A MOLDING COMPRISING A MIXED OXIDE COMPRISING OXYGEN, LANTHANUM, ALUMINUM, AND COBALT

Abstract

A molding comprising a mixed oxide, wherein the mixed oxide comprises oxygen, lanthanum, aluminum, and cobalt, wherein in the mixed oxide, the weight ratio of cobalt relative to aluminum, calculated as elements, is at least 0.17:1. A preparation method by a dry route. Use of the molding as a catalyst for the reforming of hydrocarbons into a synthesis gas.

Claims

1.-15. (canceled)

16. A molding, comprising a mixed oxide, wherein the mixed oxide comprises oxygen, lanthanum, aluminum, and cobalt, wherein in the mixed oxide, the weight ratio of cobalt relative to aluminum, calculated as elements, is at least 0.17:1.

17. The molding of claim 16, wherein in the mixed oxide, the weight ratio of cobalt relative to aluminum, calculated as elements, is in the range of from 0.17:1 to 0.24:1.

18. The molding of claim 16, wherein in the mixed oxide, the weight ratio of cobalt relative to lanthanum, calculated as elements, is in the range of from 0.35:1 to 0.48:1.

19. The molding of claim 16, wherein from 99 to 100 weight-% of the mixed oxide consist of oxygen, lanthanum, aluminum, cobalt, and optionally hydrogen.

20. The molding of claim 16, wherein the mixed oxide comprises one or more of a crystalline phase of LaCoAl.sub.11O.sub.19 and a crystalline phase of LaAl(Co)O.sub.3.

21. The molding of claim 20, wherein the mixed oxide comprises a crystalline phase of LaCoAl.sub.11O.sub.19 and a crystalline phase of LaAl(Co)O.sub.3, wherein in the mixed oxide, the weight ratio of LaCoAl.sub.11O.sub.19 relative to LaAl(Co)O.sub.3 is in the range of from 5:1 to 30:1.

22. The molding of claim 16, wherein from 99 to 100 weight-% of the molding consist of the mixed oxide.

23. The molding of claim 16, having a BET specific surface area in the range of from 1 to 10 m.sup.2/g.

24. A process for preparing the molding comprising a mixed oxide of claim 16, the process comprising (i) preparing a mixture comprising a lanthanum salt, a cobalt salt, an oxidic aluminum compound, and an acid, wherein one or more of the lanthanum salt and the cobalt salt are not a nitrate; (ii) preparing a molding from the mixture obtained from (i), comprising (ii.1) subjecting the mixture obtained from (i) to a shaping process, obtaining a first molding; (ii.2) preferably drying the first molding obtained from (ii.1) in a gas atmosphere; (ii.3) calcining the first molding obtained from (ii.1) or (ii.2), preferably from (ii.2), in a gas atmosphere having a temperature in the range of from 350 to 470° C.; (iv) calcining the molding obtained from (ii) or (iii), preferably from (iii), in a gas atmosphere having a temperature in the range of from 1100 to 1400° C., obtaining the molding comprising the mixed oxide.

25. The process of claim 24, wherein the process further comprises a third step (iii), prior to step (iv), the third step comprising subjecting the calcined first molding obtained from (ii) to a re-shaping process, obtaining a second molding having a geometry different from the geometry of the first molding.

26. The process of claim 24, wherein the acid according to (i) is one or more of formic acid, acetic acid, propionic acid, nitric acid, nitrous acid, citric acid, tartaric acid, and oxalic acid.

27. The process of claim 24, wherein in the mixture prepared in (i), the molar ratio of the acid relative to cobalt is in the range of from 1:2 to 9:1.

28. The process of claim 24, consisting of (i), (ii), (iii) and (iv).

29. A molding comprising a mixed oxide comprising oxygen, lanthanum, aluminum, and cobalt, obtainable or obtained by a process according to any claim 24.

30. Use of a molding of claim 16 as a catalytically active material, as a catalyst component or as a catalyst for reforming one or more hydrocarbons, wherein the hydrocarbons are selected from the group consisting of methane, ethane, propane and butane, to a synthesis gas comprising hydrogen and carbon monoxide, in the presence of carbon dioxide.

Description

EXAMPLES

Reference Example 1: Determination of the Side Crushing Strength

[0191] The side crushing strength was determined on a semi-automatic tablet testing system SotaxST50 WTDH. The side crushing strength was measured with a constant speed of 0.05 mm/s. A range of from 0 to 800 N could be tested. For each measurement, the orientation of the sample was adjusted with a horizontal rotating table and fine adjustment has been made manually. Further, several measurement parameters were adjusted—if applicable—depending on the orientation and properties of the sample, such as the mass, the height/thickness, the diameter and strength at rupture. The gained data were evaluated with the scientific program q-doc prolab (version 4fsp2 (4.10)). Moldings having a four-hole cross-section were tested, whereby three positions being perpendicular to each other were probed allowing determination of the side crushing strength 1, side crushing strength 2 and side crushing strength 3. The relative standard deviation for crushing strength 1, 2, and 3 was 7.48%.

[0192] As can be seen in FIG. 1, side crushing strength 1 refers to a position of the molding in the semi-automatic tablet testing system where the sample stands on two cylindrical segments sided by a flute on the rotating table, side crushing strength 2 refers to a position where the sample stands on one cylindrical segment on the rotating table, and side crushing strength 3 refers to a position where the holes are in parallel to the direction of the force applied on the sample during the test.

Reference Example 2: Determination of the BET Specific Surface Area and the Langmuir Specific Surface Area

[0193] The BET specific surface area and the Langmuir specific surface area were determined via nitrogen physisorption at 77K according to the method disclosed in DIN 66131.

Reference Example 3: Determination of Crystallinity Via XRD

[0194] Powder X-ray Diffraction (PXRD) data were collected using a laboratory diffractometer (D8 Discover, Bruker AXS GmbH, Karlsruhe). The instrument was set up with a Molybdenum X-ray tube. The characteristic K-alpha radiation was monochromatized using a bent Germanium Johansson type primary monochromator. Data were collected in the Bragg-Brentano reflection geometry. A LYNXEYE area detector was utilized to collect the scattered X-ray signal.

[0195] The powders were ground using an IKA Tube Mill and an 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). DIFFRAC.EVA was used to estimate the crystallinity. Default values were used as input for the algorithm (DIFFRAC.EVA User Manual, 2014, Bruker AXS GmbH, Karlsruhe). All other parameters were determined using DIFFRAC.TOPAS. The entire diffraction pattern was simulated using the crystal structures of hexagonal LaCoAl.sub.11O.sub.19, rhombohedral LaAlO.sub.3, cubic CoAl.sub.2O.sub.4, hexagonal La(OH).sub.3, cubic Co-doped LaAlO.sub.3 and Corundum. During the simulation 29 parameters were refined to fit the simulated diffraction to the measured data.

[0196] The parameters are listed in the following Table 1.

TABLE-US-00001 TABLE 1 Parameters for refining Parameter Structure No. of variables Background via Chebychev global 2 polynomial Background via peak global 3 at ca. 6.6° 2theta Specimen displacement global 1 hexagonal LaCoAl.sub.11O.sub.19 Crystallite size 1 Scale factor 1 Lattice 2 Preferred orientation* 1 cubic Co-doped LaAlO.sub.3 Crystallite size 1 Scale factor 1 Lattice 1 Co doping factor 1 rhombohedral LaAlO.sub.3 Crystallite size 1 Scale factor 1 Lattice 2 Corundum Crystallite size 1 Scale factor 1 Lattice 2 cubic CoAl.sub.2O.sub.4 Crystallite size 1 Scale factor 1 Lattice 1 hexagonal La(OH).sub.3 Scale factor 1 Lattice 2 *Using the March-Dollase model along the (110) direction.

[0197] All 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). The following Table 2 lists the reference numbers of the structures used.

TABLE-US-00002 TABLE 2 Numbers of structures used ICSD Number PCD Number hexagonal LaCoAl.sub.11O.sub.19 1502158 cubic Co-doped LaAlO.sub.3 1501066 rhombohedral LaAlO.sub.3  28629 Corundum 1520618 cubic CoAl.sub.2O.sub.4 163275 hexagonal La(OH).sub.3 192271

[0198] The crystallite size values are those reported as Lvol-FWHM in DIFFRAC.TOPAS. To ensure reliable crystallite size values the geometry of the diffractometer was entered into the software to enable the calculation of the instrumental resolution based on the fundamental parameter approach (DIFFRAC.TOPAS User Manual, 2014, Bruker AXS GmbH, Karlsruhe). Scale factors were recomputed into mass percent values by DIFFRAC.TOPAS and have been reported.

Reference Example 4: Determination of UV/Vis Spectrum

[0199] UV/Vis data were collected using a spectrophotometer (Cary 5000 spectrophotometer; performance range from 175 to 3300 nm; controlled by Cary WinUV software). The apparatus was calibrated with a white standard. A sample was tested using a sample cell. Further, an External Diffuse Reflectance Accessories (DRAs) and a powder cell kit were used. The powder cell kit contained a pre-packed PTFE cell for use as a reflectance standard and an empty powder cell holder for sample measurements. Each cell had a quartz window and measures samples across 200 to 2500 nm wavelength ranges.

Reference Example 5: Determination of the Side Crushing Strength

[0200] The side crushing strength was determined on a tablet testing system (Typ BZ2.5/TS1S, Zwick). The side crushing strength was been measured using a punching tool. The side crushing strength was recorded as soon as the sample broke. For each measurement, the orientation of the sample was adjusted manually on a horizontal table. The punching tool was arranged to punch from above. Further, several measurement parameters were adjusted—if applicable—depending on the orientation and properties of the sample, such as the mass, the height/thickness, the diameter and strength at rupture. Moldings having a four-hole cross-section were tested, whereby three positions being perpendicular to each other were probed allowing determination of the side crushing strength 1, side crushing strength 2 and side crushing strength 3.

[0201] As can be seen in FIG. 1, side crushing strength 1 refers to a position of the molding in the semi-automatic tablet testing system where the sample stands on two cylindrical segments sided by a flute on the rotating table, side crushing strength 2 refers to a position where the sample stands on one cylindrical segment on the rotating table, and side crushing strength 3 refers to a position where the holes are in parallel to the direction of the force applied on the sample during the test.

Example 1: Preparation of an Inventive Molding

[0202] 70 kg aqueous AlOOH (Disperal; Sasol; containing 77.6 weight-% of Al calculated as Al.sub.2O.sub.3), 13.04 kg cobalt(II)carbonate hydrate (containing 55.92 weight-% of Co, calculated as CoO; Umicore), 49.27 kg lanthanum(III)carbonate hydrate (containing 49.26 weight-% La calculated as La.sub.2O.sub.3; Inner Mongolia) were pre-mixed for several minutes in a Koller or in a mixer. Then, 50.79 kg aqueous formic acid (containing 37 weight-% formic acid; based on formic acid having 98-100 weight-%, Bernd Kraft GmbH, CAS #: 64-18-6) were added in three portions, wherein the first portion contains about 50 weight-%, the second and the third portion each about 25 weight % of the total aqueous formic acid, under mixing and a dough-like homogeneous pink mass was formed. The obtained mass was then extruded to strands with 4 mm in diameter. The extrudates were dried at 90° C. for 16 hours. Subsequently, the dried extrudates were calcined in air at 400° C. for 4 hours. Thereafter, the calcined extrudates were grinded. Then, the material was sieved using sieves with a mesh of 1000 micrometer. The sieved powder was then mixed with 3 weight-% graphite (Asbury Graphite 3160) and 3 weight-% microcrystalline cellulose (Vivapur SCG102). The resulting mixture was tableted to moldings having a four-hole cross-section as shown in FIG. 1. Ten samples of the moldings were characterized as concerns the side crushing strengths, the diameter and the height. The moldings had a side crushing strength 1 of (100±29) N, a side crushing strength 2 of (75±11.9) N and a side crushing strength 3 of (217±22.1) N, determined according to Reference Example 1. The diameter of a molding was 16.74 mm and the height was 9.84 mm. For calcination, the moldings were heated within 3 hours to a temperature of 700° C. and said temperature was hold for 1 hour. Then the moldings were heated further to a temperature in the range of from 1170 to 1200° C., and the temperature was hold in this range for 4 hours. The calcination was done in an annealing furnace. The cobalt content of the calcined moldings was 7.4 weight-%, the lanthanum content 17.7 weight-% and the aluminum content 36 weight-%, calculated as the elements, respectively. Five samples of the finally calcined moldings of Example 1 were characterized as concerns the side crushing strength 1, 2, and 3, determined according to Reference Example 1. The results are listed in table 1 below. Further, the diameter, the height and the mass of each sample is listed in Table 3.

TABLE-US-00003 TABLE 3 Results for testing the side crushing strength 1, 2 and 3 for five samples # Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 SCS1 [N] 507 459 422 561 500 SCS2 [N] 236 202 260 259 256 SCS3 [N] 563 530 636 763 636 Diameter [mm] 15.24 15.09 15.18 15.29 15.5 Height [mm] 8.90 8.72 8.82 8.79 8.88 Mass 1.923 1.845 1.924 1.946 1.971

[0203] Four samples of the calcined moldings of example 1 have been characterized as concerns the BET specific surface area and the Langmuir specific surface area, determined according to Reference Example 2. The results are listed in Table 4 below.

TABLE-US-00004 TABLE 4 Results for testing the BET specific surface area and the Langmuir specific surface area for four samples # Sample A Sample B Sample C Sample D BET [m.sup.2/g] 9.3 9.3 8.0 8.6 Langmuir [m.sup.2/g] 13.2 13.1 11.3 12.2

Comparative Example 2: Preparation of a Molding According to the Prior Art as Regards a Comparison of the Catalytic Activity

[0204] Comparative Example 2 was prepared in accordance with WO 2013/118078 A1.

[0205] 6.000 kg aqueous AlOOH (Disperal; Sasol; containing 78.1 weight-% of Al calculated as Al.sub.2O.sub.3), 2.042 kg cobalt(II)nitrate hexahydrate (containing 25.7 weight-% of Co, calculated as CoO; Merck), 4.962 kg lanthanum(III)nitrate hexahydrate (containing 37.6 weight-% La calculated as La.sub.2O.sub.3; Sigma-Aldrich) were mixed for several minutes in a kneader or in a mixer. Then, 0.68 kg deionized water were added. Under mixing a dough-like homogeneous pink mass was formed. The obtained mass was then extruded to strands with 4 mm in diameter. The extrudates were dried at 105° C. for 16 hours. Subsequently, the dried extrudates were calcined in air at 520° C. for 2 hours. Thereafter, the calcined extrudates were grinded. The split fraction between 0.5 to 1.0 mm was calcined. The split was heated within 4.5 hours to a temperature of 1100° C., and said temperature was hold for 30 hours. The calcination was done in an annealing furnace. The cobalt content of the calcined moldings was 5.4 weight-%, the lanthanum content 22.6 weight-% and the aluminum content 35 weight-%, calculated as the elements, respectively.

Comparative Example 3: Preparation of a Molding According to the Prior Art as Regards a Comparison of the Mechanical Strength

[0206] Comparative Example 3 was prepared in accordance with WO 2013/118078 A1.

[0207] 21.57 kg aqueous AlOOH (Disperal; Sasol; containing 78.0 weight-% of Al calculated as Al.sub.2O.sub.3), 39.01 kg Al.sub.2O.sub.3 (Puralox SCCa 150/200; Sasol; containing 99.1 weight-% of Al calculated as Al.sub.2O.sub.3), 22.9 kg cobalt(II)nitrate hexahydrate (containing 20.0 weight-% of Co, calculated as element; Sheperd), 56.52 kg lanthanum(III)nitrate hexahydrate (containing 37.5 weight-% La calculated as La.sub.2O.sub.3; Treibacher) were mixed for several minutes in a kneader or in a mixer. Then, 9.8 kg deionized water were added. Under mixing a dough-like homogeneous pink mass was formed. The obtained mass was then extruded to strands with 4 mm in diameter. The extrudates were dried at 140° C. for 16 hours. Subsequently, the dried extrudates were calcined in air at 550° C. for 4 hours, with a period of 2 h at 280° C. during heating up to allow for NOx evolution.

[0208] Then, the material was sieved using sieves with a mesh of 1000 micrometer. The sieved powder was then mixed with 3 weight-% graphite (Asbury Graphite 3160) and 3 weight-% microcrystalline cellulose (Spheres 2000). The resulting mixture was tableted to moldings having a four-hole cross-section as shown in FIG. 1. Ten samples of the moldings were characterized as concerns the side crushing strengths, the diameter and the height. The moldings had a side crushing strength 1 of (175±53) N, a side crushing strength 2 of (57±6) N, determined according to Reference Example 5. The diameter of a molding was 16.79 mm and the height was 10.50 mm. For calcination, the moldings were heated within 5 hours to a temperature of 1200° C., and said temperature was hold for 4 hours. The calcination was done in an annealing furnace. The cobalt content of the calcined moldings was 5.6 weight-%, the lanthanum content 22.2 weight-% and the aluminum content 36 weight-%, calculated as the elements, respectively. Ten samples of the finally calcined moldings were characterized as concerns the side crushing strength 1, 2, and 3, determined according to Reference Example 5. The results are listed in table 5 below. Further, the diameter, the height and the mass of each sample is listed in Table 5.

TABLE-US-00005 TABLE 5 Results for testing the side crushing strength 1, 2 and 3 # Sample SCS1 [N] 283 SCS2 [N] 143 SCS3 [N] 232 Diameter [mm] 15.36 Height [mm] 9.73 Mass 2.2

[0209] When comparing the results for the side crushing strength 1, 2, and 3 for the moldings in accordance with the Inventive Example 1 as shown in table 3 with the results for Comparative Example 3 as shown in above table 5, it can be seen that each of the side crushing strength 1, 2, and 3 is clearly lower for the molding of Comparative Example 3 even though it was tableted and calcined at similar conditions according to Inventive Example 1. Therefore, the molding according to the present invention shows superior properties in particular with regard to the mechanical strength in comparison to the molding according to Comparative Example 3 representing the prior art.

Example 4: Catalytic Performance of Inventive Example 1 and of Comparative Example 2

[0210] Catalytic tests were performed on a single reactor test unit. This unit allowed for test conditions in a broad temperature and pressure regime up to 1100° C. and 20 bar (gauge). As gas feeds carbon dioxide (also designated as carbon dioxide-in or CO.sub.2-in), methane (also designated as methane-in or CH.sub.4-in), hydrogen (also designated as hydrogen-in), nitrogen (also designated as nitrogen-in) and argon (also designated as argon-in) were provided and online controlled by mass flow controllers (MFCs). Water was added as steam to the feed stream by an evaporator connected to a water reservoir. Analysis of the product gas composition was carried out by online-gas chromatography using argon as internal standard. Gas chromatographic analytics allowed the quantification of hydrogen, carbon monoxide, carbon dioxide (also designated as CO.sub.2-out), methane (also designated as CH.sub.4-out) and C.sub.2 components. Duration of the gas chromatographic method was set to 24 min. For the catalytic test, the prepared molding was split (0.5 to 1.0 mm) and 15 ml of the split were then tested as a catalyst. The sample was placed in the isothermal zone of the reactor using a ceramic fitting. Prior to the start of the experiment the back pressure was determined. The catalyst was tested according to a standard test protocol according to Table 6.

TABLE-US-00006 TABLE 6 Test protocol used for catalytic testing. In each phase the pressure was adjusted to 20 bar (gauge) Time on Phase stream T GHSV Methane-in CO.sub.2-in Steam-in Argon-in Nitrogen-in [#] [h] [° C.] [h.sup.−1] [Vol.-%] [Vol.-%] [Vol.-%] [Vol.-%] [Vol.-%]  1.a) 14 25-900 8000 0.0 0.0 0.0 5.0 95.0  1.b) 0.3 900 8000 0.0 0.0 15.0 5.0 80.0 2 6 900 8000 40.0 40.0 15.0 5.0 0.0 3 30 950 4000 40.0 40.0 15.0 5.0 0.0 4 24 950 4000 37.5 37.5 20.0 5.0 0.0 5 12 950 8000 37.5 37.5 20.0 5.0 0.0 6 12 950 8000 40.0 40.0 15.0 5.0 0.0 7 12 950 4000 37.5 37.5 20.0 5.0 0.0 8 12 950 4000 40.0 40.0 15.0 5.0 0.0 Shut- 20 950-25  8000 0.0 0.0 0.0 5.0 95.0 down GHSV: gas hourly space velocity

[0211] Phases 1.a) and 1.b) were the start-up phase. Phase 3 was an activation phase in which the conversion increased with a certain rate as a function of time on stream. In phases 4 to 8 the performance of the catalyst fully evolved, and conversion values either decreased due to progressing deactivation of the catalyst or remained constant with increasing reaction time. Based on the quantification of the product gas stream the methane conversion [1], carbon dioxide conversion [2], hydrogen/carbon monoxide ratio as well as the product gas composition and C.sub.2-components fraction were calculated:

Methane conversion: X(CH.sub.4)=1-(CH.sub.4-out/CH.sub.4-in)  [1]

Carbon dioxide conversion: X(CO.sub.2)=1-(CO.sub.2-out/CO.sub.2-in)  [2]

[0212] In addition, the relative conversions of methane [3] and carbon dioxide [4] were calculated and represent the conversions related to the thermodynamic maximum conversions X_max (equilibrium composition). The equilibrium composition was calculated taking the test conditions accordingly into account:

Methane-relative conversion: X_rel(CH.sub.4)=X(CH.sub.4)/X_max(CH.sub.4)  [3]

Carbon dioxide-relative conversion: X_rel(CO.sub.2)=X(CO.sub.2)/X_max(CO.sub.2)  [4]

[0213] The experimental values for the relative methane and carbon dioxide conversion were averaged (averaged methane is designated as a-CH.sub.4 and averaged carbon dioxide is designated as a-CO.sub.2) over time on stream for each reaction phase (n=number of measurement points) according to equation [5] and [6].

a-CH.sub.4=1/nΣ[X_rel(CH.sub.4)]  [5]

a-CO.sub.2=1/nΣ[X_rel(CO.sub.2)]  [6]

[0214] As it can be gathered from FIG. 2 for Inventive Example 1, the absolute conversion reached a level of about 95% relative to a gas hourly space velocity of 4000 1/h, whereby at a gas hourly space velocity of 8000 1/h the conversion was still above 80%. As can be seen in FIG. 4 for Comparative Example 2, the conversion reached a level of less than 70% relative to a gas hourly space velocity of 4000 1/h, whereby at a gas hourly space velocity of 8000 1/h the conversion dropped at about 45% and stayed below a level of 50% for both the conversion of methane as well as of carbon dioxide.

[0215] As regards the absolute conversion shown in FIGS. 2 and 4, the catalyst in accordance with the Inventive Example 1 reached conversion levels of above 80% with respect to carbon dioxide and methane for the first time after a time on stream (TOS) between 15 and 20 h, whereas the catalyst in accordance with Comparative Example 2 reached conversion levels of above 60% with respect to carbon dioxide and methane for the first time after a time on stream (TOS) between 25 and 30 h, not to mention that the maximum level of conversion stayed for Comparative Example 2 below 70% for the whole time on stream. Said results clearly indicate a superior activity of the catalyst in accordance with Inventive Example 1 compared to the catalyst in accordance with Comparative Example 2.

[0216] Further, it is shown in FIGS. 3 and 5 that the relative conversion as regards methane and carbon dioxide for a gas hourly space velocity of 4000 1/h for Inventive Example 1 reached a maximum level of about 95% for the first time at around 20 h time on stream, but for Comparative Example 2 the relative conversion reached a maximum level of about 80% for the first time at around 55 to 60 h time on stream. Further, the relative conversion stayed in the range of 80 to 90% for Inventive Example 1 when the gas hourly space velocity was 8000 1/h, whereas the relative conversion stayed in the range of 50 to 60% for Comparative Example 2 when the gas hourly space velocity was 8000 1/h. Said results clearly indicate that the catalyst in accordance with the present invention shows superior catalytic activity with regard to the conversion of methane and carbon dioxide in comparison to the catalyst in accordance with Comparative Example 2.

[0217] Thus, it can be clearly seen that the catalyst in accordance with Inventive Example 1 shows superior catalytic properties in comparison to the catalyst in accordance with Comparative Example 2 representing the prior art.

BRIEF DESCRIPTION OF FIGURES

[0218] FIG. 1: shows on the left the side view for the arrangement for determining side crushing strength 1 (SCS1), in the middle the side view for the arrangement for determining side crushing strength 2 (SCS2), and on the right the side view for the arrangement for determining side crushing strength 3 (SCS3).

[0219] FIG. 2: shows on the ordinate (left) the conversion of carbon dioxide and methane in % for a process for producing a synthesis gas using the split (powder fraction of 0.5 to 1.0 mm) of the molding according to inventive example 1. The temperature (in ° C.), the composition of the reactant gas stream (in volume-%), and the gas hourly space velocity (GHSV; in 1/h) are also shown on the ordinate (right). The time on stream (TOS) is shown on the abscissa.

[0220] FIG. 3: shows on the ordinate (left) the relative conversion of carbon dioxide and methane in % for a process for producing a synthesis gas using the split (powder fraction of 0.5 to 1.0 mm) of the molding according to inventive example 1. The temperature (in ° C.), the composition of the reactant gas stream (in volume-%), and the gas hourly space velocity (GHSV; in 1/h) are also shown on the ordinate (right). The time on stream (TOS) is shown on the abscissa.

[0221] FIG. 4: shows on the ordinate (left) the conversion of carbon dioxide and methane in % for a process for producing a synthesis gas using the split (powder fraction of 0.5 to 1.0 mm) of the molding according to Comparative Example 2. The temperature (in ° C.), the composition of the reactant gas stream (in volume-%), and the gas hourly space velocity (GHSV; in 1/h) are also shown on the ordinate (right). The time on stream (TOS) is shown on the abscissa.

[0222] FIG. 5: shows on the ordinate (left) the relative conversion of carbon dioxide and methane in % for a process for producing a synthesis gas using the split (powder fraction of 0.5 to 1.0 mm) of the molding according to Comparative Example 2. The temperature (in ° C.), the composition of the reactant gas stream (in volume-%), and the gas hourly space velocity (GHSV; in 1/h) are also shown on the ordinate (right). The time on stream (TOS) is shown on the abscissa.

CITED LITERATURE

[0223] WO 2013/118078 A1 [0224] U.S. Pat. No. 9,259,712 B2