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STABLE CATALYSTS FOR OXIDATIVE COUPLING OF METHANE

20200048164 ยท 2020-02-13

    Inventors

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    International classification

    Abstract

    A method of selecting a stable mixed metal oxide catalyst for an oxidative coupling of methane (OCM) reaction is disclosed. The method may include, obtaining a mixed metal oxide material having catalytically active metal oxides for the OCM reaction and identifying the Tammann temperature (TTam) of at least one of the catalytically active metals oxides of the mixed metal oxide material. The method further includes selecting the mixed metal oxide material for use as a catalyst in the OCM reaction if the at least one catalytically active metal oxides present in the mixed metal oxide material has a TTam greater than a predetermined temperature.

    Claims

    1. A method of selecting a stable mixed metal oxide catalyst for an oxidative coupling of methane (OCM) reaction, the method comprising: (a) obtaining a mixed metal oxide material having catalytically active metal oxides for the OCM reaction; (b) identifying the Tammann temperature (T.sub.Tam) of at least one of the catalytically active metals oxides of the mixed metal oxide material; and (c) selecting the mixed metal oxide material for use as a catalyst in the OCM reaction if the at least one catalytically active metal oxides present in the mixed metal oxide material has a T.sub.Tam greater than 750 C.

    2. The method of claim 1, wherein the T.sub.Tam for the at least one catalytically active metal oxide is greater than 850 C., preferably greater than 950 C., or more preferably greater than 1000 C., or 750 C. to 1700 C.

    3. The method of claim 1, wherein each of the metal oxides in the mixed metal oxide material has a T.sub.Tam greater than 750 C.

    4. The method of claim 1, wherein the T.sub.Tam of the mixed metal oxide material is above 750 C.

    5. The method of claim 1, wherein the mixed metal oxide material has two catalytically active metal oxides having a metal selected from the group consisting of thorium (Th), magnesium (Mg), strontium (Sr), cerium (Ce), ytterbium (Yb), samarium (Sm), and lanthanum oxide (La.sub.2O.sub.3).

    6. The method of claim 1, wherein the mixed metal oxide material has three catalytically active metal oxides having a metal selected from the group consisting of thorium (Th), magnesium (Mg), strontium (Sr), cerium (Ce), ytterbium (Yb), samarium (Sm), lanthanum (La), erbium (Er), neodymium (Nd), dysprosium (Dy), gadolinium (Gd), europium (Eu), praseodymium (Pr), thulium (Tm), scandium (Sc), yttrbium (Yb), promethium (Pm), terbium (Tb) holmium (Ho), lutetium (Lu), zirconium (Zr), titanium (Ti), zinc (Zn), aluminum (Al), silicon (Si).

    7. The method of claim 1, wherein the OCM reaction operating temperature is 750 C. to 1100 C., most preferably 850 C. to 950 C.

    8. The method of claim 7, wherein the T.sub.Tam is no less than 10% or 20% of the OCM reaction operating temperature.

    9. The method of claim 1, wherein each catalytically active metal oxide present in the mixed metal oxide material is chemically inert with respect to components present in a product stream produced from the OCM reaction.

    10. The method of claim 9, wherein the components in the product stream include C2+ hydrocarbons, carbon dioxide (CO2), and carbon monoxide (CO).

    11. The method of claim 1, further comprising: (d) contacting the selected mixed metal oxide material with a reactant feed comprising methane (CH.sub.4) and oxygen (O.sub.2) to produce a product stream comprising C.sub.2+ hydrocarbons, wherein C.sub.2+ hydrocarbons comprises mixture of ethane, ethylene and C.sub.3 and higher hydrocarbons.

    12. The method of claim 11, wherein reaction step (d) is performed for greater than 500 hours without regenerating the selected mixed metal oxide material.

    13. The method of claim 11, wherein the oxygen (O.sub.2) conversion is greater than 70% or greater than 90% after 500 hours, preferably greater than 1500 hours, time on the stream.

    14. The method of claim 11, wherein the C.sub.2+ hydrocarbon selectivity is greater than 60% or 60% to 85% after 500 hours, preferably greater than 1500 hours, time on the stream.

    15. The method of claim 11, wherein the product stream further comprises carbon dioxide (CO.sub.2) and carbon monoxide (CO).

    16. A method of making a stable mixed metal oxide catalyst for an oxidative coupling of methane (OCM) reaction, the method comprising: (a) selecting at least a first metal oxide material and a second metal oxide material based on the Tammann temperature (T.sub.Tam) of the corresponding metal oxides thereof, wherein the T.sub.Tam of at least one corresponding metal oxide is greater than 750 C.; and (b) combining the first metal oxide material and the second metal oxide material to form a stable material; (c) calcining the stable material to obtain a mixed metal oxide catalyst.

    17. The method of claim 16, wherein the first and second metal oxide materials are metal salts, and wherein combining in step (b) comprises: obtaining a solution comprising the first and second metal oxide metal salts; and (ii) drying the solution at 110 C. to 130 C. to obtain a stable mixture.

    18. The method of claim 16, wherein the first and second metal oxide materials are metal salts, and wherein combining in step (b) comprises: (i) obtaining a first solution comprising the first and a second solution comprising the second metal oxide metal salts; and (ii) adding the first solution to the second solution to precipitate the mixed metal oxide; (iii) drying the solution at 110 C. to 130 C. to obtain the stable mixture.

    19. The method of claim 16, wherein the first and second metal oxide materials are metal oxides, and wherein combining in step (b) comprises pulverizing the metal oxides to form the stable material.

    20. The method of claim 15, wherein step (d) calcining comprises subjecting the material to a temperature greater than 350 C., preferably great than 800 C. in the presence of an oxygen source, preferably air.

    Description

    BRIEF DESCRIPTION OF THE DRAWINGS

    [0018] For a more complete understanding of the present invention, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which:

    [0019] FIG. 1 shows a method of selecting a stable mixed metal oxide catalyst for an oxidative coupling of methane reaction, according to embodiments of the invention;

    [0020] FIG. 2 shows a method of making a stable mixed metal oxide catalyst for an oxidative coupling of methane reaction, according to embodiments of the invention; and

    [0021] FIG. 3 illustrates the performance of SrCeYb oxide catalyst with time on a feed stream of CH.sub.4/O.sub.2.

    DETAILED DESCRIPTION OF THE DISCLOSURE

    [0022] The invention provides for an efficient selection process to identify and prepare oxidative coupling of methane catalysts that have a substantially longer lifetime when compared with currently known OCM catalysts. As illustrated in non-limiting embodiments in the Examples section, this selection process allows for the identification and preparation of such catalysts that remain catalytically active for the OCM reaction for at least 500 hours, preferably at least 1000 hours, or more preferably at least 1500 hours of use (time-on-stream or TOS). Notably, the conversion and selectivity parameters remain stable during such prolonged uses. These and other non-limiting aspects of the present invention are discussed in more detail in the following paragraphs.

    [0023] FIG. 1 shows method 10 for selecting a stable mixed metal oxide catalyst for an oxidative coupling of methane reaction, according to embodiments of the invention. Method 10 may start at block 100, which involves identifying metal oxide materials that are active components for the OCM reaction.

    [0024] It has been discovered that selecting the appropriate mixed metal oxide material for use in the mixed metal oxide catalyst for the oxidative coupling of methane can result in a mixed metal oxide catalyst that is sufficiently stable to catalyze the oxidative coupling of methane reaction over periods not previously achieved. One aspect of the discovery is that one of the features that may be used in selecting the appropriate mixed metal oxide material is the Tammann temperature of at least one or more catalytically active metal oxide(s) in the mixed metal oxide material. The Tammann temperature is the temperature of a solid in degrees K that is sufficient to make atoms or ions of the bulk of the solid sufficiently mobile to cause bulk-to-surface migrations.

    [0025] In method 10, block 101 may include determining (identifying) the Tammann temperature (T.sub.Tam) of the catalytically active metal oxides identified in block 100. Identifying the Tammann temperature of the catalytically active metal oxides may involve testing the identified metal oxides or receiving previously determined Tammann temperature of the catalytically active metal oxides, for example, from publications.

    [0026] Tables 1 and 2 show the Tammann and Wittig temperatures for various metal oxides that can be used for oxidative coupling of methane reaction. It should be noted that this list is exemplary only and embodiments of the invention are not limited to metal oxides selected from this list.

    TABLE-US-00001 TABLE 1 Tammann and Huttig Temperature for Various Metal Oxides used for Oxidative Coupling of Methane Tammann Httig Metal Oxide Temperature, C. Temperature, C. Magnesium oxide, MgO 1290 665 Lanthanum Oxide, La.sub.2O.sub.3 1021 503 Cerium Oxide, CeO2 1064 529 Samarium Oxide, Sm.sub.2O.sub.3 1031 509 Thorium Oxide, ThO.sub.2 1559 826 Ytterbium Oxide, Yb.sub.2O.sub.3 1041 515 Strontium Oxide, SrO 1129 568 Barium Oxide, BaO 825 386 Manganese Oxide, MnO 836 392 Manganese Oxide, Mn.sub.3O.sub.4 647 279 Lead Oxide, PbO 308 75

    TABLE-US-00002 TABLE 2 Tammann and Httig temperature for various metal oxides Compound T.sub.melting T.sub.Tammann T.sub.Httig Pt 2028 1014 608 PtO 823 412 247 PtO.sub.2 723 362 217 PtCl.sub.2 854.sup.c 427 256 PtCl.sub.4 643.sup.c 322 193 Pd 1828 914 548 PdO 1023.sup.c 512 307 Rh 2258 1129 677 Rh.sub.2O.sub.3 1373.sup.c 687 412 Ru 2723 1362 817 Fe 1808 904 542 Co 1753 877 526 Ni 1725 863 518 NiO 2228 1114 669 NiCl.sub.2 1281 641 384 Ni(CO).sub.4 254 127 76 NiS 1249 625 375 Ag 1233 617 370 Au 1336 668 401 Cu 1356 678 407 CuO 1599 800 480 Cu.sub.2O 1508 754 452 CuCl.sub.2 893 447 268 Cu.sub.2Cl.sub.2 703 352 211 Mo 2883 1442 865 MoO.sub.3 1068 534 320 MoS.sub.2 1458 729 437 Zn 693 347 208 ZnO 2248 1124 675 Al.sub.2O.sub.3 2318 1159 695 SiO.sub.2.sup.a 1986 993 596 SiO.sub.2.sup.b 1883 942 565 .sup.a Crystobalite. .sup.b Quartz. .sup.c Decomposes at this temperature. Source: J. A. Moulijn, A. E. van Diepen, F. Kapteijn Catalyst Deactivation: is it Predictable? What to do?, Applied Catalysis A: General 212(2001) 3-16.

    [0027] In embodiments of the invention, by selecting metal oxide materials so that the one or more of the catalytically active metal oxides therein have a Tammann temperature higher than the operating temperature of the oxidative coupling of methane reaction, stable performance of the mixed metal oxide catalyst can be achieved. In embodiments of the invention, the operating temperature of the oxidative coupling of methane reaction may be about 750 C. Thus, at block 102, according to embodiments of the invention, method 10 may include selecting the one or more catalytically active metal oxide materials having a Tammann temperature greater than 750 C. In embodiments of the invention, the oxidative coupling of methane reaction operating temperature is 750 C. to 1100 C., most preferably 850 C. to 950 C. In embodiments of the invention, the Tammann temperature is no less than 10% or 20% of the oxidative coupling of methane reaction operating temperature. Therefore, in embodiments of the invention, for example, as may be dictated by the operating temperature of the oxidative coupling of methane reaction, the one or more catalytically active metal oxide materials that is selected for the mixed metal oxide catalyst may have a Tammann temperature that is greater than 850 C., preferably greater than 950 C., or more preferably greater than 1000 C., or 750 C. to 1700 C.

    [0028] In embodiments of the invention, at least one or all of the catalytically active metal oxides in the metal oxide material can have a Tammann temperature of greater than 750 C. In embodiments of the invention, for example, as may be dictated by the operating temperature of the oxidative coupling of methane reaction, each of the metal oxides in the mixed metal oxide material may have a Tammann temperature greater than 750 C., preferably greater than 850 C., more preferably greater than 950 C., or even more preferably greater than 1000 C., or 750 C. to 1700 C.

    [0029] It is possible that one or more components of a mixed metal oxide catalyst may have a Tammann temperature greater than a particular value, yet the Tammann temperature of the entire mixed metal oxide catalyst has a Tammann temperature below that value. In view of this, in embodiments of the invention, selections of the one or more of the metal oxides may be carried out such that the Tammann temperature of the mixed metal oxide material (as opposed to only the Tammann temperature of a given metal oxide that makes up the mixed metal oxide material) is above 750 C. In embodiments of the invention, the mixed metal oxide material has a Tammann temperature greater than 750 C., preferably greater than 850 C., more preferably greater than 950 C., or even more preferably greater than 1000 C., or 750 C. to 1700 C.

    [0030] It is possible that one or more components of a mixed metal oxide catalyst material may have a Tammann temperature lower than a particular value, yet the Tammann temperature of the entire mixed metal oxide catalyst material has a Tammann temperature above that value. In view of this, in embodiments of the invention, selections of the one or more of the metal oxides may be carried out such that the Tammann temperature of the mixed metal oxide material (as opposed to only the Tammann temperature of a given metal oxide that makes up the mixed metal oxide material) is above 750 C. In embodiments of the invention, the mixed metal oxide material has a Tammann temperature greater than 750 C., preferably greater than 850 C., more preferably greater than 950 C., or even more preferably greater than 1000 C., or 750 C. to 1700 C.

    [0031] Embodiments of the invention may use a SrCeYb oxide catalyst. Alternatively or additionally, embodiments of the invention may use other oxidative coupling of methane reaction catalysts such as mixed metal oxides selected from La.sub.2O.sub.3/CeO.sub.2, SrO/La.sub.2O.sub.3, Li/MgO, etc. Further, embodiments of the invention may include any compounds (e.g., new crystalline phases) formed during catalyst synthesis and pretreatment (e.g., calcination).

    [0032] In embodiments of the invention, for example, as may be dictated by the operating temperature of the oxidative coupling of methane reaction, the mixed metal oxide material can include metals from Column 1, Column 2, transitions metals, post-transition metals, or the lanthanides, and/or actinides of the Periodic Table. Non-limiting examples of Column 2 metals include magnesium (Mg), and/or strontium (Sr). Lanthanide metals can include lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and/or lutetium (Lu). Non-limiting examples of actinides include thorium. Transition metals can include Column 4 metals, for example, zirconium and titanium, and Column 12 metals, for example, zinc. Post-transition metals can include aluminum and silicon. In some instances, the mixed metal oxide material can be a mixture of La.sub.2O.sub.3 and another metal oxide from Column .sub.2, lanthanides, or actinides of the Periodic Table. By way of example, ThO.sub.2La.sub.2O.sub.3, MgOLa.sub.2O.sub.3, SrOLa.sub.2O.sub.3, CeO.sub.2La.sub.2O.sub.3, Yb.sub.2O.sub.3La.sub.2O.sub.3, Sm.sub.2O.sub.3La.sub.2O.sub.3, or mixtures thereof can be used in the context of the present invention.

    [0033] In embodiments of the invention, the mixed metal oxide material can include three catalytically active metal oxides selected from the actinides, alkaline earth metals (Column 2 metals), transition metals, lanthanides or mixtures thereof. By way of example, the three metals can be selected from thorium (Th), magnesium (Mg), strontium (Sr), cerium (Ce), ytterbium (Yb), samarium (Sm), lanthanum (La), erbium (Er), neodymium (Nd), dysprosium (Dy), gadolinium (Gd), europium (Eu), praseodymium (Pr), thulium (Tm), scandium (Sc), yttrbium (Yb), promethium (Pm), terbium (Tb), holmium (Ho), lutetium (Lu), zirconium (Zr), titanium (Ti), zinc (Zn), aluminum (Al), and silicon (Si). Non-limiting examples of mixed metal oxide materials having three active catalytic metals includes SrCeYb oxide, oxides of MgCeYb, MgCeLa, MgCePr, MgCeNd, MgCeSm, MgCeEu, MgCeGd, MgCeDy, MgCeEr, SrCeLa, SrCePr, SrCeNd, SrCeSm, SrCeEu, SrCeGd, SrCeDy, SrCeEr, BaCeYb, BaCeLa, BaCePr, BaCeNd, BaCeSm, BaCeEu, BaCeGd, BaCeDy, BaCeEr MgPrYb, MgPrLa, MgPrNd, MgPrSm, MgPrEu, MgPrGd, MgPrDy, MgPrEr, MgPrYb, SrPrYb, SrPrLa, SrPrNd, SrPrSm, SrPrEu, SrPrGd, SrPrDy, SrPrEr, SrPrYb, BaPrYb, BaPrLa, BaPrNd, BaPrSm, BaPrEu, BaPrGd, BaPrDy, BaPrEr, and BaPrYb. Other non-limiting examples of mixed metal oxides that may be used in embodiments of the invention include Sr.sub.0.9Ce.sub.0.1CoO.sub.3-x, Sr.sub.0.9Ce.sub.0.1FeO.sub.3-x, Sr.sub.0.9Ce.sub.0.1Co.sub.0.5Fe.sub.0.5O.sub.3-x, Sr.sub.0.9La.sub.0.1Co.sub.0.5Fe.sub.0.5O.sub.3-x, La.sub.0.9Sr.sub.0.1Ga.sub.0.8Mg.sub.0.2O.sub.3-x, La.sub.0.9Sr.sub.0.1(Ga.sub.0.9Fe.sub.0.1).sub.0.8Mg.sub.0.2O.sub.3-x, Sr.sub.1-yCe.sub.yFeO.sub.3-x, SrFeO.sub.2.80, Sr.sub.0.9Ce.sub.0.1FeO.sub.2.78, Sr.sub.0.8Ce.sub.0.2FeO.sub.2.795, Sr.sub.0.7Ce.sub.0.3FeO.sub.2.82, Ba.sub.1-ySr.sub.ySr.sub.yCe.sub.1-xY.sub.xO.sub.3-, BaCe.sub.0.9Y.sub.0.7O.sub.3-, BaCe.sub.0.8Y.sub.0.2Y.sub.3-, BaCe.sub.0.75Y.sub.0.25O.sub.3-, BaCe.sub.0.7Y.sub.0.3O.sub.3-, BaCe.sub.0.6Y.sub.0.4O.sub.3-, BaCe.sub.0.5Y.sub.0.5O.sub.3-, and (La,Sr)CeZrOx-based materials, where x0.5, y0.5, and 0.5.

    [0034] Referring to FIG. 1, method 10, at block 103, may involve making an active and stable mixed metal oxide catalyst by using the selected one or more metal oxides for the oxidative coupling of methane reaction. The mixed metal oxides may be made as described below in FIG. 2, method 20. Additionally or alternatively, block 103 may involve obtaining a mixed metal oxide material having catalytically active metal oxides for the oxidative coupling of methane reaction by acquiring the mixed metal oxide material from commercial sources such as those identified below.

    [0035] Once the mixed metal oxide material has been made or obtained for use as the catalyst in the oxidative coupling of methane reaction as provided by block 103, method 10 may further include, at block 104, contacting the selected mixed metal oxide material with a reactant feed comprising methane (CH.sub.4) and oxygen (O.sub.2) to produce a product stream comprising C.sub.2+ hydrocarbons, wherein C.sub.2+ hydrocarbons can include a mixture of ethane, ethylene, and C.sub.3 and higher hydrocarbons. In embodiments of the invention, the product stream may further comprise carbon dioxide (CO.sub.2) and carbon monoxide (CO).

    [0036] Based on the selection process described above, the OCM mixed metal oxide catalyst can be more stable than contemporary catalysts that are not so configured. In embodiments of the invention, contacting the selected mixed metal oxide material with the reactant feed is performed for greater than 500 hours without needing to regenerate the selected mixed metal oxide material. In embodiments of the invention, the oxygen (O.sub.2) conversion is greater than 70% or greater than 90% after 500 hours, preferably 1000 hours, or more preferably greater than 1500 hours, time on the stream. In embodiments of the invention, the C.sub.2+ hydrocarbon selectivity is greater than 60% or 60% to 85% after 500 hours, preferably 1000 hours, or more preferably greater than 1500 hours, time on the stream.

    [0037] As noted above, the individual metal oxides and/or the mixed metal oxide catalyst described in method 10 may be acquired from sources such as Sigma-Aldrich (U.S.A.) or Fisher Scientific, or Alfa Aesar, or any other commercial sources. Additionally or alternatively, the metal oxides can be made using precipitation, co-precipitation, or sol-gel methodology. FIG. 2 shows method 20, which may be used to make the mixed metal oxide catalyst for oxidative coupling of methane, according to embodiments of the invention. Method 20 may begin at block 200, which involves selecting at least a first metal oxide material and a second metal oxide material based on the Tammann temperature (T.sub.Tam) of the corresponding metal oxide. In method 20, the T.sub.Tam of at least one metal oxide is greater than 750 C. After selecting the first and second metal oxide material, at block 201, the first metal oxide material and the second metal oxide material are combined to form a stable material. Once formed, the stable material is calcined to obtain a mixed metal oxide catalyst, at block 202. Calcining may include subjecting the material to a temperature greater than 350 C., preferably greater than 800 C. in the presence of an oxygen source, preferably air.

    [0038] The first and second metal oxide materials may be metal salts or metal oxide precursors, and in that scenario combining the first metal oxide material and the second metal oxide material at block 201 may involve obtaining a solution comprising first and second metal salts and drying the solution at 110 C. to 130 C. to obtain a stable mixture. The stable mixture can be heated in the presence of an oxidant (e.g., calcined in air) to convert the stable mixture to a mixed metal oxide. By way of example, the stable mixture can be heated at 350 C. to 800 C. under a flow of air. Alternatively or additionally, when the first and second metal oxide materials are metal salts, combining the first metal oxide material and the second metal oxide material at block 201 may involve obtaining a first solution comprising the first metal salt and a second solution comprising the second metal salt. The first solution may then be added to the second solution to precipitate a mixed metal salt. Subsequently, the method may involve drying the solution at 110 C. to 130 C. to obtain the stable mixture. The stable mixture can be calcined at 350 to 800 C. to convert the mixed metal salt to mixed metal oxide catalyst. Alternatively or additionally, when the first and second metal oxide materials are metal oxides, combining the first metal oxide material and the second metal oxide material at block 201 may involve mixing and pulverizing the metal oxides to form the stable material.

    EXAMPLE

    [0039] The present invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes only, and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of noncritical parameters which can be changed or modified to yield essentially the same results. Experiments were performed to show the performance of the oxidative coupling of methane reaction in temperature-programmed sequences. The experiments show nearly stable performance of SrCeYb Oxide catalyst at the following feed conditions: feed CH.sub.4/O.sub.2 ratio of 7.4, residence time of 1.4 ms. Table 3 shows the results of the experiment at these conditions. The mass of converted methane per gram of catalyst was in excess of 33,750 g.

    TABLE-US-00003 TABLE 3 Performance of the SrCeYb Oxide catalyst at various times on stream (Conditions: Feed CH.sub.4/O.sub.2 ratio of 7.4, residence time of 1.4 ms) Time on stream, hours 167 181 942 1642 Temperature, C. 750 775 800 813 CH.sub.4 Conversion 14.5 16.6 16.2 15.1 O.sub.2 Conversion 80.0 92.4 88.7 84.5 C Selectivities C.sub.2 (ethylene) 23.1 28.5 28.0 29.7 C.sub.2 (acetylene) 0.1 0.2 0.2 0.4 C.sub.2 (ethane) 45.3 43.2 41.9 39.4 C.sub.3 (propylene) 1.3 1.5 1.6 2.0 C.sub.3 (propane) 2.8 2.2 1.8 1.7 C.sub.4 (butylene, 1-butene, 2-butene) 0.7 1.0 0.8 0.9 % C.sub.2+ 73.3 76.7 74.4 74.0 % CO 2.9 1.7 2.6 2.5 % CO.sub.2 23.8 21.6 23.0 23.5
    FIG. 3 shows the performance of the reaction in temperature-programmed sequences. FIG. 3 illustrates the performance of SrCeYb oxide catalyst with time on stream (Feed CH.sub.4/O.sub.2 ratio=7.4; Residence Time=1.4 ms).