Catalyst carrier for bi-reforming processes

Abstract

Methods for bi-reforming with a red mud catalyst support composition, one method including providing a methane feed in the presence of carbon dioxide and steam to react over the red mud catalyst support composition at increased temperature and increased pressure to produce synthesis gas comprising H.sub.2 and CO, the composition comprising red mud material produced from an alumina extraction process from bauxite ore.

Claims

1. A method for bi-reforming with a red mud catalyst support composition, the method comprising the steps of: providing a methane feed in the presence of carbon dioxide and steam to react in a bi-reforming reaction over the red mud catalyst support 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 red mud catalyst support composition comprising: red mud waste material produced from an alumina extraction process from bauxite ore with a weight ratio of aluminum oxide to iron oxide of about 1:0.74 and a weight ratio of aluminum oxide to titanium oxide of about 1:0.27, where produced H.sub.2 is at least about 1 mol. % of produced products from the bi-reforming reaction for at least about 5 hours.

2. The method according to claim 1, where the red mud catalyst support composition further comprises at least one added catalytic metal, the added catalytic metal not originally being present at greater than about 1 wt. % in the red mud material produced from the alumina extraction process from bauxite ore.

3. The method according to claim 2, where the at least one added catalytic metal is a Periodic Table Group 3-12 metal.

4. The method according to claim 1, where the increased temperature is between about 600° C. to about 800° C.

5. The method according to claim 1, where the increased temperature is about 750° C.

6. The method according to claim 1, where the increased pressure is between about 10 bar and about 15 bar.

7. The method according to claim 1, where the increased pressure is about 14 bar.

8. The method according to claim 1, where gas hourly space velocity of the methane feed in the presence of carbon dioxide and steam is between about 1000 h.sup.−1 to 10000 h.sup.−1.

9. The method according to claim 1, where the red mud catalyst support composition includes at least one component selected from the group consisting of: Fe.sub.2O.sub.3, Al.sub.2O.sub.3, SiO.sub.2, Na.sub.2O, CaO, and TiO.sub.2.

10. The method according to claim 1, where a majority of particles of the red mud catalyst support composition have a particle size of less than about 70 μm.

11. The method according to claim 1, where a molar ratio of methane:carbon dioxide:steam is about 3:1:2.

12. The method according to claim 1, where the red mud catalyst support composition includes between about 5 wt. % and about 10 wt. % CaO, between about 5 wt. % and about 15 wt. % Na.sub.2O, between about 15 wt. % and about 25 wt. % SiO.sub.2.

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 drawing. It is to be noted, however, that the drawing illustrates only several embodiments of the disclosure and is 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 mol. % of H.sub.2 out of the total products produced from bi-reforming of CH.sub.4 for unmodified red mud (RM) used as a catalyst support and for MgO used as a catalyst support.

DETAILED DESCRIPTION

(3) So that the manner in which the features and advantages of the embodiments of compositions of red mud along with systems and methods for bi-reforming with 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 drawing, which forms a part of this specification. It is to be noted, however, that the drawing illustrates only various embodiments of the disclosure and is therefore not to be considered limiting of the present disclosure's scope, as it may include other effective embodiments as well.

(4) 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.

(5) 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

(6) In one embodiment, a Saudi Arabian red mud sample was evaluated for bi-reforming activities at 750° C. and 14 bar, as shown in FIG. 1. The results are compared to MgO catalyst support material. MgO is a commercially-available catalyst support material known for a variety of reforming processes with a surface area of about 29 m.sup.2/g. The MgO was tested as received. FIG. 1 shows that red mud surprisingly and unexpectedly outperforms MgO as a support for bi-reforming catalyst support in terms of hydrogen production (also methane conversion according to Equation 1), especially at high pressure which is a preferred condition for industry application of bi-reforming.

(7) Saudi Arabian red mud from Ma'aden Aluminium Company, based at Ras Al Khair, Saudi Arabia was used in the test runs. Table 2 shows the weight percent for certain components in the 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 red mud was tested as-is without further treatment, for example acid or base treatment, for use as a catalyst support with a Brunauer-Emmett-Teller (BET) surface area of about 16 m.sup.2/g.

(10) Several tests on red mud support catalytic activity and MgO support catalytic activity for bi-reforming were experimentally conducted. Saudi Arabian red mud was tested as received as a catalyst support without any modifications, and it was placed in a Micromeritics® PID Eng & Tech brand microactivity reactor designed for catalyst activity and selectivity analysis, and similar tests were performed for the MgO catalyst support. The results are compared, for example, in FIG. 1. Results show that red mud support catalytic activity for bi-reforming is advantageously improved over MgO support catalytic activity for bi-reforming.

(11) Experimental conditions in the bi-reforming reactor included temperature at about 750° C. and pressure at about 14 bar. In some embodiments, gas hourly space velocity (GHSV) of the mixed feed is between about 1000 h.sup.−1 and 10000 h.sup.−1, or GHSV can be between about 3000 h.sup.−1 to about 8000 h.sup.−1, or about 7362 h.sup.−1. The test was conducted for 6 hours. In some embodiments, the feed was about 50 mol. % methane, 17 mol. % CO.sub.2, and 33 mol. % steam for both catalysts tested. The GHSV was calculated for the mixed feed. For bi-reforming, the feed composition can comprise, consist essentially of, or consist of CH.sub.4, CO.sub.2, and steam. Based in part on thermodynamics, a suitable molar ratio of methane:carbon dioxide:steam is about 3:1:2. 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.

(12) FIG. 1 is a graph showing mol. % of H.sub.2 out of the total products produced from bi-reforming of CH.sub.4 for unmodified red mud used as a catalyst support and for MgO used as a catalyst support. Hydrogen production illustrated in FIG. 1 shows that untreated red mud produced hydrogen at nearly double the rate of MgO for most of the experiment.

(13) 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.

(14) 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.