Catalyst compositions having enhanced acidity for dry reforming processes

Abstract

Modified red mud catalyst compositions, methods for production, and methods for use, a composition including red mud material produced from an alumina extraction process from bauxite ore; nickel oxide, the nickel oxide present at between about 5 wt. % to about 40 wt. % of the modified red mud catalyst composition; and a Periodic Table Group VIB metal oxide, the Group VIB metal oxide present at between about 1 wt. % and about 30 wt. % of the modified red mud catalyst composition.

Claims

1. A modified red mud catalyst composition, the modified red mud catalyst composition consisting of: red mud material produced from an alumina extraction process from bauxite ore, where the red mud material comprises aluminum oxide, calcium oxide, iron oxide, sodium oxide, silicon oxide, and titanium oxide such that the modified red mud catalyst composition includes between about 15 wt. % and about 30 wt. % Al.sub.2O.sub.3, between about 1 wt. % and about 5 wt. % CaO, between about 10 wt. % and about 30 wt. % Fe.sub.2O.sub.3, between about 1 wt. % and about 5 wt. % Na.sub.2O, between about 10 wt. % and about 25 wt. % SiO.sub.2, and between about 1 wt. % and about 10 wt. % TiO.sub.2; nickel oxide, the nickel oxide present at between about 15 wt. % to about 25 wt. % of the modified red mud catalyst composition; and a Periodic Table Group VIB metal oxide, the Group VIB metal oxide present at between about 1 wt. % and about 30 wt. % of the modified red mud catalyst composition, where the Group VIB metal oxide comprises at least one metal selected from the group consisting of: chromium, molybdenum, and tungsten.

2. The modified red mud catalyst according to claim 1, where the modified red mud catalyst composition comprises particles having a particle size of less than about 70 μm.

3. The modified red mud catalyst composition according to claim 1, where the nickel oxide is present at about 23 wt. % of the modified red mud catalyst composition.

4. The modified red mud catalyst composition according to claim 1, where the Group VIB metal oxide is present at between about 1 wt. % to about 20 wt. % of the modified red mud catalyst composition.

5. The modified red mud catalyst composition according to claim 1, where the Group VIB metal oxide is present at between about 1 wt. % to about 10 wt. % of the modified red mud catalyst composition.

6. The modified red mud catalyst composition according to claim 1, where the Group VIB metal oxide is present at about 5 wt. % of the modified red mud catalyst composition.

7. The modified red mud catalyst composition according to claim 1, where Brunauer-Emmett-Teller (BET) surface area of the modified red mud catalyst composition is between about 50 m.sup.2/g and about 90 m.sup.2/g.

8. A method for producing the modified red mud catalyst composition of claim 1, the method comprising the steps of: a) dissolving red mud material produced from an alumina extraction process from bauxite ore in water to produce a red mud solution; b) neutralizing the pH of the red mud solution using an acid; c) preparing a nickel-containing solution, where the nickel-containing solution consists of nickel nitrate dissolved in ethanol; d) preparing a Periodic Table Group VIB metal oxide-containing solution, where the Group VIB metal oxide comprises at least one metal selected from the group consisting of: chromium, molybdenum, and tungsten; e) mixing the red mud solution, the nickel-containing solution, and the Group VIB metal oxide-containing solution to precipitate the modified red mud catalyst composition; and f) calcining the modified red mud catalyst composition, wherein the modified red mud catalyst composition provides constant methane conversion above about 13% between 1 hour and 6 hours and provides hydrogen production above 8% between 1 hour and 6 hours in dry reforming processes at molar ratios of CH.sub.4 to CO.sub.2 between about 1:1 and about 1:1.75.

9. The method according to claim 8, where the water comprises deionized water.

10. The method according to claim 8, where the acid comprises hydrochloric acid.

11. The method according to claim 8, where the Group VIB metal oxide-containing solution comprises ammonium molybdate dissolved in ethanol.

12. The method according to claim 8, further comprising filtering the modified red mud catalyst composition and drying the modified red mud catalyst composition before the step of calcining.

13. The method according to claim 12, where the step of drying occurs at about 100° C.

14. The method according to claim 8, where the step of calcining takes place for about 4 hours at between about 500° C. to about 700° C.

15. The method according to claim 8, where the step of calcining takes place for about 4 hours at about 600° C.

16. The method according to claim 8, further comprising the step of grinding the modified red mud catalyst composition to a particle size of less than about 70 μm.

17. The method according to claim 8, where Brunauer-Emmett-Teller (BET) surface area of the modified red mud catalyst composition is between about 50 m.sup.2/g and about 90 m.sup.2/g.

18. A method for dry reforming over a modified red mud catalyst composition, the method comprising the steps of: providing a methane feed and carbon dioxide feed to react over the modified red mud catalyst composition at a temperature between about 500° C. to about 1000° C. and a pressure between about 5 bar and about 20 bar to produce synthesis gas comprising H.sub.2 and CO, the modified red mud catalyst composition consisting of: red mud material produced from an alumina extraction process from bauxite ore where the red mud material comprises aluminum oxide, calcium oxide, iron oxide, sodium oxide, silicon oxide, and titanium oxide such that the modified red mud catalyst composition includes between about 15 wt. % and about 30 wt. % Al.sub.2O.sub.3, between about 1 wt. % and about 5 wt. % CaO, between about 10 wt. % and about 30 wt. % Fe.sub.2O.sub.3, between about 1 wt. % and about 5 wt. % Na.sub.2O, between about 10 wt. % and about 25 wt. % SiO.sub.2, and between about 1 wt. % and about 10 wt. % TiO.sub.2; nickel oxide, the nickel oxide present at between about 15 wt. % to about 25 wt. % of the modified red mud catalyst composition; and a Periodic Table Group VIB metal oxide, the Group VIB metal oxide present at between about 1 wt. % and about 30 wt. % of the modified red mud catalyst composition, where the Group VIB metal oxide comprises at least one metal selected from the group consisting of: chromium, molybdenum, and tungsten.

19. The method according to claim 18, where the Group VIB metal oxide comprises at least one metal selected from the group consisting of: chromium, molybdenum, and tungsten.

20. The method according to claim 18, where the temperature is between about 600° C. to about 800° C.

21. The method according to claim 18, where the temperature is about 750° C.

22. The method according to claim 18, where the pressure is between about 10 bar and about 15 bar.

23. The method according to claim 18, where the pressure is about 14 bar.

24. The method according to claim 18, where the methane conversion rate is at least about 14% for at least about 6 hours.

25. The method according to claim 18, where the modified red mud catalyst composition comprises particles with a particle size of less than about 70 μm.

26. The method according to claim 18, where the nickel oxide is present at about 23 wt. % of the modified red mud catalyst composition.

27. The method according to claim 18, where the Group VIB metal oxide is present at between about 1 wt. % to about 20 wt. % of the modified red mud catalyst composition.

28. The method according to claim 18, where the Group VIB metal oxide is present at between about 1 wt. % to about 10 wt. % of the modified red mud catalyst composition.

29. The method according to claim 18, where the Group VIB metal oxide is present at about 5 wt. % of the modified red mud catalyst composition.

30. The method according to claim 18, where a molar ratio of the methane feed to the carbon dioxide feed is between about 1:1 and about 1:1.75.

31. The method according to claim 18, where produced H.sub.2 is at least about 9 mol. % of produced products from the reaction.

32. The method according to claim 18, where Brunauer-Emmett-Teller (BET) surface area of the modified red mud catalyst composition is between about 50 m.sup.2/g and about 90 m.sup.2/g.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) These and other features, aspects, and advantages of the present disclosure will become better understood with regard to the following descriptions, claims, and accompanying drawings. It is to be noted, however, that the drawings illustrate only several embodiments of the disclosure and are therefore not to be considered limiting of the disclosure's scope as it can admit to other equally effective embodiments.

(2) FIG. 1 is a graph showing conversion percentage for CH.sub.4 in a dry reforming process for unmodified red mud (RM) used as a catalyst and for acid nickel-molybdenum-modified red mud (ANMoMRM) used as a catalyst.

(3) FIG. 2 is a graph showing mol. % of H.sub.2 out of the total products produced from dry reforming of CH.sub.4 in a dry reforming process for unmodified red mud used as a catalyst and for ANMoMRM used as a catalyst.

DETAILED DESCRIPTION

(4) So that the manner in which the features and advantages of the embodiments of compositions of Group VIB metal modified red mud, in some embodiments including nickel, along with systems and methods for dry reforming with such compositions and for producing such compositions, may be understood in more detail, a more particular description of the embodiments of the present disclosure briefly summarized previously may be had by reference to the embodiments thereof, which are illustrated in the appended drawings, which form a part of this specification. It is to be noted, however, that the drawings illustrate only various embodiments of the disclosure and are therefore not to be considered limiting of the present disclosure's scope, as it may include other effective embodiments as well.

(5) As noted, red mud is a caustic waste material generated during alumina extraction from bauxite ore. Red mud includes a mixture of transition metals, for example as listed in Table 1.

(6) TABLE-US-00001 TABLE 1 Example composition ranges for global red mud. Component Fe.sub.2O.sub.3 Al.sub.2O.sub.3 SiO.sub.2 Na.sub.2O CaO TiO.sub.2 Approx. 30-60% 10-20% 3-50% 2-10% 2-8% 10% Weight Percentage

(7) Red mud was modified with nickel and molybdenum to be utilized and tested as a catalyst for dry reforming as follows. In some embodiments, nickel is not required. In some embodiments, nickel in addition to or alternative to any one of or any combination of chromium, molybdenum, and tungsten can be used to modify red mud. Saudi Arabian red mud from Ma'aden Aluminium Company, based at Ras Al Khair, Saudi Arabia was used to prepare a modified catalyst composition. Table 2 shows the weight percent for certain components in the unmodified Saudi Arabian red mud composition.

(8) TABLE-US-00002 TABLE 2 Certain component weight percentages in Saudi Arabian red mud (RM) catalyst/catalyst support composition. Component Fe.sub.2O.sub.3 Al.sub.2O.sub.3 SiO.sub.2 Na.sub.2O CaO TiO.sub.2 Weight 18.75% 25.22% 18.88% 11.77% 7.97% 6.89% Percentage

(9) The untreated red mud exhibited a Brunauer-Emmett-Teller (BET) surface area of about 16 m.sup.2/g.

(10) Table 3 shows an example composition for one embodiment of produced nickel-molybdenum acid treated red mud for use as a modified catalyst. The unmodified red mud used as a catalyst precursor contained no detectable nickel or molybdenum.

(11) TABLE-US-00003 TABLE 3 Example composition for a produced ANMoMRM used as a catalyst. Component Fe.sub.2O.sub.3 Al.sub.2O.sub.3 SiO.sub.2 Na.sub.2O CaO TiO.sub.2 NiO MoO Weight 16.76% 21.43% 19.56% 2.81% 2.76% 5.36% 23.7% 5.06% Percentage

(12) Because red mud is a highly variable waste material, elemental composition will vary between samples and test results.

(13) Catalyst Preparation. An acid nickel-molybdenum-modified red mud (ANMoMRM) catalyst with 23.7 wt. % nickel oxide and 5.06 wt. % molybdenum oxide was prepared using a homogeneous precipitation process. Using an unmodified red mud catalyst precursor, 20 wt. % of nickel oxide (also referred to as NiO) was targeted to be loaded in the red mud to enhance dry reforming activity, and 23.7 wt. % of nickel oxide was confirmed by X-ray fluorescence (XRF) analysis. Using the unmodified red mud catalyst precursor, 5 wt. % of molybdenum oxide (also referred to as MoO) was targeted to be loaded in the red mud to enhance dry reforming activity, and 5.06 wt. % of molybdenum oxide was confirmed by XRF analysis. Depending on the catalyst application, nickel oxide can be loaded to a red mud precursor from between about 1 wt. % to about 50 wt. %, and molybdenum oxide, in addition to or alternative to other Group VIB metals, can be loaded to a red mud precursor from between about 1 wt. % to about 50 wt. %.

(14) First, 10 g of Saudi Arabian red mud from Ma'aden Aluminium Company, based at Ras Al Khair, Saudi Arabia was modified by dissolving dried, unmodified red mud in 100 mL of deionized water, and then the pH was neutralized using 40.5 mL of 37 wt. % hydrochloric acid. Afterward, 10 g of nickel(II) nitrate hexahydrate was dissolved in 50 mL of ethanol. Then, 0.92 grams of ammonium molybdate tetrahydrate was dissolved in 50 mL of ethanol. The three separate solutions were mixed to form a mixed solution. Next, the mixed solution was filtered, filtered solids were dried in an oven at 105° C., and then calcined at 600° C. for 4 hours. The final ANMoMRM solid product was ground to have a particle size of less than about 70 The step of drying in an oven can last from about 2 to about 24 hours.

(15) Other nickel-containing compounds and molybdenum-containing compounds can be used in addition to or alternative to nickel nitrate and ammonium molybdate, including any nickel-containing compounds or molybdenum-containing compounds soluble in ethanol or other organic or inorganic alcohols, or in aqueous ammonia. XRF in embodiments of the present disclosure confirmed the presence of nickel and molybdenum oxide loading in the ANMoMRM. Nickel can be combined with red mud to result in nickel(II) oxide, NiO, in addition to or alternative to nickel(III) oxide, Ni.sub.2O.sub.3. Molybdenum can be combined with red mud to result in (molybdenum dioxide, MoO.sub.2) or Molybdenum(VI) oxide (molybdenum trioxide, MoO.sub.3).

(16) BET surface area analysis showed unmodified red mud surface area was about 16 m.sup.2/g. BET surface area for acid modified red mud was about 170 m.sup.2/g. BET surface area for acid modified red mud with nickel in addition to or alternative to molybdenum loading is, in some embodiments, between about 50 m.sup.2/g and about 90 m.sup.2/g, for example about 63 m.sup.2/g or about 89 m.sup.2/g.

(17) Catalyst testing. Several tests on red mud catalytic activity and ANMoMRM catalytic activity for dry reforming were experimentally conducted. Saudi Arabian red mud was tested as received as a catalyst support without any modifications, and it was placed in an Avantium Flowrence® catalyst testing reactor to perform dry reforming experiments. The Avantium Flowrence® reactor is a flexible, high-throughput catalyst testing system that was operated using about 0.5 g of catalyst samples. The ANMoMRM catalyst was tested in a Micromeritics® PID Eng & Tech brand microactivity reactor designed for catalyst activity and selectivity analysis. The results are compared, for example, in FIGS. 1 and 2. Results show that ANMoMRM catalytic activity for dry reforming is advantageously improved over non-modified red mud catalytic activity for dry reforming.

(18) FIG. 1 is a graph showing conversion percentage for CH.sub.4 in a dry reforming process for unmodified red mud used as a catalyst and for ANMoMRM used as a catalyst. Effects of nickel and molybdenum addition to red mud were studied. Experimental conditions in the dry reforming reactor included temperature at about 750° C., pressure at about 14 bar, and gas hourly space velocity (GHSV) at about 1477 h.sup.−1. The test was conducted for 6 hours. Catalysts tolerant at high pressure are favored for dry reforming processes. The feed was 50 mol. % methane and 50 mol. % CO.sub.2 for both catalysts tested. The GHSV was calculated for the mixed feed. GHSV generally measures the flow rate of the feed gases divided by the catalyst volume, which indicates the residence time of the reactants on the catalyst.

(19) For dry reforming, the feed composition will include CH.sub.4 and CO.sub.2. In some embodiments for dry reforming, a feed will consist essentially of or consist of CH.sub.4 and CO.sub.2. Based on thermodynamics, the molar ratio of the feed for CH.sub.4 to CO.sub.2 can be about 1:1. However, some other embodiments showed that greater CO.sub.2 concentrations up to 1:1.75 (mole CH.sub.4 to mole CO.sub.2) surprisingly and unexpectedly enhanced H.sub.2 production.

(20) Methane conversion illustrated in FIG. 1 shows ANMoMRM catalyst outperformed its counterpart, the untreated red mud. Methane conversion by ANMoMRM reached up to about 17%, and remained nearly constant at this level during the experiment's duration. On the other hand, unmodified red mud methane conversion maxed out at about 14%, then deteriorated. Slight conversion activity of unmodified red mud could be attributed to the existence of several transition metals within red mud, and the greater conversion rate of ANMoMRM can be attributed to the addition of nickel and molybdenum, and synergies of the nickel and molybdenum with the existing transition metals in the red mud.

(21) FIG. 2 is a graph showing mol. % of H.sub.2 out of the total products produced from dry reforming of CH.sub.4 in a dry reforming process for unmodified red mud (RM) used as a catalyst and for ANMoMRM used as a catalyst. Hydrogen production illustrated in FIG. 2 shows that untreated red mud produced low amounts of hydrogen, whereas ANMoMRM catalyst produced up to about 11 mol. % hydrogen. Nickel-molybdenum modification of red mud has enhanced the performance significantly for hydrogen production.

(22) The singular forms “a,” “an,” and “the” include plural referents, unless the context clearly dictates otherwise. The term “about” when used with respect to a value or range refers to values including plus and minus 5% of the given value or range.

(23) In the drawings and specification, there have been disclosed example embodiments of the present disclosure, and although specific terms are employed, the terms are used in a descriptive sense only and not for purposes of limitation. The embodiments of the present disclosure have been described in considerable detail with specific reference to these illustrated embodiments. It will be apparent, however, that various modifications and changes can be made within the spirit and scope of the disclosure as described in the foregoing specification, and such modifications and changes are to be considered equivalents and part of this disclosure.