Cobalt-based catalyst for the conversion of hydrocarbons to synthesis gas

Abstract

The present invention relates to a composite oxide containing oxygen, lanthanum, aluminum, and cobalt, wherein the Co:La weight ratio of cobalt to lanthanum in the composite oxide, calculated as elements, is in the range of 0.06:1 to 0.34:1, and to a method for producing the same. Further, the present invention relates to a method for producing a catalyst for the conversion of hydrocarbons to synthesis gas, and to a catalyst obtainable or obtained according to said method, and to a process for the conversion of hydrocarbons to synthesis gas.

Description

Technical Field

[0001] The present invention relates to a composite oxide containing oxygen, lanthanum, aluminum, and cobalt, wherein the composite oxide has a specific Co:La weight ratio. Further, the present invention relates to a method for producing the composite oxide and the composite oxide obtainable or obtained by the method. Still further, the present invention relates to a method for producing a catalyst for the conversion of hydrocarbons to synthesis gas, and the catalyst obtainable or obtained by the method. Still further, the present invention relates to a process for the conversion of hydrocarbons to synthesis gas.

Background Art

[0002] Ni- or Co-containing oxide-based catalysts are commonly used for the reforming of hydrocarbons to synthesis gas. The application of Co-containing catalysts reduces the production cost because they allow for a lower content of steam in the feed. However, the difficulty in activating Co-containing catalysts by the special activation procedures usually required leads to an increase in production cost.

[0003] WO 2013 / 118078 A1 pamphlet relates to Ni- or Co-containing hexaaluminate catalysts for the reforming of hydrocarbons. WO 2014 / 135642 A1 pamphlet relates to Ni-containing hexaaluminate catalysts for the reforming of hydrocarbons in the presence of CO2. Similarly, WO 2015 / 091310 A1 pamphlet relates to a method for reforming a mixture of hydrocarbons and CO2. US Patent Application Publication No. 2016 / 0207031 A1 and US Patent No. 9566571 B2 are particularly related to the manufacturing process of a reforming catalyst for hydrocarbons from a feed gas containing methane and CO2.

[0004] On the other hand, International Publication No. 2014 / 001423 A1 pamphlet relates to a high-pressure process for the CO2 reforming of hydrocarbons in the presence of an Ir-containing catalyst. On the other hand, International Publication No. 2015 / 135968 A1 pamphlet relates to a yttrium-containing catalyst for high-temperature CO2 hydration and / or reforming.

[0005] International Publication No. 2016 / 062853 A1 pamphlet relates to the synthesis of aluminates by flame spray pyrolysis.

[0006] Finally, International Publication No. 2020 / 157202 A1 pamphlet relates to a molded article containing a mixed oxide of lanthanum, aluminum, and cobalt, wherein the Co:La weight ratio is specified to be in the range of 0.35:1 to 0.48:1.

Summary of the Invention

Problems to be Solved by the Invention

[0007] Despite numerous improvements made in the past, there is still a need for improved catalyst formulations, particularly with regard to their cost efficiency, and more particularly with regard to the activation of Co-containing catalysts for the reforming of hydrocarbons to synthesis gas.

Means for Solving the Problems

[0008] Therefore, it was an object of the present invention to provide a Co-containing catalyst composition, in particular a Co-containing catalyst composition for the conversion of hydrocarbons to synthesis gas in the presence of steam and / or CO2, which enables easier activation of the Co-containing catalyst and in particular increases the rate at which the catalyst is activated. As a result, unexpectedly, a Co-containing catalyst composition containing lanthanum, in which the Co:La weight ratio is within a specific range, enables substantially higher reducibility of the catalyst at low temperatures, and as a result, the activation of the catalyst is significantly improved and can thus be achieved in a much shorter period. As a result, it has been found quite unexpectedly that a highly cost-effective Co-containing catalyst can be provided.

[0009] Accordingly, the present invention relates to a composite oxide containing oxygen, lanthanum, aluminum, and cobalt, wherein the Co:La weight ratio of cobalt to lanthanum in the composite oxide, calculated as elements, is in the range of 0.06:1 to 0.34:1, preferably 0.08:1 to 0.32:1, more preferably 0.10:1 to 0.30:1, more preferably 0.12:1 to 0.28:1, more preferably 0.14:1 to 0.26:1, more preferably 0.16:1 to 0.24:1, more preferably 0.18:1 to 0.22:1, and more preferably 0.20:1 to 0.21:1.

[0010] The composite oxide preferably contains, calculated as elements, 1 to 15% by weight, more preferably 3 to 10% by weight, more preferably 4 to 8% by weight, more preferably 4.5 to 7.5% by weight, more preferably 5 to 7.1% by weight, more preferably 5.5 to 6.9% by weight, more preferably 5.7 to 6.7% by weight, more preferably 5.9 to 6.5% by weight, and more preferably 6.1 to 6.3% by weight of cobalt.

[0011] The composite oxide preferably contains 5 to 50% by weight, more preferably 10 to 45% by weight, still more preferably 15 to 40% by weight, still more preferably 20 to 38% by weight, still more preferably 22 to 35% by weight, still more preferably 24 to 32% by weight, still more preferably 26 to 31% by weight, still more preferably 28 to 30% by weight of lanthanum, calculated as an element.

[0012] The composite oxide preferably contains 5 to 60% by weight, more preferably 10 to 50% by weight, still more preferably 15 to 45% by weight, still more preferably 20 to 40% by weight, still more preferably 23 to 38% by weight, still more preferably 25 to 35% by weight, still more preferably 27 to 33% by weight, still more preferably 29 to 31% by weight of aluminum, calculated as an element.

[0013] The Co:Al weight ratio of cobalt to aluminum in the composite oxide, calculated as an element, is preferably in the range of 0.05:1 to 0.50:1, more preferably 0.10:1 to 0.40:1, still more preferably 0.12:1 to 0.30:1, still more preferably 0.15:1 to 0.28:1, still more preferably 0.18:1 to 0.25:1, still more preferably 0.20:1 to 0.22:1, and still more preferably in the range of 0.205:1 to 0.22:1.

[0014] The composite oxide is LaAl 1-x Co x O3 phase, more preferably LaAl 1-x Co x O3 perovskite phase (where 0 < x < 1, and x is preferably in the range of 0.02 to 0.4, more preferably in the range of 0.03 to 0.3). In this context, the lattice constant of the LaAl 1-x Co x O3 phase is particularly preferably in the range of 3.7920 to 3.7955 Å, more preferably 3.7925 to 3.7950 Å, still more preferably 3.7928 to 3.7945 Å, still more preferably 3.7930 to 3.7940 Å, still more preferably 3.7932 to 3.7935 Å. Here, LaAl 1-x Co xThe lattice constant of the O3 phase is preferably determined according to the method of Reference Example 1. Further and independently thereof, the composite oxide is LaAl 1-x Co x The O3 phase is particularly preferably contained in an amount in the range of 5 to 50% by weight, more preferably 10 to 40% by weight, more preferably 13 to 35% by weight, more preferably 15 to 33% by weight, more preferably 18 to 30% by weight, more preferably 21 to 27% by weight, more preferably 23 to 25% by weight based on 100% by weight of the composite oxide. Here, the amount of the LaAl 1-x Co x O3 phase is preferably determined according to the method of Reference Example 1.

[0015] The composite oxide preferably contains a LaCoAl 11 O 19 phase, preferably a LaCoAl 11 O 19 hexaaluminate phase.

[0016] When the composite oxide contains a LaCoAl 11 O 19 phase, the composite oxide preferably contains the LaCoAl 11 O 19 phase in an amount in the range of 40 to 90% by weight, preferably 50 to 80% by weight, more preferably 55 to 75% by weight, more preferably 58 to 70% by weight, more preferably 60 to 66% by weight, more preferably 62 to 64% by weight based on 100% by weight of the composite oxide. Here, the amount of the LaCoAl 11 O 19 phase is preferably determined according to the method of Reference Example 1.

[0017] The composite oxide preferably contains a LaAl 1-x Co x O3 phase and a LaCoAl 11 O 19 phase. Here, the LaAl 1-x Co x O3 phase to LaCoAl 11 O 19 phase of LaAl 1-x Co xO3:LaCoAl 11 O 19 The weight ratio is in the range of 0.05:1 to 0.70:1, preferably 0.1:1 to 0.60:1, more preferably 0.15:1 to 0.55:1, more preferably 0.20:1 to 0.50:1, more preferably 0.25:1 to 0.48:1, more preferably 0.30:1 to 0.45:1, more preferably 0.35:1 to 0.42:1, more preferably 0.37:1 to 0.39:1, and the LaAl in the composite oxide 1-x Co x The amounts of the O3 phase and LaCoAl 11 O 19 phase are preferably determined according to the method of Reference Example 1.

[0018] The composite oxide preferably contains a La(OH)3 phase.

[0019] When the composite oxide contains a La(OH)3 phase, the composite oxide preferably contains the La(OH)3 phase in an amount in the range of 0.1 to 1.5% by weight, more preferably 0.3 to 1.0% by weight, more preferably 0.5 to 0.8% by weight, more preferably 0.6 to 0.7% by weight, based on 100% by weight of the composite oxide, where the amount of the (OH)3 phase in the composite oxide is preferably determined according to the method of Reference Example 1.

[0020] The composite oxide preferably contains a CoAl2O4 phase, more preferably a CoAl2O4 spinel phase.

[0021] When the composite oxide contains a CoAl2O4 phase, the composite oxide preferably contains the CoAl2O4 phase in an amount in the range of 1.0 to 10% by weight, more preferably 1.5 to 7.0% by weight, more preferably 2.0 to 5.0% by weight, more preferably 2.5 to 4.0% by weight, more preferably 2.8 to 3.5% by weight, more preferably 3.0 to 3.2% by weight, based on 100% by weight of the composite oxide, where the amount of the CoAl2O4 phase in the composite oxide is preferably determined according to the method of Reference Example 1.

[0022] The composite oxide preferably contains a LaAl 1-x Co x O3 phase and a CoAl2O4 phase, where the LaAl 1-x Co x O3 to CoAl2O4 phase weight ratio of LaAl 1-x Co x O3:CoAl2O4 is in the range of 1.0:1 to 15:1, more preferably 2.0:1 to 12:1, more preferably 4.0:1 to 10:1, more preferably 6.0:1 to 9.0:1, more preferably 7.0:1 to 8.5:1, more preferably 7.5:1 to 8.2:1, more preferably 7.8:1 to 7.9:1, and the amounts of the LaAl 1-x Co x O3 phase and the CoAl2O4 phase in the composite oxide are preferably determined according to the method of Reference Example 1.

[0023] The composite oxide preferably contains a LaCoAl 11 O 19 phase and a CoAl2O4 phase, where the LaCoAl 11 O 19 phase to CoAl2O4 phase weight ratio of LaCoAl 11 O 19 :CoAl2O4 is in the range of 1:1 to 50:1, more preferably 3:1 to 45:1, more preferably 5:1 to 40:1, more preferably 9:1 to 35:1, more preferably 11:1 to 30:1, more preferably 13:1 to 28:1, more preferably 15:1 to 26:1, more preferably 18:1 to 24:1, more preferably 20:1 to 22:1, and the amounts of the LaCoAl 11 O 19 phase and the CoAl2O4 phase in the composite oxide are preferably determined according to the method of Reference Example 1.

[0024] The composite oxide preferably exhibits a crystallinity in the range of 80 to 100%, more preferably 85 to 99%, more preferably 88 to 97%, more preferably 90 to 95%, more preferably 91 to 93%, where the crystallinity of the composite oxide is preferably determined according to the method of Reference Example 1.

[0025] 99 to 100% by weight, more preferably 99.5 to 100% by weight, and even more preferably 99.9 to 100% by weight of the composite oxide preferably consists of oxygen, lanthanum, aluminum, cobalt, and optionally hydrogen.

[0026] The composite oxide is preferably in the form of a powder or a molded article, more preferably in the form of a molded article.

[0027] When the composite oxide is in the form of a powder or a molded article, 99 to 100% by weight, more preferably 99.5 to 100% by weight, and even more preferably 99.9 to 100% by weight of the powder or the molded article preferably consists of the composite oxide.

[0028] The composite oxide is preferably obtained or available according to one of the processes of the specific and preferred embodiments of the present invention.

[0029] The present invention also relates to a method for producing a composite oxide, preferably a composite oxide according to one of the specific and preferred embodiments of the present invention, the method comprising: (i) preparing a mixture of one or more Al sources, one or more Co sources, and one or more La sources; (ii) adding an acidic aqueous solution to the mixture prepared in (i); (iii) homogenizing the mixture obtained in (ii); (iv) optionally molding the mixture obtained in (iii) to obtain a molded article, preferably by extrusion; (v) optionally drying the mixture obtained in (iii) or the molded article obtained in (iv); (vi) optionally pre-firing the mixture obtained in (iii) or (v), or the molded article obtained in (iv) or (v); (vii) optionally milling the dried and / or pre-fired mixture or molded article obtained in (v) or (vi); (viii) Optionally, tabletizing the ground product obtained in (vii); (ix) Firing the mixture obtained in (iii), (v), or (vi), or the molded article obtained in (iv), (v), or (vi), or the ground product obtained in (vii), or the tabletized product obtained in (viii) relates to a production method including the above.

[0030] Furthermore and independently thereof, the one or more Al sources are preferably selected from the group consisting of aluminum trihydroxide, Al2O3·0.5H2O, Al2O3, AlO(OH), more preferably boehmite, sodium aluminate, and mixtures of two or more thereof, preferably from the group consisting of gibbsite (alpha-aluminum trihydroxide), bayerite (beta-aluminum trihydroxide), nordstrandite (gamma-aluminum trihydroxide), pseudo-amorphous aluminum trihydroxide, Al2O3·0.5H2O, Al2O3, AlO(OH), more preferably boehmite, sodium aluminate, and mixtures of two or more thereof, where the one or more alumina sources are more preferably AlO(OH).

[0031] The one or more Co sources are preferably selected from the group consisting of cobalt carbonate, cobalt oxalate, cobalt acetate, cobalt tartrate, cobalt formate, cobalt sulfate, cobalt sulfide, cobalt fluoride, cobalt chloride, cobalt bromide, and cobalt iodide, where the one or more Co sources are more preferably cobalt carbonate, more preferably cobalt carbonate containing CoCO3·yH2O (where 0≦y≦7, preferably 0≦y≦6) more preferably, and more preferably is cobalt carbonate.

[0032] The one or more La sources are preferably selected from the group consisting of lanthanum carbonate, lanthanum oxalate, lanthanum acetate, lanthanum tartrate, lanthanum formate, lanthanum sulfate, lanthanum sulfide, lanthanum fluoride, lanthanum chloride, lanthanum bromide, and lanthanum iodide. Here, the one or more La sources are more preferably lanthanum carbonate, and lanthanum carbonate more preferably contains La2(CO3)3·xH2O (where 0≦x≦10, more preferably 0≦x≦6), and more preferably is that.

[0033] The mixture in (i) is preferably prepared by kneading one or more Al, Co, and La sources.

[0034] The acidic aqueous solution added in (ii) preferably contains one or more of formic acid, acetic acid, propionic acid, nitric acid, nitrous acid, citric acid, tartaric acid, and oxalic acid, more preferably one or more of formic acid and nitric acid. Here, the acidic aqueous solution added in (ii) more preferably contains formic acid.

[0035] The homogenization in (iii) is preferably achieved by stirring, preferably kneading, the mixture obtained in (ii).

[0036] The drying in (v) is preferably carried out at a temperature in the range of 80 to 150°C, more preferably in the range of 95 to 120°C, and more preferably in the range of 100 to 110°C.

[0037] The drying in (v) is preferably carried out for a duration in the range of 4 to 18 h, more preferably in the range of 6 to 12 h, and more preferably in the range of 8 to 10 h.

[0038] The pre-firing in (vi) is preferably carried out at a temperature in the range of 300 to 600°C, more preferably in the range of 350 to 500°C, and more preferably in the range of 400 to 450°C.

[0039] The preliminary firing in (vi) is preferably carried out for a duration in the range of 1 to 8 h, more preferably in the range of 3 to 5 h, and even more preferably in the range of 3.5 to 4.5 h.

[0040] The firing in (ix) is preferably carried out at a temperature in the range of 800 to 1500 °C, more preferably in the range of 1000 to 1400 °C, and even more preferably in the range of 1100 to 1300 °C.

[0041] The firing in (ix) is preferably carried out for a duration in the range of 1 to 8 h, more preferably in the range of 3 to 5 h, and even more preferably in the range of 3.5 to 4.5 h.

[0042] In addition thereto, the present invention relates to a composite oxide obtainable or obtained according to the method according to any one of the specific and preferred embodiments of the present invention.

[0043] The present invention also relates to a method for producing a catalyst for the conversion of hydrocarbons into synthesis gas, the method comprising: (1) providing a composite oxide according to any one of the specific and preferred embodiments of the present invention, or preparing a composite oxide according to the method according to any one of the specific and preferred embodiments of the present invention; (2) reducing the composite oxide prepared in (1) to obtain a catalyst and relates to a production method.

[0044] The reduction in (2) is preferably carried out in an atmosphere containing one or more reducing agents, wherein the one or more reducing agents include one or more of methane, hydrogen, and carbon monoxide, more preferably include methane and / or hydrogen, and even more preferably, methane is used as the reducing agent in (2).

[0045] The reduction in (2) is preferably carried out at a temperature in the range of 500 to 1200 °C, more preferably 600 to 1100 °C, more preferably 700 to 1050 °C, more preferably 750 to 1000 °C, more preferably 800 to 950 °C, and even more preferably 850 to 900 °C.

[0046] The reduction in (2) is preferably carried out at a pressure in the range of 5 to 40 bara, more preferably 10 to 35 bara, more preferably 12 to 30 bara, more preferably 14 to 25 bara, more preferably 16 to 22 bara, and even more preferably 18 to 20 bara.

[0047] The reduction in (2) is preferably carried out for a duration in the range of 0.5 to 24 h, more preferably 1 to 18 h, more preferably 3 to 10 h, and more preferably 5 to 7 h.

[0048] The present invention also relates to a catalyst for the conversion of hydrocarbons to synthesis gas obtainable or obtained according to the method described in any one of the specific and preferred embodiments of the present invention.

[0049] Furthermore, the present invention is a process for the conversion of hydrocarbons to synthesis gas, the process comprising: (A) providing a composite oxide according to any one of the specific and preferred embodiments of the present invention, or a catalyst for the conversion of hydrocarbons to synthesis gas obtainable or obtained according to the method described in any one of the specific and preferred embodiments of the present invention; (B) preparing a gas stream comprising one or more hydrocarbons and one or more of CO2 and H2O; (C) contacting the gas stream prepared in (B) with the composite oxide provided in (A) at a temperature in the range of 700 to 1200 °C, preferably 750 to 1100 °C, more preferably 800 to 1050 °C, more preferably 850 to 1000 °C, and even more preferably 900 to 950 °C. The present invention relates to a process comprising the above.

[0050] The gas stream prepared in (B) preferably contains one or more hydrocarbons, CO2 and H2O.

[0051] The one or more hydrocarbons are preferably selected from the group consisting of C1-C10 alkanes, more preferably from C1-C8 alkanes, more preferably from C1-C6 alkanes, more preferably from C1-C4 alkanes, more preferably from C1-C3 alkanes, more preferably from C1-C2 alkanes, where more preferably the gas stream prepared in (B) contains one or more of methane, ethane, and propane, more preferably the gas stream prepared in (B) contains methane and / or ethane, preferably methane, and more preferably the one or more hydrocarbons contained in the gas stream prepared in (B) consist of methane and / or ethane, preferably methane.

[0052] The gas stream prepared in (B) preferably contains 20-80% by volume, more preferably 25-60% by volume, more preferably 30-50% by volume, more preferably 35-45% by volume, more preferably 38-42% by volume of one or more hydrocarbons.

[0053] The gas stream prepared in (B) preferably contains 20-80% by volume, more preferably 25-60% by volume, more preferably 30-50% by volume, more preferably 35-45% by volume, more preferably 38-42% by volume of CO2.

[0054] The gas stream prepared in (B) preferably contains 1-30% by volume, more preferably 5-25% by volume, more preferably 10-20% by volume, more preferably 12-18% by volume, more preferably 14-16% by volume of H2O.

[0055] The gas stream prepared in (B) preferably further contains one or more inert gases, where the inert gas is more preferably selected from the group consisting of noble gases, nitrogen, and mixtures of two or more thereof, and more preferably the gas stream further contains nitrogen and / or argon, preferably nitrogen.

[0056] When the gas stream prepared in (B) further contains one or more inert gases, the gas stream prepared in (B) preferably contains one or more inert gases in an amount of 0 to 25% by volume, more preferably 0.5 to 15% by volume, more preferably 1 to 10% by volume, more preferably 3 to 8% by volume, and more preferably 4 to 6% by volume.

[0057] The contacting in (C) is preferably carried out at a pressure in the range of 5 to 40 bara, more preferably 10 to 35 bara, more preferably 12 to 30 bara, more preferably 14 to 25 bara, more preferably 16 to 22 bara, and more preferably 18 to 20 bara.

[0058] (C) The contacting in (C) is 500 to 25,000 h -1 , preferably 1,000 to 15,000 h -1 , more preferably 3,000 to 10,000 h -1 , more preferably 4,000 to 8,000 h -1 , more preferably 5,000 to 7,000 h -1 and is preferably carried out at a gas hourly space velocity in the range of.

[0059] The present invention is further illustrated by the following series of embodiments and combinations of embodiments obtained from the dependencies and cross-references shown. In particular, whenever the scope of an embodiment is referred to in connection with terms such as "the composite oxide according to any one of Embodiments 1 to 4", it is meant that all embodiments within this scope are explicitly disclosed to those skilled in the art, i.e., it is pointed out that the syntax of this term should be understood by those skilled in the art as being synonymous with "the composite oxide according to any one of Embodiments 1, 2, 3, and 4". Further, it is explicitly pointed out that the following series of embodiments represent a properly structured part of this description directed to general and preferred aspects of the present invention, rather than a series of claims that define the scope of protection.

[0060] 1. A composite oxide containing oxygen, lanthanum, aluminum, and cobalt, wherein the Co:La weight ratio of cobalt to lanthanum in the composite oxide, calculated as elements, is in the range of 0.06:1 to 0.34:1, preferably 0.08:1 to 0.32:1, more preferably 0.10:1 to 0.30:1, more preferably 0.12:1 to 0.28:1, more preferably 0.14:1 to 0.26:1, more preferably 0.16:1 to 0.24:1, more preferably 0.18:1 to 0.22:1, and more preferably 0.20:1 to 0.21:1.

[0061] 2. The composite oxide according to Embodiment 1, wherein the composite oxide contains 1 to 15% by weight, preferably 3 to 10% by weight, more preferably 4 to 8% by weight, more preferably 4.5 to 7.5% by weight, more preferably 5 to 7.1% by weight, more preferably 5.5 to 6.9% by weight, more preferably 5.7 to 6.7% by weight, more preferably 5.9 to 6.5% by weight, and more preferably 6.1 to 6.3% by weight of cobalt, calculated as elements.

[0062] 3. The composite oxide according to Embodiment 1 or 2, wherein the composite oxide contains 5 to 50% by weight, preferably 10 to 45% by weight, more preferably 15 to 40% by weight, more preferably 20 to 38% by weight, more preferably 22 to 35% by weight, more preferably 24 to 32% by weight, more preferably 26 to 31% by weight, and more preferably 28 to 30% by weight of lanthanum, calculated as elements.

[0063] 4. The composite oxide according to any one of Embodiments 1 to 3, wherein the composite oxide contains 5 to 60% by weight, preferably 10 to 50% by weight, more preferably 15 to 45% by weight, more preferably 20 to 40% by weight, more preferably 23 to 38% by weight, more preferably 25 to 35% by weight, more preferably 27 to 33% by weight, and more preferably 29 to 31% by weight of aluminum, calculated as elements.

[0064] 5. The Co:Al weight ratio of cobalt to aluminum in the composite oxide, calculated as an element, is in the range of 0.05:1 to 0.50:1, preferably 0.10:1 to 0.40:1, more preferably 0.12:1 to 0.30:1, more preferably 0.15:1 to 0.28:1, more preferably 0.18:1 to 0.25:1, more preferably 0.20:1 to 0.22:1, and more preferably 0.205:1 to 0.22:1, the composite oxide according to any one of Embodiments 1 to 4.

[0065] 6. The composite oxide is LaAl 1-x Co x O3 phase, preferably LaAl 1-x Co x O3 perovskite phase (where 0 < x < 1, and x is preferably in the range of 0.02 to 0.4, more preferably in the range of 0.03 to 0.3), the composite oxide according to any one of Embodiments 1 to 5.

[0066] 7. The lattice constant a of the LaAl 1-x Co x O3 phase is in the range of 3.7920 to 3.7955 Å, preferably 3.7925 to 3.7950 Å, more preferably 3.7928 to 3.7945 Å, more preferably 3.7930 to 3.7940 Å, more preferably 3.7932 to 3.7935 Å, where the lattice constant a of the LaAl 1-x Co x O3 phase in the composite oxide is preferably determined according to the method of Reference Example 1, the composite oxide according to Embodiment 6.

[0067] 8. The composite oxide contains the LaAl 1-x Co x O3 phase in an amount in the range of 5 to 50% by weight, preferably 10 to 40% by weight, more preferably 13 to 35% by weight, more preferably 15 to 33% by weight, more preferably 18 to 30% by weight, more preferably 21 to 27% by weight, more preferably 23 to 25% by weight, based on 100% by weight of the composite oxide, where the LaAl 1-x Cox The amount of the O3 phase is preferably determined according to the method of Reference Example 1, the composite oxide according to Embodiment 6 or 7.

[0068] 9. The composite oxide is LaCoAl 11 O 19 phase, preferably LaCoAl 11 O 19 The composite oxide according to any one of Embodiments 1 to 8, including a hexaaluminate phase.

[0069] 10. The composite oxide contains the LaCoAl 11 O 19 phase in an amount in the range of 40 to 90% by weight, preferably 50 to 80% by weight, more preferably 55 to 75% by weight, more preferably 58 to 70% by weight, more preferably 60 to 66% by weight, more preferably 62 to 64% by weight, based on 100% by weight of the composite oxide, wherein the amount of the LaCoAl 11 O 19 phase in the composite oxide is preferably determined according to the method of Reference Example 1, the composite oxide according to Embodiment 9.

[0070] 11. The composite oxide contains a LaAl 1-x Co x O3 phase and a LaCoAl 11 O 19 phase, wherein the weight ratio of the LaAl 1-x Co x O3 phase to the LaCoAl 11 O 19 phase, LaAl 1-x Co x O3:LaCoAl 11 O 19 is in the range of 0.05:1 to 0.70:1, preferably 0.1:1 to 0.60:1, more preferably 0.15:1 to 0.55:1, more preferably 0.20:1 to 0.50:1, more preferably 0.25:1 to 0.48:1, more preferably 0.30:1 to 0.45:1, more preferably 0.35:1 to 0.42:1, more preferably 0.37:1 to 0.39:1, LaAl in the composite oxide 1-x Co x O3 phase and LaCoAl 11 O 19 The respective amounts of the phases are preferably determined according to the method of Reference Example 1, The composite oxide according to any one of Embodiments 1 to 10.

[0071] 12. The composite oxide according to any one of Embodiments 1 to 11, wherein the composite oxide contains a La(OH)3 phase.

[0072] 13. The composite oxide contains a La(OH)3 phase in an amount in the range of 0.1 to 1.5% by weight, preferably 0.3 to 1.0% by weight, more preferably 0.5 to 0.8% by weight, still more preferably 0.6 to 0.7% by weight, based on 100% by weight of the composite oxide, wherein the amount of the La(OH)3 phase in the composite oxide is preferably determined according to the method of Reference Example 1, The composite oxide according to Embodiment 12.

[0073] 14. The composite oxide according to any one of Embodiments 1 to 13, wherein the composite oxide contains a CoAl2O4 phase, preferably a CoAl2O4 spinel phase.

[0074] 15. The composite oxide contains a CoAl2O4 phase in an amount in the range of 1.0 to 10% by weight, preferably 1.5 to 7.0% by weight, more preferably 2.0 to 5.0% by weight, still more preferably 2.5 to 4.0% by weight, still more preferably 2.8 to 3.5% by weight, still more preferably 3.0 to 3.2% by weight, based on 100% by weight of the composite oxide, wherein the amount of the CoAl2O4 phase in the composite oxide is preferably determined according to the method of Reference Example 1, The composite oxide according to Embodiment 14.

[0075] 16. The composite oxide contains a LaAl 1-x Co x O3 phase and a CoAl2O4 phase, where LaAl 1-x Co xLaAl of the O3 phase relative to the CoAl2O4 phase 1-x Co x The weight ratio of the O3:CoAl2O4 phases is in the range of 1.0:1 to 15:1, preferably 2.0:1 to 12:1, more preferably 4.0:1 to 10:1, more preferably 6.0:1 to 9.0:1, more preferably 7.0:1 to 8.5:1, more preferably 7.5:1 to 8.2:1, more preferably 7.8:1 to 7.9:1, LaAl in the composite oxide 1-x Co x The amounts of the O3 phase and the CoAl2O4 phase are preferably determined according to the method of Reference Example 1, The composite oxide according to any one of Embodiments 1 to 15.

[0076] 17. The composite oxide is LaCoAl 11 O 19 comprises a phase and a CoAl2O4 phase, where LaCoAl 11 O 19 The weight ratio of the LaCoAl 11 O 19 phase to the CoAl2O4 phase is in the range of 1:1 to 50:1, preferably 3:1 to 45:1, more preferably 5:1 to 40:1, more preferably 9:1 to 35:1, more preferably 11:1 to 30:1, more preferably 13:1 to 28:1, more preferably 15:1 to 26:1, more preferably 18:1 to 24:1, more preferably 20:1 to 22:1, LaCoAl in the composite oxide 11 O 19 The amounts of the phase and the CoAl2O4 phase are preferably determined according to the method of Reference Example 1, The composite oxide according to any one of Embodiments 1 to 16.

[0077] 18. The composite oxide exhibits a crystallinity in the range of 80 to 100%, preferably 85 to 99%, more preferably 88 to 97%, more preferably 90 to 95%, more preferably 91 to 93%, where the crystallinity of the composite oxide is preferably determined according to the method of Reference Example 1, The composite oxide according to any one of Embodiments 1 to 17.

[0078] 19. 99 to 100% by weight, preferably 99.5 to 100% by weight, more preferably 99.9 to 100% by weight of the composite oxide is the composite oxide according to any one of Embodiments 1 to 18, which consists of oxygen, lanthanum, aluminum, cobalt, and optionally hydrogen.

[0079] 20. The composite oxide according to any one of Embodiments 1 to 19, which is in the form of a powder or a molded article, preferably in the form of a molded article.

[0080] 21. 99 to 100% by weight, preferably 99.5 to 100% by weight, more preferably 99.9 to 100% by weight of the powder or the molded article is the composite oxide according to Embodiment 20, which consists of a mixed oxide.

[0081] 22. The composite oxide according to any one of Embodiments 1 to 21, which is obtained or available according to the process described in any one of Embodiments 23 to 39.

[0082] 23. A method for producing a composite oxide, preferably the composite oxide according to any one of Embodiments 1 to 21, wherein the method comprises: (i) preparing a mixture of one or more Al sources, one or more Co sources, and one or more La sources; (ii) adding an acidic aqueous solution to the mixture prepared in (i); (iii) homogenizing the mixture obtained in (ii); (iv) optionally molding the mixture obtained in (iii) to obtain a molded article, preferably by extrusion; (v) optionally drying the mixture obtained in (iii) or the molded article obtained in (iv); (vi) optionally pre-firing the mixture obtained in (iii) or (v), or the molded article obtained in (iv) or (v). (vii) Optionally, milling the dried and / or pre-fired mixture or shaped body obtained in (v) or (vi); (viii) Optionally, tabletting the milled product obtained in (vii); (ix) Firing the mixture obtained in (iii), (v), or (vi), or the shaped body obtained in (iv), (v), or (vi), or the milled product obtained in (vii), or the tabletted product obtained in (viii) A production method comprising the above steps.

[0083] 24. The method according to embodiment 23, wherein the one or more Al sources are selected from the group consisting of aluminum trihydroxide, Al2O3·0.5H2O, Al2O3, AlO(OH), preferably boehmite, sodium aluminate, and mixtures of two or more thereof, preferably from the group consisting of gibbsite (alpha-aluminum trihydroxide), bayerite (beta-aluminum trihydroxide), nordstrandite (gamma-aluminum trihydroxide), pseudo-amorphous aluminum trihydroxide, Al2O3·0.5H2O, Al2O3, AlO(OH), preferably boehmite, sodium aluminate, and mixtures of two or more thereof, and wherein the one or more alumina sources are more preferably AlO(OH).

[0084] 25. The method according to embodiment 23 or 24, wherein the one or more Co sources are selected from the group consisting of cobalt carbonate, cobalt oxalate, cobalt acetate, cobalt tartrate, cobalt formate, cobalt sulfate, cobalt sulfide, cobalt fluoride, cobalt chloride, cobalt bromide, and cobalt iodide, and wherein the one or more Co sources are preferably cobalt carbonate, more preferably cobalt carbonate containing CoCO3·yH2O (where 0≤y≤7, preferably 0≤y≤6) more preferably, and more preferably it is cobalt carbonate.

[0085] 26. The at least one La source is selected from the group consisting of lanthanum carbonate, lanthanum oxalate, lanthanum acetate, lanthanum tartrate, lanthanum formate, lanthanum sulfate, lanthanum sulfide, lanthanum fluoride, lanthanum chloride, lanthanum bromide, and lanthanum iodide, wherein the at least one La source is preferably lanthanum carbonate, more preferably containing La2(CO3)3·xH2O (where 0≦x≦10, more preferably 0≦x≦6), and more preferably being lanthanum carbonate, the method according to any one of Embodiments 23 to 25.

[0086] 27. The mixture in (i) is prepared by kneading the at least one Al, Co, and La source, the method according to any one of Embodiments 23 to 26.

[0087] 28. The acidic aqueous solution added in (ii) contains at least one of formic acid, acetic acid, propionic acid, nitric acid, nitrous acid, citric acid, tartaric acid, and oxalic acid, preferably at least one of formic acid and nitric acid, wherein the acidic aqueous solution added in (ii) more preferably contains formic acid, the method according to any one of Embodiments 23 to 27.

[0088] 29. The homogenization in (iii) is achieved by stirring, preferably kneading, the mixture obtained in (ii), the method according to any one of Embodiments 23 to 28.

[0089] 30. The drying in (v) is carried out at a temperature in the range of 80 to 150 °C, preferably in the range of 95 to 120 °C, more preferably in the range of 100 to 110 °C, the method according to any one of Embodiments 23 to 29.

[0090] 31. The drying in (v) is carried out for a duration in the range of 4 to 18 h, preferably in the range of 6 to 12 h, more preferably in the range of 8 to 10 h, the method according to any one of Embodiments 23 to 30.

[0091] The preliminary firing in 32.(vi) is carried out at a temperature in the range of 300 to 600 °C, preferably in the range of 350 to 500 °C, more preferably in the range of 400 to 450 °C, according to any one of Embodiments 23 to 31.

[0092] The preliminary firing in 33.(vi) is carried out for a duration in the range of 1 to 8 h, preferably in the range of 3 to 5 h, more preferably in the range of 3.5 to 4.5 h, according to any one of Embodiments 23 to 32.

[0093] The firing in 34.(ix) is carried out at a temperature in the range of 800 to 1500 °C, preferably in the range of 1000 to 1400 °C, more preferably in the range of 1100 to 1300 °C, according to any one of Embodiments 23 to 33.

[0094] The firing in 35.(ix) is carried out for a duration in the range of 1 to 8 h, preferably in the range of 3 to 5 h, more preferably in the range of 3.5 to 4.5 h, according to any one of Embodiments 23 to 34.

[0095] A composite oxide obtainable or obtainable according to the method according to any one of Embodiments 23 to 35.

[0096] A method for producing a catalyst for the conversion of hydrocarbons to synthesis gas, the method comprising: (1) providing a composite oxide according to any one of Embodiments 1 to 22 and 36, or preparing a composite oxide according to the method according to any one of Embodiments 23 to 35; (2) reducing the composite oxide prepared in (1) to obtain a catalyst The production method comprising.

[0097] The reduction in 38.(2) is carried out in an atmosphere containing one or more reducing agents, where the one or more reducing agents include one or more of methane, hydrogen, and carbon monoxide, preferably include methane and / or hydrogen, and more preferably methane is used as the reducing agent in (2), according to the method according to Embodiment 37.

[0098] 39. The reduction in (2) is carried out at a temperature in the range of 500 to 1,200 °C, preferably 600 to 1,100 °C, more preferably 700 to 1,050 °C, more preferably 750 to 1,000 °C, more preferably 800 to 950 °C, more preferably 850 to 900 °C, according to the method described in Embodiment 37 or 38.

[0099] 40. The reduction in (2) is carried out at a pressure in the range of 5 to 40 bara, preferably 10 to 35 bara, more preferably 12 to 30 bara, more preferably 14 to 25 bara, more preferably 16 to 22 bara, more preferably 18 to 20 bara, according to the method described in any one of Embodiments 37 to 39.

[0100] 41. The reduction in (2) is carried out for a duration in the range of 0.5 to 24 h, preferably 1 to 18 h, more preferably 3 to 10 h, more preferably 5 to 7 h, according to the method described in any one of Embodiments 37 to 40.

[0101] 42. A catalyst for the conversion of hydrocarbons to synthesis gas obtainable or obtained according to the method described in any one of Embodiments 37 to 41.

[0102] 43. A process for the conversion of hydrocarbons to synthesis gas, the process comprising: (A) providing a composite oxide described in any one of Embodiments 1 to 22 and 36, or a catalyst described in Embodiment 42; (B) preparing a gas stream containing one or more hydrocarbons and one or more of CO2 and H2O; (C) contacting the gas stream prepared in (B) with the composite oxide provided in (A) at a temperature in the range of 700 to 1,200 °C, preferably 750 to 1,100 °C, more preferably 800 to 1,050 °C, more preferably 850 to 1,000 °C, more preferably 900 to 950 °C A conversion process comprising.

[0103] The gas stream prepared in (B) is the process according to embodiment 43, comprising one or more hydrocarbons, CO2 and H2O.

[0104] 45. The one or more hydrocarbons are selected from the group consisting of C1-C10 alkanes, preferably C1-C8 alkanes, more preferably C1-C6 alkanes, more preferably C1-C4 alkanes, more preferably C1-C3 alkanes, more preferably C1-C2 alkanes. More preferably, the gas stream prepared in (B) contains one or more of methane, ethane, and propane. More preferably, the gas stream prepared in (B) contains methane and / or ethane, preferably methane. More preferably, the one or more hydrocarbons contained in the gas stream prepared in (B) consist of methane and / or ethane, preferably methane. It is the process according to embodiment 43 or 44.

[0105] 46. The gas stream prepared in (B) contains 20-80% by volume, preferably 25-60% by volume, more preferably 30-50% by volume, more preferably 35-45% by volume, more preferably 38-42% by volume of one or more hydrocarbons. It is the process according to any one of embodiments 43-45.

[0106] 47. The gas stream prepared in (B) contains 20-80% by volume, preferably 25-60% by volume, more preferably 30-50% by volume, more preferably 35-45% by volume, more preferably 38-42% by volume of CO2. It is the process according to any one of embodiments 43-46.

[0107] 48. The gas stream prepared in (B) contains 1-30% by volume, preferably 5-25% by volume, more preferably 10-20% by volume, more preferably 12-18% by volume, more preferably 14-16% by volume of H2O. It is the process according to any one of embodiments 43-47.

[0108] The gas stream prepared in (B) further contains one or more inert gases, which are preferably selected from the group consisting of noble gases, nitrogen, and mixtures of two or more thereof, and more preferably the gas stream further contains nitrogen and / or argon, preferably nitrogen, according to any one of Embodiments 43 to 48.

[0109] The gas stream prepared in (B) contains 0 to 25% by volume, preferably 0.5 to 15% by volume, more preferably 1 to 10% by volume, more preferably 3 to 8% by volume, more preferably 4 to 6% by volume of one or more inert gases, according to the process of Embodiment 49.

[0110] The contacting in (C) is carried out at a pressure in the range of 5 to 40 bara, preferably 10 to 35 bara, more preferably 12 to 30 bara, more preferably 14 to 25 bara, more preferably 16 to 22 bara, more preferably 18 to 20 bara, according to any one of Embodiments 43 to 50.

[0111] 52. The contacting in (C) is carried out at a gas hourly space velocity in the range of 500 to 25,000 h -1 , preferably 1,000 to 15,000 h -1 , more preferably 3,000 to 10,000 h -1 , more preferably 4,000 to 8,000 h -1 , more preferably 5,000 to 7,000 h -1 , according to the process of any one of Embodiments 43 to 51.

Brief Description of the Drawings

[0112]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Mode for Carrying Out the Invention

Examples

[0113] The present invention is further illustrated by the following examples, comparative examples, and reference examples.

[0114] Reference Example 1: Composition and Structure Analysis by X-ray Diffraction Powder X-ray diffraction (PXRD) data were collected using a laboratory diffractometer (D8 Discover, Bruker AXS GmbH, Karlsruhe). The instrument was set up using a molybdenum X-ray tube (40 mA, 40 kV). The characteristic K-alpha line was monochromatized using a bent germanium Johannsen-type primary monochromator. Data were collected in Bragg-Brentano reflection geometry (2 - 40° (2θ), 0.02° step size, 2.4 s / step). The scattered X-ray signal was collected using a LYNXEYE XE area detector. The powder was milled using an IKA tube mill and a MT40.100 disposable grinding chamber. The powder was placed in a sample holder and flattened using a glass plate. Data analysis was performed using DIFFRAC.EVA V4 and DIFFRAC.TOPAS V4 software (Bruker AXS GmbH). The crystallinity was estimated using DIFFRAC.EVA. The default values were used as input data for the algorithm (DIFFRAC.EVA User Manual, 2014, Bruker AXS GmbH, Karlsruhe). All other parameters were determined using DIFFRAC.TOPAS. The hexagonal LaCoAl 11 O 19 , rhombohedral LaAlO3, cubic CoAl2O4, hexagonal La(OH)3, cubic Co-doped LaAlO3 and the crystal structure of corundum were used to simulate the overall diffraction pattern. During the simulation, 29 parameters were refined to fit the simulated diffraction to the measured data. The parameters are listed in Table 1 below.

[0115]

Table 1

[0116] All the crystal structures used were retrieved from the Inorganic Crystal Structure Database (ICSD) (ICSD, FIZ Karlsruhe (https: / / icsd.fiz-karlsruhe.de / )) or the Pearson’s Crystal Data (PCD) (Pearson’s Crystal Data - Crystal Structure Database for Inorganic Compounds, Release 2016 / 2017, ASM International, Materials Park, Ohio, USA). Table 2 below lists the reference numbers of the structures used.

[0117]

Table 2

[0118] The microcrystalline size values are those reported as Lvol-FWHM in DIFFRAC.TOPAS. To ensure reliable microcrystalline size values, the geometric configuration of the diffractometer was input into the software to enable the calculation of the instrumental resolution based on the fundamental parameters approach (DIFFRAC.TOPAS User Manual, 2014, Bruker AXS GmbH, Karlsruhe). The scale factors were recalculated by DIFFRAC.TOPAS to mass percent values and reported.

[0119] Reference Example 2: Temperature Programmed Reduction (TPR) Analysis The reduction behavior of the formed product was determined by temperature programmed reduction. A 190 mg sample with particles of an average particle size of 0.2 - 0.4 mm was used. As the feed gas, a flow of 5 vol% hydrogen in argon was used, thereby setting the feed rate to 50 ml / min. The temperature was raised from room temperature to 950 °C at a heating rate of 5 K / min during the measurement. The thermal conductivity detector (TCD) signal was recorded against the temperature to obtain the TPR profile. The TPR profiles of Examples 4 - 6 and Comparative Example 1 are shown in Figures 1 and 2, and those of Examples 7 and 9 and Comparative Examples 2 and 8 are shown in Figure 3.

[0120] Comparative Example 1: Preparation of a Composite Oxide of Co, La, and Al 70 kg of aqueous AlOOH (Disperal; Sasol; containing 77.6 wt% Al calculated as Al2O3), 13.04 kg of cobalt(II) carbonate hydrate (containing 55.92 wt% Co calculated as CoO; Umicore), and 34.37 kg of lanthanum(III) carbonate hydrate (containing 49.26 wt% La calculated as La2O3; Inner Mongolia) were premixed in a Koller or in a mixer for several minutes. Then, 50.79 kg of aqueous formic acid (containing 37 wt% formic acid; Bernd Kraft GmbH, CAS#: 64-18-6, based on formic acid having 98 - 100 wt%) was added in three portions under mixing (where the first portion contains about 50 wt% of the total aqueous formic acid, and the second and third portions each contain about 25 wt%) to form a homogeneous pink-colored mass like dough. An appropriate amount of Disperal, CoCO3, La2(CO3)3, and 37 wt% aqueous HCOOH were mixed in a kneader. Then, the kneaded mass was formed into 4 mm ropes. The ropes were dried at 90 °C for 10 h and then calcined at 400 °C for 4 h. The extrudate passed through a tabletting step to form tablets lobed into four. Then, the calcined extrudate was ground. Then, the material was sieved using a 1000 micrometer mesh sieve. Then, the sieved powder was mixed with 3 wt% graphite (Asbury Graphite 3160) and 3 wt% microcrystalline cellulose (Vivapur SCG102). The resulting mixture was tabletted into compacts having a four-hole cross-section. The diameter of the compact was 16.74 mm and the height was 9.84 mm. The tablets were calcined.

[0121] For calcination, the compacts were heated to a temperature of 700 °C within 3 hours and the temperature was held for 1 hour. Then, the compacts were further heated to a temperature in the range of 1170 - 1200 °C and the temperature was held within this range for 4 hours. The calcination was carried out in a tempering furnace.

[0122] Next, the molded product was divided into particles having an inner diameter of 0.5 to 1 mm.

[0123] Comparative Example 2: Preparation of a composite oxide of Co, La, and Al 30.7 kg of aqueous AlOOH (Disperal; Sasol; containing 77.9 wt% Al calculated as Al2O3), 5.5 kg of cobalt(II) carbonate hydrate (containing 46 wt% Co; Umicore, Todini), and 16.1 kg of lanthanum(III) carbonate hydrate (containing 39.3 wt% La; Mongolia Baotuo Steel Rare Earth Int.trade co.ltd) were premixed in a kneader for several minutes. Then, 23 kg of aqueous formic acid (containing 37 wt% formic acid; BASF SE based on formic acid having 98 - 100 wt%) was added under mixing to form a uniform pink-colored mass like dough.

[0124] Next, the kneaded mass was formed into a 6 mm rope. The rope was dried at 95 - 120 °C for 10 h, then calcined at 400 - 440 °C for 4 h, and then divided into particles having an inner diameter of 0.5 to 1 mm. Before the catalyst test, the divided product was calcined. For calcination, the molded product was heated to a temperature of 700 °C within 3 hours and the temperature was held for 1 hour. Then the molded product was further heated to a temperature of 1200 °C and the temperature was held for 4 hours. The calcination was carried out in a tempering furnace.

[0125] Example 3: Preparation of a composite oxide of Co, La, and Al 162.36 g of aqueous AlOOH (Disperal; Sasol; containing 71.6 wt% Al calculated as Al2O3), 29.59 g of cobalt(II) carbonate hydrate (containing 46 wt% Co; abcr_Germany_GmbH), and 97.57 g of lanthanum(III) carbonate hydrate (containing 41 wt% La; Alfa_Aesar_USA_GmbH&CoKG) were premixed in a kneader for several minutes. Then, 140 ml of aqueous formic acid (containing 37 wt% formic acid; Bernd Kraft GmbH based on formic acid having 98 - 100 wt%) was added under mixing to form a uniform pink-colored mass like dough.

[0126] Next, the kneaded mass was formed into a 3.5 mm rope. The rope was dried at 90 °C for 16 h, then calcined at 400 °C for 4 h, and then divided into particles having an inner diameter of 0.5 - 1 mm. Before the catalyst test, the divided product was calcined. For calcination, the formed product was heated to a temperature of 700 °C within 3 hours and the temperature was held for 1 hour. Then the formed product was further heated to a temperature of 1200 °C and the temperature was held for 4 hours. The calcination was carried out in a tempering furnace.

[0127] Example 4: Preparation of a composite oxide of Co, La, and Al 165.8 g of aqueous AlOOH (Disperal; Sasol; containing 77.6 wt% Al calculated as Al2O3), 30.9 g of cobalt(II) carbonate hydrate (containing 45 wt% Co; ABCR lot1102550), and 119.5 g of lanthanum(III) carbonate hydrate (containing 41 wt% La; Alfa Aesar lotY04D030) were premixed in a kneader for several minutes. Then, 120 ml of aqueous formic acid (containing 30 wt% formic acid; Bernd Kraft GmbH based on formic acid having 98 - 100 wt%) was added under mixing to form a uniform pink-colored mass like dough.

[0128] Next, the kneaded mass was formed into 3.5 mm ropes. The ropes were dried at 90 °C for 16 h, then calcined at 400 °C for 4 h, and then divided into particles having an inner diameter of 0.5 - 1 mm. Before the catalyst test, the divided product was calcined. For calcination, the formed product was heated to a temperature of 700 °C within 3 hours and the temperature was maintained for 1 hour. Then the formed product was further heated to a temperature of 1200 °C and the temperature was maintained for 4 hours. The calcination was carried out in a tempering furnace.

[0129] Example 5: Preparation of a composite oxide of Co, La, and Al 155.8 g of aqueous AlOOH (Disperal; Sasol; containing 77.9 wt% Al calculated as Al2O3), 29.7 g of cobalt(II) carbonate hydrate (containing 46 wt% Co; ABCR lot1102550), 132.1 g of lanthanum(III) carbonate hydrate (containing 41 wt% La; Alfa Aesar lotY04D030) were premixed in a kneader for several minutes. Then, 140 ml of aqueous formic acid (containing 37 wt% formic acid; Bernd Kraft GmbH having 98 - 100 wt% formic acid) was added under mixing to form a uniform pink-colored mass like dough.

[0130] Next, the kneaded mass was formed into 3.5 mm ropes. The ropes were dried at 90 °C for 16 h, then calcined at 400 °C for 4 h, and then divided into particles having an inner diameter of 0.5 - 1 mm. Before the catalyst test, the divided product was calcined. For calcination, the formed product was heated to a temperature of 700 °C within 3 hours and the temperature was maintained for 1 hour. Then the formed product was further heated to a temperature of 1200 °C and the temperature was maintained for 4 hours. The calcination was carried out in a tempering furnace.

[0131] Example 6: Preparation of a composite oxide of Co, La, and Al 151.9 g of aqueous AlOOH (Disperal; Sasol; containing 77.9 wt% Al calculated as Al2O3), 29.7 g of cobalt(II) carbonate hydrate (containing 46 wt% Co; ABCR lot1102550), and 152.5 g of lanthanum(III) carbonate hydrate (containing 41 wt% La; Alfa Aesar lotY04D030) were premixed in a kneader for several minutes. Then, 140 ml of aqueous formic acid (containing 51 wt% formic acid; Bernd Kraft GmbH based on formic acid having 98 - 100 wt%) was added under mixing to form a uniform pink-colored mass like dough.

[0132] The kneaded mass was then formed into 3.5 mm ropes. The ropes were dried at 90 °C for 16 h, then calcined at 400 °C for 4 h, and then divided into particles having an inner diameter of 0.5 - 1 mm. Before the catalyst test, the divided product was calcined. For calcination, the formed product was heated to a temperature of 700 °C within 3 hours and the temperature was held for 1 hour. Then the formed product was further heated to a temperature of 1200 °C and the temperature was held for 4 hours. The calcination was carried out in a tempering furnace.

[0133] Example 7: Preparation of a composite oxide of Co, La, and Al 160 g of aqueous AlOOH (Disperal; Sasol; containing 77.6 wt% Al calculated as Al2O3), 31.1 g of cobalt(II) carbonate hydrate (containing 46 wt% Co; Umicore lot29371A0205 / BASF SE), and 160.1 of lanthanum(III) carbonate hydrate (containing 41 wt% La; Mongolia Baotuo Steel Rare Earth Int.trade co.ltd) were premixed in a kneader for several minutes. Then, 140 ml of aqueous formic acid (containing 51 wt% formic acid; Bernd Kraft GmbH based on formic acid having 98 - 100 wt%) was added under mixing to form a uniform pink-colored mass like dough.

[0134] Subsequently, the kneaded mass was formed into a 3.5 mm rope. The rope was dried at 90 °C for 16 h, then calcined at 400 °C for 4 h, and then divided into particles having an inner diameter of 0.5 - 1 mm. Before the catalyst test, the divided product was calcined. For calcination, the formed product was heated to a temperature of 700 °C within 3 hours and the temperature was maintained for 1 hour. Subsequently, the formed product was further heated to a temperature of 1200 °C and the temperature was maintained for 4 hours. The calcination was carried out in a tempering furnace.

[0135] Comparative Example 8: Preparation of a composite oxide of Co, La, and Al 160 g of aqueous AlOOH (Disperal; Sasol; containing 77.6 wt% Al calculated as Al2O3), 28.6 g of cobalt(II) carbonate hydrate (containing 46 wt% Co; Umicore lot29371A0205 BASF SE), 80.5 g of lanthanum(III) carbonate hydrate (containing 41 wt% La; Mongolia Baotuo Steel Rare Earth Int.trade co.ltd) were premixed in a kneader for several minutes. Subsequently, 120 ml of aqueous formic acid (containing 37 wt% formic acid; Bernd Kraft GmbH based on formic acid having 98 - 100 wt%) was added under mixing to form a uniform pink-colored mass like dough.

[0136] Subsequently, the kneaded mass was formed into a 3.5 mm rope. The rope was dried at 90 °C for 16 h, then calcined at 400 °C for 2 h, and then divided into particles having an inner diameter of 0.5 - 1 mm. Before the catalyst test, the divided product was calcined. For calcination, the formed product was heated to a temperature of 700 °C within 3 hours and the temperature was maintained for 1 hour. Subsequently, the formed product was further heated to a temperature of 1200 °C and the temperature was maintained for 4 hours. The calcination was carried out in a tempering furnace.

[0137] Example 9: Preparation of a composite oxide of Co, La, and Al 160 g of aqueous AlOOH (Disperal; Sasol; containing 77.6 wt% Al calculated as Al2O3), 31.9 g of cobalt(II) carbonate hydrate (containing 46 wt% Co; Umicore lot29371A0205), and 186.3 g of lanthanum(III) carbonate hydrate (containing 41 wt% La; Mongolia Baotuo Steel Rare Earth Int. trade co., ltd) were premixed in a kneader for several minutes. Subsequently, 140 ml of aqueous formic acid (containing 59 wt% formic acid; Bernd Kraft GmbH, based on formic acid having 98 - 100 wt%) was added under mixing to form a uniform pink-colored paste-like mass.

[0138] Subsequently, the kneaded mass was formed into 3.5 mm ropes. The ropes were dried at 90 °C for 16 h, then calcined at 400 °C for 2 h, and then divided into particles having an inner diameter of 0.5 - 1 mm. Before the catalyst test, the divided product was calcined. For calcination, the formed product was heated to a temperature of 700 °C within 3 hours and the temperature was held for 1 hour. Then the formed product was further heated to a temperature of 1200 °C and the temperature was held for 4 hours. The calcination was carried out in an annealing furnace.

[0139] Evaluation of Catalyst Characteristics As can be understood from the elemental analysis shown in Table 1, the La content increased in the examples of the present invention, while both Al and Co decreased, resulting in a sample with an increased amount of the LaAlO3 (Co-doped) phase (see Table 2).

[0140] [Table 3]

[0141] [Table 4]

[0142] From the results of the TPR analysis performed for Comparative Example 1 shown in FIGS. 1 and 2 and for Examples 4, 5, and 6, it is worth noting that by increasing the amount of the LaAlO3 (Co-doped) phase, a lower temperature peak that has a beneficial effect on the activation behavior appears in the TPR. These observations are confirmed by the results from the TPR analysis shown in FIG. 3 performed for Comparative Examples 2 and 8 and for Examples 7 and 9, and the latter examples have an increased amount of Co-doped LaAlO3 and show a lower temperature peak in the TPR compared to the results obtained using the samples from Comparative Examples 2 and 8.

[0143] As can be understood from the results shown in Table 3, the lattice constant of the LaAl (Co) O3-phase decreases with a decrease in the Co content and an increase in the La content in the composite material. This seems to correlate with the fact that the LaAl 3+ O3-phase would show a lower value for the lattice constant a when it contains less cobalt compared to Al 3+ due to the somewhat larger ionic radius of Co. Thus, the LaAl (Co) O3-phase of the examples of the present invention contains less cobalt than the LaAl (Co) O3-phase of the comparative examples. (Co)

[0144]

Table 5

[0145] Example 10: Catalyst test in the reforming of methane in the presence of H2O and CO2 The catalytic tests were carried out in a single reactor test unit on samples from Comparative Examples 1 and 2 and Examples 3, 5, and 6. CO2, CH4, N2, and Ar were provided as gas feeds and were controlled online by an MFC. Water was added to the feed stream by an evaporator connected to a water storage tank. Analysis of the product gas composition was carried out by online-GC using Ar as an internal standard. The GC-analysis enables quantification of H2, CO, CO2, CH4, and C2 components. The duration of the GC method was set to 24 minutes.

[0146] For the catalytic tests, typically, 15 ml of catalyst as a split (0.5 - 1.0 mm) was tested. The sample was placed in the isothermal zone of the reactor using ceramic accessories. The back pressure was measured before the start of the experiment. All catalysts were tested at a pressure of 20 bar, where, for the starting stage (Stage #1), a feed of 95% N2 and 5% Ar was applied to the catalyst surface at a GHSV of 8000 h -1 −1, and the reactor was heated to 900 °C (14 h) with a ramp of 1.07 K / min, followed by a feed of 80% N2, 5% Ar, and 15% H2O at a GHSV of 8000 h -1 −1 at 900 °C for 20 minutes on the catalyst surface. After the starting stage, each catalyst sample was tested under the conditions shown in Table 4 according to a test protocol comprising five further phases.

[0147]

Table 6

[0148] As can be understood from the results from the catalytic tests shown in Figures 4 and 5 and showing the conversion rate of methane (Figure 4) and the conversion rate of CO2 (Figure 5) during the course of the test, Stage 3 is an activation stage where the conversion rate increases at a certain rate as a function of time-on-stream. In Stages 4 and 5, the performance of the catalyst usually evolves sufficiently and the conversion rate values can either decrease due to progressive deactivation of the catalyst or remain constant with increasing reaction time.

[0149] Based on the quantification of the product gas stream, the CH4 conversion rate [1], CO2 - conversion rate [2], H2 / CO ratio, as well as the product gas composition and C2 - component ratio were calculated. CH4 - conversion rate: X(CH4)=1-(CH4 - out / CH4 - in) [1] CO2 - conversion rate: X(CO2)=1-(CO2 - out / CO2 - in) [2]

[0150] In addition, the relative conversion rates of CH4 [3] and CO2 [4] were calculated. It represents the conversion rate related to the thermodynamic maximum conversion rate X_max (equilibrium composition). The equilibrium composition is calculated taking into account the test conditions appropriately. CH4 - relative conversion rate: X_rel(CH4)=X(CH4) / X_max(CH4) [3] CO2 - relative conversion rate: X_rel(CO2)=X(CO2) / X_max(CO2) [4]

[0151] As described above, the experimental conversion rates are compared for the catalyst examples in Figures 4 and 5. As can be understood from the results, compared with Comparative Examples 1 and 2, Example 3 already shows a significantly improved methane conversion rate during the activation stage (see Figure 4), and the highest conversion rates for both methane and CO2 conversions for the samples from Example 3 not only reach well before the highest conversion rates of the samples from Comparative Examples 1 and 2, but are also substantially higher than the latter's highest conversion rates (see stage (4) in Figures 4 and 5 respectively). On the other hand, Examples 5 and 6 show a much easier activation that clearly starts already at 900 °C, especially for the samples from Example 6 (see stage (3) in Figures 4 and 5 respectively).

[0152] Therefore, quite unexpectedly, the unique composition of the samples of the present invention leads to a distinct jump in the conversion activity during the activation stage, and it has been found that it provides a clearly higher highest conversion rate at a much earlier stage of the reaction compared to the samples from Comparative Examples 1 and 2.

[0153] Cited references - International Publication No. WO 2013 / 118078 A1 Pamphlet - International Publication No. WO 2014 / 135642 A1 Pamphlet - International Publication No. WO 2015 / 091310 A1 Pamphlet - US Patent Application Publication No. 2016 / 0207031 A1 Specification - US Patent No. 9,566,571 B2 Specification - International Publication No. WO 2014 / 001423 A1 Pamphlet - International Publication No. WO 2015 / 135968 A1 Pamphlet - International Publication No. WO 2016 / 062853 A1 Pamphlet - International Publication No. WO 2020 / 157202 A1 Pamphlet

Claims

1. A composite oxide comprising oxygen, lanthanum, aluminum, and cobalt, wherein the Co:La weight ratio of cobalt to lanthanum in the composite oxide, calculated as elements, is in the range of 0.06:1 to 0.34:

1.

2. The composite oxide according to claim 1, wherein the composite oxide contains 1 to 15% by weight of cobalt as calculated as an element.

3. The composite oxide according to claim 1, wherein the composite oxide contains 5 to 50% by weight of lanthanum, calculated as an element.

4. The composite oxide according to claim 1, wherein the composite oxide contains 5 to 60% by weight of aluminum, calculated as an element.

5. The composite oxide according to claim 1, wherein the Co:Al weight ratio of cobalt to aluminum in the composite oxide, calculated as an element, is in the range of 0.05:1 to 0.50:

1.

6. The aforementioned composite oxide is LaAl １－ｘ Co ｘ O ３ The composite oxide according to claim 1, comprising a phase (wherein 0 < x < 1 in the formula).

7. The LaAl １－ｘ Co ｘ O ３ The composite oxide according to claim 6, wherein the lattice constant a of the phase is in the range of 3.7920 to 3.7955 Å.

8. The aforementioned composite oxide is LaCoAl １１ O １９ A composite oxide according to claim 1, comprising a phase.

9. The composite oxide according to claim 1, wherein the composite oxide exhibits a degree of crystallinity in the range of 80 to 100%.

10. A method for producing a composite oxide according to Claim 1, wherein the method is (i) Prepare a mixture of one or more Al sources, one or more Co sources, and one or more La sources; (ii) Adding an acidic aqueous solution to the mixture prepared in (i); (iii) Homogenizing the mixture obtained in (iii); (iv) optionally, to obtain a molded article, the mixture obtained in (iii) is molded; (v) optionally drying the mixture obtained in (iii) or the molded article obtained in (iv); (vi) optionally pre-calcining the mixture obtained in (iii) or (v), or the molded body obtained in (iv) or (v); (vii) optionally milling the dried and / or pre-calcined mixture or molded body obtained in (v) or (vi); (vii) Optionally, tablet the pulverized material obtained in (vii); A manufacturing method comprising calcining the mixture obtained in (ix), (iii), (v), or (vi), or the molded article obtained in (iv), (v), or (vi), or the pulverized material obtained in (vii), or the tablet obtained in (viiii).

11. A composite oxide that is available or obtainable according to the method described in claim 10.

12. A method for producing a catalyst for the conversion of hydrocarbons into synthesis gas, wherein the method is (1) To provide the composite oxide described in claim 1, or to prepare the composite oxide according to claim 10; (2) Reduction of the composite oxide prepared in (1) to obtain a catalyst A manufacturing method that includes this.

13. The method according to claim 12, wherein the reduction in (2) is carried out in an atmosphere containing one or more reducing agents, wherein the one or more reducing agents include one or more of methane, hydrogen, and carbon monoxide.

14. A catalyst for the conversion of hydrocarbons to synthesis gas, as available or obtainable according to the method described in Claim 12.

15. A process for converting hydrocarbons into synthesis gas, wherein the process is: (A) To provide the composite oxide described in claim 1, or the catalyst described in claim 14; (B) preparing a gas stream comprising one or more hydrocarbons and one or more of CO ２ and H ２ O; (C) The gas stream prepared in (B) is brought into contact with the composite oxide provided in (A) at a temperature in the range of 700 to 1,200°C. The conversion process, including the conversion process.

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