Cobalt- and strontium-based catalysts for the conversion of hydrocarbons to synthesis gas

Abstract

The present invention relates to a composite oxide containing oxygen, lanthanum, aluminum, strontium, and cobalt, wherein the Co:Sr weight ratio of cobalt to strontium in the composite oxide, calculated as elements, is in the range of 0.01:1 to 20:1, to a method for producing such a composite oxide, to a method for producing a catalyst for the conversion of hydrocarbons to synthesis gas, and to a catalyst for the conversion of hydrocarbons to synthesis gas obtained from such a method. Finally, the present invention relates 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, strontium, and cobalt, wherein the composite oxide has a specific Co:Sr 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 production costs 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 costs.

[0003] WO 2013 / 118078 A1 relates to Ni- or Co-containing hexaaluminate catalysts for the reforming of hydrocarbons. WO 2014 / 135642 A1 relates to Ni-containing hexaaluminate catalysts for the reforming of hydrocarbons in the presence of CO2. Similarly, WO 2015 / 091310 A1 relates to a method for reforming a mixture of hydrocarbons and CO2. US 2016 / 0207031 A1 and US 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 one 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.

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 formulation, particularly a Co-containing catalyst formulation 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, particularly a catalyst formulation in which the rate at which the catalyst is activated is increased. Thus, unexpectedly, a Co-containing catalyst formulation containing lanthanum and further containing Sr at a specific Co:Sr weight ratio within a specific range enables substantially higher reducibility of the catalyst at low temperatures, as a result of which the activation of the catalyst is significantly improved and can thus be achieved in a much shorter period of time. As a result, it has been found, quite unexpectedly, that a highly cost-effective Co-containing catalyst can be provided.

[0009] Therefore, the present invention relates to a composite oxide containing oxygen, lanthanum, aluminum, strontium, and cobalt, wherein the Co:Sr weight ratio of cobalt to strontium in the composite oxide, calculated as elements, is in the range of 0.01:1 to 20:1, preferably 0.03:1 to 10:1, more preferably 0.05:1 to 5:1, more preferably 0.08:1 to 2:1, more preferably 0.10:1 to 1.50:1, more preferably 0.15:1 to 1.25:1, more preferably 0.20:1 to 1.10:1, more preferably 0.25:1 to 0.95:1, more preferably 0.30:1 to 0.80:1, more preferably 0.35:1 to 0.65:1, more preferably 0.40:1 to 0.55:1, more preferably 0.43:1 to 0.47:1.

[0010] The composite oxide preferably contains 1 to 15% by weight, more preferably 2.5 to 12.0% by weight, more preferably 4.0 to 10.5% by weight, more preferably 5.5 to 9.0% by weight, more preferably 6.1 to 8.4% by weight, more preferably 6.3 to 8.2% by weight, more preferably 6.5 to 8.0% by weight, more preferably 6.7 to 7.8% by weight, more preferably 6.8 to 7.7% by weight of cobalt, calculated as elements.

[0011] The composite oxide preferably contains 1 to 22.0% by weight, more preferably 2.5 to 20.0% by weight, more preferably 4.0 to 18.5% by weight, more preferably 5.0 to 17.5% by weight, more preferably 5.3 to 17.2% by weight, more preferably 5.6 to 16.9% by weight, more preferably 5.8 to 16.7% by weight, more preferably 5.9 to 16.6% by weight, more preferably 6.0 to 16.5% by weight of strontium, calculated as elements.

[0012] The composite oxide preferably contains 3.0 to 20.0% by weight, more preferably 5.0 to 18.0% by weight, more preferably 6.0 to 17.0% by weight, more preferably 6.8 to 16.2% by weight, more preferably 7.1 to 15.9% by weight, more preferably 7.4 to 15.6% by weight, more preferably 7.6 to 15.4% by weight, more preferably 7.7 to 15.3% by weight, more preferably 7.8 to 15.2% by weight of lanthanum, calculated as an element.

[0013] The composite oxide preferably contains 26.0 to 45% by weight, more preferably 27.8 to 43.1% by weight, more preferably 28.8 to 42.1% by weight, more preferably 29.8 to 41.1% by weight, more preferably 30.3 to 40.6% by weight, more preferably 30.8 to 40.1% by weight, more preferably 31.1 to 39.8% by weight, more preferably 31.3 to 39.6% by weight, more preferably 31.4 to 39.5% by weight of aluminum, calculated as an element.

[0014] The Co:Al weight ratio of cobalt to aluminum in the composite oxide, calculated as an element, is preferably in the range of 0.02:1 to 0.50:1, more preferably 0.05:1 to 0.45:1, more preferably 0.08:1 to 0.38:1, more preferably 0.10:1 to 0.33:1, more preferably 0.12:1 to 0.30:1, more preferably 0.14:1 to 0.27:1, more preferably 0.16:1 to 0.25:1, more preferably 0.18:1 to 0.23:1, more preferably 0.19:1 to 0.22:1.

[0015] The Sr:La weight ratio of strontium to lanthanum in the composite oxide, calculated as an element, is preferably in the range of 0.10:1 to 2.70:1, more preferably 0.20:1 to 2.50:1, more preferably 0.30:1 to 2.40:1, more preferably 0.40:1 to 2.30:1, more preferably 0.50:1 to 2.20:1, more preferably 0.60:1 to 2.10:1, more preferably 0.64:1 to 2.06:1, more preferably 0.66:1 to 2.04:1, more preferably 0.67:1 to 2.03:1.

[0016] The composite oxide preferably contains SrAl 12 O 19 phase.

[0017] When the composite oxide contains SrAl 12 O 19 phase, the composite oxide preferably contains SrAl 12 O 19 phase in an amount in the range of 10 to 80% by weight, more preferably 15 to 70% by weight, more preferably 20 to 60% by weight, 25 to 55% by weight, more preferably 30 to 53% by weight, more preferably 35 to 51% by weight, more preferably 37 to 49% by weight, more preferably 39 to 47% by weight, more preferably 41 to 45% by weight, based on 100% by weight of the composite oxide, wherein the amount of SrAl 12 O 19 phase in the composite oxide is preferably determined according to the method of Reference Example 1.

[0018] The composite oxide preferably contains Sr(Al2O4) phase.

[0019] When the composite oxide contains the Sr(Al2O4) phase, the composite oxide preferably contains the Sr(Al2O4) phase in an amount in the range of 0.5 to 50% by weight, more preferably 1 to 40% by weight, more preferably 2 to 30% by weight, more preferably 3 to 25% by weight, 3 to 25% by weight, more preferably 4 to 20% by weight, more preferably 5 to 18% by weight, more preferably 6 to 15% by weight, more preferably 7 to 12% by weight, more preferably 8 to 10% by weight, based on 100% by weight of the composite oxide. Here, the amount of the Sr(Al2O4) phase in the composite oxide is preferably determined according to the method of Reference Example 1.

[0020] The composite oxide preferably contains the LaSrAl3O7 phase.

[0021] When the composite oxide contains the LaSrAl3O7 phase, the composite oxide preferably contains the LaSrAl3O7 phase in an amount in the range of 0 to 6% by weight, more preferably 0.1 to 4% by weight, more preferably 0.2 to 3% by weight, more preferably 0.4 to 2.5% by weight, more preferably 0.6 to 2% by weight, 0.6 to 2% by weight, more preferably 0.8 to 1.8% by weight, more preferably 1.0 to 1.6% by weight, more preferably 1.2 to 1.4% by weight, based on 100% by weight of the composite oxide. Here, the amount of the LaSrAl3O7 phase in the composite oxide is preferably determined according to the method of Reference Example 1.

[0022] The composite oxide preferably contains the LaAlO3 phase.

[0023] When the composite oxide contains the LaAlO3 phase, the composite oxide preferably contains the LaAlO3 phase in an amount in the range of 1 to 35% by weight, more preferably 3 to 32% by weight, more preferably 5 to 30% by weight, 10 to 28% by weight, more preferably 12 to 25% by weight, more preferably 13 to 23% by weight, more preferably 15 to 20% by weight, more preferably 17 to 18% by weight, based on 100% by weight of the composite oxide. Here, the amount of the LaAlO3 phase in the composite oxide is preferably determined according to the method of Reference Example 1.

[0024] The composite oxide preferably contains a CoAl2O4 phase, more preferably a CoAl2O4 spinel phase.

[0025] When the composite oxide contains a CoAl2O4 phase, preferably a CoAl2O4 spinel phase, the composite oxide contains the CoAl2O4 phase in an amount in the range of 15.4 to 40% by weight, more preferably 16.4 to 32% by weight, more preferably 17.4 to 28% by weight, more preferably 17.9 to 26% by weight, more preferably 19 to 24% by weight, more preferably 19.5 to 23% by weight, more preferably 20 to 22% by weight, based on 100% by weight of the composite oxide, and here, the amount of the CoAl2O4 phase in the composite oxide is preferably determined according to the method of Reference Example 1.

[0026] The composite oxide preferably contains an Sr2CoO4 phase.

[0027] When the composite oxide contains an Sr2CoO4 phase, the composite oxide preferably contains the Sr2CoO4 phase in an amount in the range of 1 to 20% by weight, more preferably 3 to 16% by weight, 4 to 14% by weight, more preferably 5 to 12% by weight, more preferably 6 to 10% by weight, more preferably 7 to 8% by weight, based on 100% by weight of the composite oxide, and here, the amount of the Sr2CoO4 phase in the composite oxide is preferably determined according to the method of Reference Example 1.

[0028] The composite oxide preferably contains 1% by weight or less, more preferably 0.5% by weight or less, more preferably 0.1% by weight or less, more preferably 0.05% by weight or less, more preferably 0.01% by weight or less, more preferably 0.005% by weight or less, more preferably 0.001% by weight or less of LaCoAl 11 O 19 phase, and here, more preferably, the composite oxide does not contain the LaCoAl 11 O 19 phase, and here, the LaCoAl in the composite oxide 11 O19 The amount of the phase is preferably determined according to the method of Reference Example 1.

[0029] The composite oxide preferably exhibits a crystallinity in the range of 30 to 95%, more preferably 38 to 87%, more preferably 43 to 82%, more preferably 46 to 79%, more preferably 48 to 77%, and more preferably 49 to 76%. Here, the crystallinity of the composite oxide is preferably determined according to the method of Reference Example 1.

[0030] 99 to 100% by weight, more preferably 99.5 to 100% by weight, and more preferably 99.9 to 100% by weight of the composite oxide preferably consists of oxygen, lanthanum, aluminum, strontium, cobalt, and optionally hydrogen.

[0031] The composite oxide is preferably in the form of a powder or a molded article, more preferably in the form of a molded article.

[0032] When the composite oxide is in the form of a powder or a molded article, preferably in the form of a molded article, it is more preferable that 99 to 100% by weight, more preferably 99.5 to 100% by weight, and more preferably 99.9 to 100% by weight of the powder or the molded article consists of the composite oxide.

[0033] The composite oxide is preferably obtained or available according to the method described in any one of the specific and preferred embodiments of the present invention relating to the production of the composite oxide.

[0034] The present invention relates to a method for producing a composite oxide, preferably a composite oxide according to any one of the specific and preferred embodiments of the present invention, (i) preparing a mixture of one or more Al sources, one or more Co sources, one or more strontium 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, in order to obtain a shaped body, preferably by extrusion, shaping the mixture obtained in (iii); (v) Optionally, drying the mixture obtained in (iii) or the shaped body obtained in (iv); (vi) Optionally, pre-firing the mixture obtained in (iii) or (v), or the shaped body 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) relates to a production method comprising the above steps.

[0035] In this context, 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, wherein the one or more alumina sources are more preferably AlO(OH).

[0036] 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, cobalt iodide, and mixtures of two or more thereof. Here, one or more Co sources are more preferably cobalt carbonate, and more preferably, cobalt carbonate contains CoCO3·yH2O (where 0 ≦ y ≦ 7, preferably 0 ≦ y ≦ 6), and more preferably is cobalt carbonate itself.

[0037] 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, lanthanum iodide, and mixtures of two or more thereof. Here, one or more lanthanum sources are more preferably lanthanum carbonate, and more preferably, lanthanum carbonate contains La2(CO3)3·xH2O (where 0 ≦ x ≦ 10, more preferably 0 ≦ x ≦ 6), and more preferably is lanthanum carbonate itself.

[0038] One or more Sr sources are preferably selected from the group consisting of strontium carbonate, strontium fluoride, strontium chloride, strontium bromide, strontium iodide, strontium sulfate, strontium nitrate, strontium hydroxide, strontium oxide, and mixtures of two or more thereof. Here, one or more strontium sources are more preferably strontium carbonate.

[0039] The mixture in (i) is preferably prepared by kneading one or more sources of Al, Co, Sr, and La.

[0040] 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, and more preferably contains one or more of formic acid and nitric acid. Here, the acidic aqueous solution added in (ii) more preferably contains formic acid.

[0041] The homogenization in (iii) is preferably achieved by stirring, more preferably kneading, the mixture obtained in (ii).

[0042] 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, even more preferably in the range of 100 to 110 °C.

[0043] 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, even more preferably in the range of 8 to 10 h.

[0044] 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, even more preferably in the range of 400 to 450 °C.

[0045] The pre-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, even more preferably in the range of 3.5 to 4.5 h.

[0046] The firing in (vi) 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, even more preferably in the range of 1100 to 1300 °C.

[0047] The 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, even more preferably in the range of 3.5 to 4.5 h.

[0048] The present invention also 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 relating to the production of the composite oxide.

[0049] 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 described in any one of the specific and preferred embodiments of the present invention regarding the production of the composite oxide; (2)Reducing the composite oxide prepared in (1) to obtain a catalyst >, relating to a production method.

[0050] The reduction in (2) is preferably 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, more preferably include methane and / or hydrogen, and more preferably methane used in (2) as the reducing agent.

[0051] 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, more preferably 850 to 900 °C.

[0052] 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, more preferably 18 to 20 bara.

[0053] 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, more preferably 5 to 7 h.

[0054] 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 regarding the production of a catalyst for the conversion of hydrocarbons to synthesis gas.

[0055] The present invention also relates to a process for the conversion of hydrocarbons to synthesis gas, wherein this process (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 according to any one of the specific and preferred embodiments of the present invention; (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 or catalyst 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 Regarding a process comprising.

[0056] The gas stream prepared in (B) preferably contains one or more hydrocarbons, CO2 and H2O.

[0057] The one or more hydrocarbons are preferably selected from the group consisting of C1-C10 alkanes, more preferably C1-C8 alkanes, more preferably C1-C6 alkanes, more preferably C1-C4 alkanes, more preferably C1-C3 alkanes, more preferably 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.

[0058] The gas stream prepared in (B) preferably contains one or more hydrocarbons in the range of 20 to 80% by volume, more preferably 25 to 60% by volume, more preferably 30 to 50% by volume, more preferably 35 to 45% by volume, more preferably 38 to 42% by volume.

[0059] The gas stream prepared in (B) preferably contains 20 to 80% by volume, more preferably 25 to 60% by volume, more preferably 30 to 50% by volume, more preferably 35 to 45% by volume, and more preferably 38 to 42% by volume of CO2.

[0060] The gas stream prepared in (B) preferably contains 1 to 30% by volume, more preferably 5 to 25% by volume, more preferably 10 to 20% by volume, more preferably 12 to 18% by volume, and more preferably 14 to 16% by volume of H2O.

[0061] 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.

[0062] When the gas stream prepared in (B) further contains one or more inert gases, the gas stream prepared in (B) preferably contains 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 of one or more inert gases.

[0063] 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.

[0064] (C) The contacting in is 500 to 25,000 h -1 more 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.

[0065] The present invention is further illustrated by the following series of embodiments and combinations of embodiments obtained from the shown dependencies and backward references. In particular, in each case where the scope of an embodiment is referred to in connection with terms such as "a 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, that is, it is pointed out that the syntax of this term should be understood by those skilled in the art as being synonymous with "a 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 appropriately structured parts 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.

[0066] 1. A composite oxide comprising oxygen, lanthanum, aluminum, strontium, and cobalt, wherein the Co:Sr weight ratio of cobalt to strontium in the composite oxide, calculated as elements, is in the range of 0.01:1 to 20:1, preferably 0.03:1 to 10:1, more preferably 0.05:1 to 5:1, more preferably 0.08:1 to 2:1, more preferably 0.10:1 to 1.50:1, more preferably 0.15:1 to 1.25:1, more preferably 0.20:1 to 1.10:1, more preferably 0.25:1 to 0.95:1, more preferably 0.30:1 to 0.80:1, more preferably 0.35:1 to 0.65:1, more preferably 0.40:1 to 0.55:1, more preferably 0.43:1 to 0.47:1.

[0067] 2. The composite oxide according to Embodiment 1, wherein the composite oxide contains cobalt in an amount of 1 to 15% by weight, preferably 2.5 to 12.0% by weight, more preferably 4.0 to 10.5% by weight, more preferably 5.5 to 9.0% by weight, more preferably 6.1 to 8.4% by weight, more preferably 6.3 to 8.2% by weight, more preferably 6.5 to 8.0% by weight, more preferably 6.7 to 7.8% by weight, more preferably 6.8 to 7.7% by weight, calculated as elements.

[0068] 3. The composite oxide contains strontium in an amount of 1 to 22.0% by weight, preferably 2.5 to 20.0% by weight, more preferably 4.0 to 18.5% by weight, more preferably 5.0 to 17.5% by weight, more preferably 5.3 to 17.2% by weight, more preferably 5.6 to 16.9% by weight, more preferably 5.8 to 16.7% by weight, more preferably 5.9 to 16.6% by weight, more preferably 6.0 to 16.5% by weight, calculated as an element, and is the composite oxide according to Embodiment 1 or 2.

[0069] 4. The composite oxide contains lanthanum in an amount of 3.0 to 20.0% by weight, preferably 5.0 to 18.0% by weight, more preferably 6.0 to 17.0% by weight, more preferably 6.8 to 16.2% by weight, more preferably 7.1 to 15.9% by weight, more preferably 7.4 to 15.6% by weight, more preferably 7.6 to 15.4% by weight, more preferably 7.7 to 15.3% by weight, more preferably 7.8 to 15.2% by weight, calculated as an element, and is the composite oxide according to any one of Embodiments 1 to 3.

[0070] 5. The composite oxide contains aluminum in an amount of 26.0 to 45% by weight, preferably 27.8 to 43.1% by weight, more preferably 28.8 to 42.1% by weight, more preferably 29.8 to 41.1% by weight, more preferably 30.3 to 40.6% by weight, more preferably 30.8 to 40.1% by weight, more preferably 31.1 to 39.8% by weight, more preferably 31.3 to 39.6% by weight, more preferably 31.4 to 39.5% by weight, calculated as an element, and is the composite oxide according to any one of Embodiments 1 to 4.

[0071] 6. The Co:Al weight ratio of cobalt to aluminum in the composite oxide, calculated as an element, is in the range of 0.02:1 to 0.50:1, preferably 0.05:1 to 0.45:1, more preferably 0.08:1 to 0.38:1, more preferably 0.10:1 to 0.33:1, more preferably 0.12:1 to 0.30:1, more preferably 0.14:1 to 0.27:1, more preferably 0.16:1 to 0.25:1, more preferably 0.18:1 to 0.23:1, more preferably 0.19:1 to 0.22:1, and is the composite oxide according to any one of Embodiments 1 to 5.

[0072] 7. The Sr:La weight ratio of strontium to lanthanum in the composite oxide, calculated as an element, is in the range of 0.10:1 to 2.70:1, preferably 0.20:1 to 2.50:1, more preferably 0.30:1 to 2.40:1, more preferably 0.40:1 to 2.30:1, more preferably 0.50:1 to 2.20:1, more preferably 0.60:1 to 2.10:1, more preferably 0.64:1 to 2.06:1, more preferably 0.66:1 to 2.04:1, more preferably 0.67:1 to 2.03:1, and is the composite oxide according to any one of Embodiments 1 to 6.

[0073] 8. The composite oxide is SrAl 12 O 19 and contains a phase, and is the composite oxide according to any one of Embodiments 1 to 7.

[0074] 9. The composite oxide contains SrAl 12 O 19 in an amount in the range of 10 to 80% by weight, preferably 15 to 70% by weight, more preferably 20 to 60% by weight, 25 to 55% by weight, more preferably 30 to 53% by weight, more preferably 35 to 51% by weight, more preferably 37 to 49% by weight, more preferably 39 to 47% by weight, more preferably 41 to 45% by weight, based on 100% by weight of the composite oxide, wherein the amount of the SrAl 12 O 19 phase in the composite oxide is preferably determined according to the method of Reference Example 1. The composite oxide according to Embodiment 8.

[0075] 10. The composite oxide is the composite oxide according to any one of Embodiments 1 to 9, which contains an Sr(Al2O4) phase.

[0076] 11. The composite oxide contains the Sr(Al2O4) phase in an amount in the range of 0.5 to 50% by weight, preferably 1 to 40% by weight, more preferably 2 to 30% by weight, still more preferably 3 to 25% by weight, 3 to 25% by weight, still more preferably 4 to 20% by weight, still more preferably 5 to 18% by weight, still more preferably 6 to 15% by weight, still more preferably 7 to 12% by weight, still more preferably 8 to 10% by weight, based on 100% by weight of the composite oxide, wherein the amount of the Sr(Al2O4) phase in the composite oxide is preferably determined according to the method of Reference Example 1. The composite oxide according to Embodiment 10.

[0077] 12. The composite oxide is the composite oxide according to any one of Embodiments 1 to 11, which contains a LaSrAl3O7 phase.

[0078] 13. The composite oxide contains the LaSrAl3O7 phase in an amount in the range of 0 to 6% by weight, preferably 0.1 to 4% by weight, more preferably 0.2 to 3% by weight, still more preferably 0.4 to 2.5% by weight, still more preferably 0.6 to 2% by weight, 0.6 to 2% by weight, still more preferably 0.8 to 1.8% by weight, still more preferably 1.0 to 1.6% by weight, still more preferably 1.2 to 1.4% by weight, based on 100% by weight of the composite oxide, wherein the amount of the LaSrAl3O7 phase in the composite oxide is preferably determined according to the method of Reference Example 1. The composite oxide according to Embodiment 12.

[0079] 14. The composite oxide is the composite oxide according to any one of Embodiments 1 to 13, which contains a LaAlO3 phase.

[0080] 15. The composite oxide contains a LaAlO3 phase in an amount of 1 to 35% by weight, preferably 3 to 32% by weight, more preferably 5 to 30% by weight, 10 to 28% by weight, more preferably 12 to 25% by weight, more preferably 13 to 23% by weight, more preferably 15 to 20% by weight, more preferably 17 to 18% by weight, based on 100% by weight of the composite oxide. Here, the amount of the LaAlO3 phase in the composite oxide is preferably determined according to the method of Reference Example 1. The composite oxide according to Embodiment 14.

[0081] 16. The composite oxide contains a CoAl2O4 phase, preferably a CoAl2O4 spinel phase, and is the composite oxide according to any one of Embodiments 1 to 15.

[0082] 17. The composite oxide contains a CoAl2O4 phase in an amount in the range of 15.4 to 40% by weight, preferably 16.4 to 32% by weight, more preferably 17.4 to 28% by weight, more preferably 17.9 to 26% by weight, more preferably 19 to 24% by weight, more preferably 19.5 to 23% by weight, more preferably 20 to 22% by weight, based on 100% by weight of the composite oxide. Here, 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 16.

[0083] 18. The composite oxide contains an Sr2CoO4 phase and is the composite oxide according to any one of Embodiments 1 to 17.

[0084] 19. The composite oxide contains an Sr2CoO4 phase in an amount in the range of 1 to 20% by weight, preferably 3 to 16% by weight, 4 to 14% by weight, more preferably 5 to 12% by weight, more preferably 6 to 10% by weight, more preferably 7 to 8% by weight, based on 100% by weight of the composite oxide. Here, the amount of the Sr2CoO4 phase in the composite oxide is preferably determined according to the method of Reference Example 1. The composite oxide according to Embodiment 18.

[0085] 20. The composite oxide contains 1 wt% or less, preferably 0.5 wt% or less, more preferably 0.1 wt% or less, still more preferably 0.05 wt% or less, still more preferably 0.01 wt% or less, still more preferably 0.005 wt% or less, still more preferably 0.001 wt% or less of LaCoAl, based on 100 wt% of the composite oxide. 11 O 19 phase, and more preferably the composite oxide does not contain the LaCoAl 11 O 19 phase. Here, 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 any one of Embodiments 1 to 19.

[0086] 21. The composite oxide exhibits a crystallinity in the range of 30 to 95%, preferably 38 to 87%, more preferably 43 to 82%, still more preferably 46 to 79%, still more preferably 48 to 77%, still more preferably 49 to 76%. Here, 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 20.

[0087] 22. 99 to 100 wt%, preferably 99.5 to 100 wt%, more preferably 99.9 to 100 wt% of the composite oxide is the composite oxide according to any one of Embodiments 1 to 21, which consists of oxygen, lanthanum, aluminum, strontium, cobalt, and optionally hydrogen.

[0088] 23. The composite oxide is in the form of a powder or a molded article, preferably in the form of a molded article, and is the composite oxide according to any one of Embodiments 1 to 22.

[0089] 24. 99 to 100 wt%, preferably 99.5 to 100 wt%, more preferably 99.9 to 100 wt% of the powder or the molded article consists of the composite oxide, and is the composite oxide according to Embodiment 23.

[0090] 25. The composite oxide is the composite oxide according to any one of Embodiments 1 to 24, which is obtained or available according to the method described in any one of Embodiments 26 to 37.

[0091] 26. A method for producing a composite oxide, preferably the composite oxide according to any one of Embodiments 1 to 24, the method comprising: (i) preparing a mixture of one or more Al sources, one or more Co sources, one or more strontium 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, shaping the mixture obtained in (iii) to obtain a shaped body, preferably by extrusion; (v) optionally, drying the mixture obtained in (iii) or the shaped body obtained in (iv); (vi) optionally, pre-firing the mixture obtained in (iii) or (v), or the shaped body 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.

[0092] 27. The at least one Al source is 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 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 the at least one alumina source is more preferably AlO(OH), the method according to embodiment 26.

[0093] 28. The at least one Co source is 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, cobalt iodide, and mixtures of two or more thereof, and the at least one Co source is 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, the method according to embodiment 26 or 27.

[0094] 29. 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, lanthanum iodide, and mixtures of two or more thereof, and the at least one lanthanum source is preferably lanthanum carbonate containing La2(CO3)3·xH2O (where 0≦x≦10, more preferably 0≦x≦6) more preferably, and more preferably it is lanthanum carbonate, the method according to any one of embodiments 26 to 28.

[0095] The at least one Sr source is selected from the group consisting of strontium carbonate, strontium fluoride, strontium chloride, strontium bromide, strontium iodide, strontium sulfate, strontium nitrate, strontium hydroxide, strontium oxide, and mixtures of two or more thereof, and the at least one strontium source is preferably strontium carbonate, the method according to any one of Embodiments 26 to 29.

[0096] The mixture in (i) is prepared by kneading at least one source of Al, Co, Sr, and La, the method according to any one of Embodiments 26 to 30.

[0097] The acidic aqueous solution added in (ii) contains one or more of formic acid, acetic acid, propionic acid, nitric acid, nitrous acid, citric acid, tartaric acid, and oxalic acid, preferably one or more of formic acid and nitric acid, and the acidic aqueous solution added in (ii) more preferably contains formic acid, the method according to any one of Embodiments 26 to 31.

[0098] The homogenization in (iii) is achieved by stirring, preferably kneading, the mixture obtained in (ii), the method according to any one of Embodiments 26 to 32.

[0099] 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 26 to 33.

[0100] 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 26 to 34.

[0101] The pre-firing in (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, the method according to any one of Embodiments 26 to 35.

[0102] The preliminary firing in 37.(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 26 to 36.

[0103] The firing in 38.(vi) 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 26 to 37.

[0104] The firing in 39.(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 26 to 38.

[0105] A composite oxide obtainable or obtained according to the method according to any one of Embodiments 26 to 39.

[0106] 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 Embodiments 1 to 25 and 40, or preparing a composite oxide according to the method according to any one of Embodiments 26 to 39; (2) reducing the composite oxide prepared in (1) to obtain a catalyst The production method comprising.

[0107] The reduction in 42.(2) is carried out in an atmosphere containing one or more reducing agents, and 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 41.

[0108] 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 °C to 1,000 °C, more preferably 800 to 950 °C, and even more preferably 850 to 900 °C, according to the method described in Embodiment 41 or 42.

[0109] 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, and even more preferably 18 to 20 bara, according to the method described in any one of Embodiments 41 to 43.

[0110] 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, and more preferably 5 to 7 h, according to the method described in any one of Embodiments 41 to 44.

[0111] A catalyst for the conversion of hydrocarbons to synthesis gas obtainable or obtainable according to the method described in any one of Embodiments 41 to 45.

[0112] 47. A hydrocarbon conversion process to synthesis gas, the process comprising: (A) providing a composite oxide described in any one of Embodiments 1 to 25 and 40, or a catalyst described in Embodiment 46; (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 or catalyst 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, and even more preferably 900 to 950 °C comprising a conversion process.

[0113] The gas stream prepared in (B) is the process according to embodiment 47, comprising one or more hydrocarbons, CO2 and H2O.

[0114] 49. 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, and more preferably, the gas stream prepared in (B) contains one or more of methane, ethane, and propane, and 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, which is the process according to embodiment 47 or 48.

[0115] 50. 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, which is the method according to any one of embodiments 47-49.

[0116] 51. 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, which is the process according to any one of embodiments 47-50.

[0117] 52. 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, which is the process according to any one of embodiments 47-51.

[0118] 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 47 to 52.

[0119] 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 53.

[0120] 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 47 to 54.

[0121] 56. 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 any one of Embodiments 47 to 55.

Brief Description of the Drawings

[0122]

Figure 1

Modes for Carrying Out the Invention

Examples

[0123] The present invention will be further illustrated by the following Examples, Comparative Examples and Reference Examples.

[0124] Reference Example 1: Composition and Structure Analysis by X-ray Diffraction The sample is ground using a mill until it becomes a fine powder. The mill used is an IKA Tube Mill 100. The milling program used is 20,000 rpm for 60 seconds repeated once.

[0125] Thereafter, the sample is transferred to a standard sample holder (material PMMA, manufacturer Bruker AXS) and flattened using a glass plate. The sample is measured with a D8 Advance diffractometer (Bruker AXS) using MoKa1 radiation, a fixed slit set at 0.1°, and a linear integration area detector (LynxEye, Bruker AXS) with a step size of 0.01° 2θ in the angular range of 2° to 40° 2θ.

[0126] Data analysis is performed using software TOPAS 6 (TOPAS 6 User Manual, Bruker AXS GmbH, Karlsruhe, Germany, 2017). The modeled phase composition is set to SrAl 12 O 19 , CoAl2O4, LaAlO3, SrAl2O4, Sr2CoO4, LaSrAl3O7. For all phases, the lattice constants and microcrystalline sizes are refined. A third 次 -order polynomial is used to model the background. The sample height is also refined. Intensity corrections for Lorentz and polarization effects are considered. Phase quantification is performed by the standard procedure described in Klug, H.P. & Alexander, L.E. (1974), X-ray Diffraction Procedures, 2nd ed. New York: John Wiley. An additional cost factor that suppresses the elemental composition to that measured using an elemental analysis technique (inductively coupled plasma (ICP)) is used to ensure the reliability of the refinement.

[0127] 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 having particles with 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 1 - 3 are shown in Figure 1.

[0128] Example 1: Preparation of a Composite Oxide of Co, La, Sr, and Al 160 g of aqueous AlOOH (Disperal; Sasol; containing 77.6 wt% Al calculated as Al2O3), 28.57 g of cobalt(II) carbonate hydrate (containing 46 wt% Co; Umicore lot29371A0205 / BASF SE), 40.23 g of lanthanum(III) carbonate hydrate (containing 41 wt% La; Mongolia Baotuo Steel Rare Earth Int.trade co.ltd)) and 17.89 g of strontium carbonate (Sigma_Aldrich_Chemie_Germany_GmbH: containing 58.165 wt% Sr) were premixed in a kneader for several minutes. Then, 120 ml of aqueous formic acid (containing 37 wt% formic acid; Bernd Kraft GmbH having 98 - 100 wt%) was added under mixing to form a uniform pink-colored mass like dough.

[0129] 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 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 a tempering furnace.

[0130] The structural analysis based on the X-ray diffraction data obtained for the fired samples was carried out according to the procedure of Reference Example 1 using the elemental composition values of the samples as measured using inductively coupled plasma (ICP) as an elemental analysis technique (see the values in Table 1). The analysis provided the following results regarding the phases in the samples and their relative amounts.

[0131]

Table 1

[0132] Example 2: Preparation of a composite oxide of Co, La, Sr 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), 80.1 g of lanthanum(III) carbonate hydrate (containing 41 wt% La; Mongolia Baotuo Steel Rare Earth Int.trade co.ltd) and 35.6 g of strontium carbonate (Sigma_Aldrich_Chemie_Germany_GmbH: containing 58.165 wt% Sr) 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 homogeneous pink-colored mass like dough.

[0133] 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 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 a tempering furnace.

[0134] The structural analysis based on the X-ray diffraction data obtained for the fired sample was carried out according to the procedure of Reference Example 1 using the elemental composition values of the sample as measured using inductively coupled plasma (ICP) as an elemental analysis technique (see the values in Table 1). The analysis provided the following results regarding the phases in the sample and their relative amounts.

[0135]

Table 2

[0136] Example 3: Preparation of a composite oxide of Co, Sr, 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), 40.03 g of lanthanum(III) carbonate hydrate (containing 41 wt% La; Mongolia Baotuo Steel Rare Earth Int.trade co.ltd) and 53.39 g of strontium carbonate (Sigma_Aldrich_Chemie_Germany_GmbH: containing 58.165 wt% Sr) 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 homogeneous pink-colored mass like dough.

[0137] 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 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 a tempering furnace.

[0138] The structural analysis based on the X-ray diffraction data obtained for the fired samples was carried out according to the procedure of Reference Example 1 using the elemental composition values of the samples as measured by inductively coupled plasma (ICP) as an elemental analysis technique (see the values in Table 1). The analysis provided the following results regarding the phases in the samples and their relative amounts.

[0139]

Table 3

[0140] Catalyst property evaluation The elemental analysis of the samples of Examples 1 to 3 is shown in Table 1.

[0141]

Table 4

[0142] From the results of the TPR analysis carried out for Examples 1 to 3 shown in Figure 1, it is noteworthy that by lowering the Co:Sr weight ratio, lower temperature peaks that have a beneficial effect on the activation behavior are increasingly appearing in the TPR.

[0143] Thus, it was unexpectedly found that a lanthanum-containing Co-containing catalyst formulation in which Sr is further included at a Co:Sr weight ratio 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.

[0144] 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 - International Publication No. WO 2016 / 0207031 A1 Pamphlet - US Patent No. 9,566,571 B2 Specification - Pamphlet of International Publication No. WO 2014 / 001423 A1 - Pamphlet of International Publication No. WO 2015 / 135968 A1 - Pamphlet of International Publication No. WO 2016 / 062853 A1 - Pamphlet of International Publication No. WO 2020 / 157202 A1

Claims

1. A composite oxide comprising oxygen, lanthanum, aluminum, strontium, and cobalt, wherein the Co:Sr weight ratio of cobalt to strontium in the composite oxide, calculated as elements, is in the range of 0.01:1 to 20:

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 1 to 22.0% by weight of strontium, calculated as an element.

4. The composite oxide according to claim 1, wherein the composite oxide contains 3.0 to 20.0% by weight of lanthanum, calculated as an element.

5. The composite oxide according to claim 1, wherein the composite oxide contains 26.0 to 45% by weight of aluminum, calculated as an element.

6. The aforementioned composite oxide is SrAl １２ O １９ A composite oxide according to claim 1, comprising a phase.

7. The aforementioned composite oxide is Sr(Al ２ O ４ The composite oxide according to claim 1, comprising the ) phase.

8. The aforementioned composite oxide is LaSrAl ３ O ７ A composite oxide according to claim 1, comprising a phase.

9. The aforementioned composite oxide is LaAlO ３ A composite oxide according to claim 1, comprising a phase.

10. The composite oxide is CoAl ２ O ４ The composite oxide according to claim 1, which contains a phase.

11. The aforementioned composite oxide is Sr ２ CoO ４ A composite oxide according to claim 1, comprising a phase.

12. A method for producing a composite oxide according to Claim 1, wherein the method comprises (i) preparing a mixture of one or more Al sources, one or more Co sources, one or more strontium 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).

13. 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 a composite oxide according to the method described in claim 12; (2) Reduction of the composite oxide prepared in (1) to obtain a catalyst A manufacturing method that includes this.

14. A catalyst for the conversion of hydrocarbons to synthesis gas, as available or obtainable according to the method described in claim 13.

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) One or more hydrocarbons and CO ２ and H ２ Prepare a gas stream containing one or more types of oxygen; (C) The gas stream prepared in (B) is brought into contact with the composite oxide or catalyst 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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