of shaped bodies from powdery raw materials can be carried out using conventional methods known to those skilled in the art, for example, Handbook of Heterogeneous Catalysis, Vol. 1, VCH Verlagsgesellschaft Weinheim, 1997, S. 414-417 beschrieben sind, erfolgen].

Adjuvants known to those skilled in the art, for example binders, lubricants and / or solvents, may be added during molding or application.

The described manufacturing process is simple and inexpensive. The catalyst of the present invention is highly active for the conversion reaction but inhibits the methanation reaction; For example, less than 100 ppm, preferably less than 50 ppm and (in each case 450 ° C) less than 500 ppm, preferably less than 300 ppm, of the methane content (in each case at 350 ° C) .

The catalyst described can be used in a process for converting a gas mixture comprising at least carbon monoxide and water into hydrogen and carbon dioxide.

The process can be carried out under the general conditions of the conversion reaction, usually in the LTS range at temperatures of 150 to 280 DEG C and in the HTS range at temperatures of usually 280 to 550 DEG C.

Due to the low tendency of methanation, when the catalyst of the present invention is used, even at high temperatures, this catalyst is particularly useful in HTS where prior catalysts of the prior art are not suitable. The conversion reaction according to the invention is carried out particularly successfully within the temperature range of 180 to 550 占 폚. It is therefore possible and advantageous to use the catalyst of the invention both in the stage of HTS and in the stage of LTS.

The catalyst of the present invention also reduces to a single conversion step which can be carried out at a moderate temperature, for example 230 DEG C to 450 DEG C, because the high activity of the catalyst allows for good conversion even at low temperatures .

The method of the present invention for reducing the concentration of carbon monoxide (CO) by the method of conversion reaction through the highly active conversion catalyst of the present invention is characterized in that the reaction gas comprising CO and water is passed through a catalyst, Handbook of heterogeneous catalysis, 2nd edition, Vol. 1, VCH Verlagsgesellschaft Weinheim, 2008, Seiten 354-355), and under conventional conditions.

The reaction gas used is a gas mixture which usually contains additional gases such as hydrogen, carbon dioxide and nitrogen in addition to the carbon monoxide and hydrogen reacted in the conversion reactions described.

The present invention thus also provides the use of the catalysts of the present invention for the conversion of carbon monoxide and water to carbon dioxide and hydrogen.

The present invention further provides a method of converting a gas mixture comprising at least carbon monoxide and water to carbon dioxide and hydrogen using a catalyst according to the present invention.

Degree:

Figure 1 shows an exemplary measurement diagram. Wherein each abbreviation has the following meaning:

A CO amount at reactor outlet [ppm]

B Methane content [ppm]

T Temperature [캜]

MG ₁ Methane content at 350 ° C [ppm]

MG ₂ Methane content at 450 ° C [ppm]

The present invention is illustrated by the following examples, but does not include any limitations.

Example

The catalyst according to the present invention and the catalyst used as a comparative example were prepared by the following method.

One. In impregnation (I)  Manufacturing by:

The catalysts according to the present invention and the comparative catalysts can be prepared by impregnation as shown by the following examples of catalyst preparation.

Starting material:

Manufacturing method:

The required amount of iron nitrate was dissolved in the stated amount of platinum nitrate solution and diluted with distilled H ₂ O to a volume corresponding to 90% of the water absorption of the Ce / Zr support material. The extrudate was introduced into the vessel and spray-impregnated with a platinum / iron nitrate solution while circulating. After impregnation, the extrudate was again circulated for an additional 5 minutes, then dried and then calcined. In the next manufacturing step, a platinum / iron obtained by use of the H ₂ O distilled potassium hydroxide solution were diluted to a volume corresponding to 90% of the dope extrudate moisture absorption. These extrudates were then spray-impregnated with a dilute potassium hydroxide solution obtained with continuous circulation. After impregnation, the extrudate was again circulated for an additional 5 minutes, then dried and then calcined.

Dry: 4 h at 200 ° C in a convection drying oven

Calcination: 2h at 500 ° C

Product weight: 1001.8 g

Doping obtained: Pt 0.9 g < RTI ID = 0.0 >

Fe 0.2 g per 100 g of catalyst

K 2.0 g per 100 g of catalyst

2. Production by Dough (K):

The catalysts according to the present invention and the comparative catalysts can be prepared by kneading as shown by the following examples of catalyst preparation.

Starting material:

Preparation method: CeO2 / Zr powder was introduced into a kneader together with Pural SB. Diluted nitric acid was added slowly to a total volume of 20 ml using distilled H ₂ O and the mixture was kneaded for 10 minutes. The iron nitrate was then dissolved in a platinum nitrate solution, diluted to a total volume of 30 ml with distilled H ₂ O, added and the mixture was kneaded for an additional 5 minutes. An undiluted potassium hydroxide solution was then added and the mixture was kneaded for an additional 10 minutes. A small amount of distilled H ₂ O was added until the plastic composition was formed. The plastic composition was molded using an extruder to obtain a 1.5 mm extrudate.

Total consumption of distilled H ₂ O: 69 ml (containing distilled H ₂ O to dilute HNO ₃ and Pt / Fe solution)

Pressure: 60 bar

Dough time: 49 minutes

Dry: 4 h at 200 ° C in a convection drying oven

Calcination: 2 h at 500 ° C in a convection furnace

Doping obtained: Pt 0.9 g < RTI ID = 0.0 >

Fe 0.2 g per 100 g of catalyst

K 1.0 g per 100 g of catalyst

3. Testing of catalysts:

To demonstrate the suitability of the prepared catalysts, they were used in the conversion reaction. The test was carried out as follows:

1. Catalyst installation: 15 ml catalyst (bed) or 8-12 ml (volume of monolith) installed in the reactor,

2. Test the entire device for leaks after catalyst installation and before startup,

Simultaneous reduction of the catalyst used the first mixture: 3.1 of H ₂ and N ₂ and heated to 220 ℃

4. Keeping it for 5 minutes while reaching a temperature of 220 캜 and then starting the test,

5. Start recording data,

6. Start the temperature program, ie 600 min (continuous), then heat from 220 ° C to 450 ° C,

7. Keep at 450 ° C for 20 minutes,

8. After 600 minutes (continuous), cool from 450 to 220 ° C.

The composition of the reaction gas used in the test is as follows:

7% by weight of CO,

7% by weight of CO ₂ ,

33% by weight of H ₂ ,

27% by weight of N ₂ and

26% by weight of H ₂ O.

The GHSV for the catalyst during the test was 12279 / h. This test variant will be referred to below as test method M.

As an alternative to this test method M, for example, the temperature program can be varied by reducing the final temperature to, for example, 380 占 폚 at an initial temperature and heating rate (占 폚 / min) unchanged from the method M.

The following devices were used:

- Heating: Convection furnace with temperature range up to 600 ℃,

- a temperature meter outside the reactor,

- Gas measurement: Mass flowmeter (Brooks)

- Water measurement: liquid flow rate

- Analyzer for CO and CO2: Siemens Ultramat 23

- Analytical instrument for methane: J.U.M. FID of Engineering Model 3-300A

- Pressure adjustment using Reco pressure regulating valve

- Linseis 36 channel recorder as interface for data storage

- Evaluation of data by software

The following parameters were measured:

1. Temperature T ₁ (temperature [° C] of the lowest CO content at the beginning of the first ramp)

2. Temperature T ₂ (temperature [° C] of the lowest CO content in the first temperature ramp)

3. The methane content at a temperature of 350 ℃ MG ₁ [ppm]

4. At a temperature of 450 ° C, the methane content MG ₂ [ppm]

5. Method M (lamp from 220-440 DEG C, Chevron, etc.)

4. result

The results of the catalysts according to the invention and the catalysts prepared for comparison are shown in the following Table 1:

Results of various catalysts according to the invention and catalysts for comparison number Pt
[weight%] Doping ¹⁾ Alkali metal / alkaline earth metal ²⁾ Manufacturing ³⁾ T ₁
[° C] T ₂
[° C] MG ₁
[ppm] MG ₂
[ppm] M One 0.95 Fe; 0.2 K; 2 I 260.8 301.18 30.62 278.5 × 2 0.95 Fe; 0.2 K; One K 260 300 71.33 - Only 380 ° C 3 0.9 Fe; 0.2 K; One K 270 305 67.39 - Only 380 ° C 4 0.8 Fe; 0.2 K; One K 280 310 54.49 - Only 380 ° C 5 0.9 Fe; 0.2 K; 2 K 292.44 345.22 28.66 145.54 × 6 0.35 Fe; 0.2 K; 2 I 320 325 19.67 285.33 × C7 ⁴⁾ 0.35 Fe; 0.07 K; 0.7 I 330 345 180.69 1383.89 × 8 0.95 Fe; 0.3 K; 2 I 268.66 280.96 48.62 216.3 × 9 0.95 Fe; 0.4 K; 2 I 285.22 314 17.77 101.96 × 10 0.95 Fe; 0.25 K; 2 K 286.29 293.57 45.27 - × 11 0.95 Fe; 0.15 K; 2 K 284.81 285.2 68.98 - Only 380 ° C 12 0.95 Fe; 0.2 K; 3 I 262.48 321.29 - - Only 380 ° C C13 ⁴⁾ 0.95 Fe; 0.2 - I 282.23 307.46 291.56 1885.45 × C14 ⁴⁾ 0.95 Fe; 0.5 - I 296.27 319.63 77.23 329.51 × C15 ⁴⁾ 0.95 Fe; 0.8 - I 315.15 351.55 68.31 246.63 × C16 ⁴⁾ 0.95 Fe; 1.0 Na; 2 I 310.87 331.72 30.07 43.38 × 17 0.95 Fe; 0.5 Na; 2 I 310.38 343.08 54.52 208.73 × C18 ⁴⁾ 0.95 Fe; 1.0 Na; 2 K 331.61 363.68 30.89 75.98 × C19 ⁴⁾ 0.95 - K; 5 I 292.74 346.69 72.06 913.61 × C20 ⁴⁾ 0.95 Fe; 5 Ni; One I 359.03 358.8 25698.78 32595.57 × 21 0.95 Fe; 0.5 Li; 2 I 285.63 297.78 104.51 786.67 × 22 0.95 Fe; 0.5 Rb; 2 I 293.08 304.74 52.34 179.14 × 23 0.95 Fe; 0.5 Cs; 2 I 259.89 - 109.03 554.88 × C24 ⁴⁾ 0.95 Mn; 0.2 K; 2 I 276.89 314.25 291.41 4111.02 × C25 ⁴⁾ 0.95 Co; 0.2 K; 2 I 304.19 318.84 590.55 4731.53 × 26 0.95 Fe; 0.2 Mg; 2 I 321.44 311.44 80.09 694.34 × 27 0.95 Fe; 0.2 Ca; 2 I 300.59 323.29 143.21 1194.77 × 28 0.95 Fe; 0.2 Cs; 2 I 293.18 294.92 178.32 1626.74 × 29 0.95 Fe; 0.2 K; 2 I 281.56 307.02 - - × 30 0.95 Fe; 0.5 K; 2 I 282.83 209.57 24.15 108.47 × C31 ⁴⁾ 0.95 Fe; 5 - I 265.95 298.15 43.72 388.31 × ¹⁾ element; Record amount [wt%]
²⁾ element; Record amount [wt%]
³⁾ I = impregnation; K = kneading
⁴⁾ Comparative Example

Claims (11)

The method of claim 1 wherein at least one noble metal selected from Au, Pt, Pd, Rh and mixtures thereof is applied on the support material in an amount of from 0.1 to 0.96 wt.%, Based on the total weight of the catalyst, of at least one alkali metal and / In an amount of from 1.0 to 4.0% by weight, based on the total weight of the catalyst, and as a dopant, in an amount of at least 0.01 to 5% by weight based on the total weight of the catalyst. The aqueous gas conversion catalyst according to claim 1, wherein the alkali metal and / or alkaline earth metal is selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr and mixtures thereof. The aqueous gas conversion catalyst according to claim 1, wherein the support material comprises at least Ce and / or Zr. The water gas shift catalyst according to claim 3, wherein the support material further comprises La and / or Al. The method according to any one of claims 1 to 4, wherein Pt is present as a noble metal and the alkali metal and / or alkaline earth metal is selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Wherein the dopant is Fe and a support material comprising Ce and / or Zr is present. The process according to any one of claims 1 to 4, wherein in each case at least one noble metal is present in an amount of from 0.1 to 0.96% by weight, based on the total weight of the catalyst, and wherein at least one alkali metal and / To 4.0% by weight, wherein at least Fe as the dopant is present in an amount of 0.05 to 2.5% by weight, and the support material comprises at least Ce and / or Zr. A process for producing a water gas shift catalyst according to any one of claims 1 to 4,
At least one noble metal, at least one alkali metal and / or alkaline earth metal and at least a portion of Fe as a dopant is applied as a solution or dispersion to the support material and the support material is mixed with the remaining components without application,
At least one noble metal, at least one alkali metal and / or alkaline earth metal, and at least all of Fe as a dopant is applied as a solution or dispersion to the support material. A process for the conversion of carbon monoxide and water to carbon dioxide and hydrogen using the aqueous gas conversion catalyst according to any one of claims 1 to 4. A process for the conversion of a gas mixture comprising at least carbon monoxide and water to carbon dioxide and hydrogen using a water gas shift catalyst according to any one of claims 1 to 4. delete delete

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