Patent Publication Number: US-11396006-B2

Title: Nickel-containing catalyst composition having enhanced acidity for bi-reforming processes

Description:
BACKGROUND 
     Field 
     Embodiments of the disclosure relate to catalyst compositions for use in reforming processes. In particular, certain embodiments of the disclosure relate to nickel-containing catalyst compositions for and methods of bi-reforming. 
     Description of the Related Art 
     Bi-reforming is a green method for the production of synthesis gas (syngas, H 2  and CO), since it utilizes the two greenhouse gases of CH 4  and CO 2  as reactants. In addition, it can offer certain advantages over dry reforming and steam reforming with respect to catalyst deactivation and final product ratio. The general chemical equation representing bi-reforming is shown below.
 
3CH 4 +CO 2 +2H 2 O⇄8H 2 +4CO  Eq. 1
 
     Bi-reforming technology combines dry reforming and steam reforming of methane to produce syngas. Unlike dry reforming, bi-reforming produces a syngas that is both flexible (with variability in the CO 2 /H 2 O ratio) and meets the 2/1 H 2 /CO ratio required by many higher-value products, for example, higher oxygenates. In addition, the presence of steam provides a higher oxidant level in bi-reforming that addresses the inevitable and typically intolerable carbon deposition in dry reforming. 
     However, one of the main challenges of bi-reforming is to develop catalysts that are resistant to high temperatures and the presence of a more oxidative environment due to steam. Suitable catalysts for bi-reforming should be resistant to high temperatures and the presence of a more oxidative environment due to steam addition. Methane reforming can quickly deactivate catalysts due to coke formation on the surface of catalysts. In addition, high temperatures for methane conversion can lead to catalyst deactivation by coking or sintering. Nickel catalyst with aluminum oxide and magnesium oxide as supports is used for methane reforming. 
     However, present catalyst technology is insufficient in some processes to provide cost-effective and durable means for bi-reforming. 
     SUMMARY 
     Applicant has recognized a need for compositions of nickel-modified red mud to be applied in systems and processes for bi-reforming. An enhanced-acidity nickel-containing catalyst composition is disclosed. The enhanced-acidity nickel-containing catalyst also contains in some embodiments Fe, Al, Si, Na, Ca, and Ti oxides from red mud. In embodiments of the present disclosure, red mud acts as a catalyst in addition to or alternative to a catalyst carrier. Disclosed compositions are useful as a catalyst in bi-reforming processes for the conversion of methane to syngas, according to Equation 1. Utilization of red mud in bi-reforming processes provides the concurrent advantages of utilizing a waste material (red mud) and producing useful H 2 , while also using two greenhouse gases (CO 2  and CH 4 ) as reactants. 
     Red mud is a caustic waste material produced from bauxite ore processing for alumina extraction, and is utilized here as a catalyst for bi-reforming processes. Surprisingly and unexpectedly, without being specifically designed as a catalyst (for example using specific zeolitic structure), red mud waste material can be readily modified for use as a catalyst. Red mud generally includes a mixture of transition metals such as Ti, Fe, and Al, which make it an advantageous catalyst for bi-reforming processes, for example once modified with nickel. 
     Embodiments disclosed here apply red mud as an active catalyst support, promotor, in addition to or alternative to catalyst to produce hydrogen through bi-reforming of methane, optionally followed by a water-gas shift reaction to produce additional H 2 . 
     Therefore, disclosed here are methods for bi-reforming over a modified red mud catalyst composition, one method including providing a methane feed in the presence of carbon dioxide and steam to react over the modified red mud catalyst composition at increased temperature and increased pressure to produce synthesis gas comprising H 2  and CO, the composition comprising: red mud material produced from an alumina extraction process from bauxite ore; and nickel oxide, the nickel oxide present at between about 5 wt. % to about 40 wt. % of the modified red mud catalyst composition. In some embodiments, the increased temperature is between about 500° C. to about 1000° C. In other embodiments, the increased temperature is between about 600° C. to about 800° C. Still in other embodiments, the increased temperature is about 750° C. In certain embodiments, the increased pressure is between about 5 bar and about 20 bar. In some other embodiments, the increased pressure is between about 10 bar and about 15 bar. In yet other embodiments, the increased pressure is about 14 bar. 
     Still in other embodiments of bi-reforming, the methane conversion rate is at least about 40% for at least about 6 hours. In certain other embodiments, gas hourly space velocity of the methane feed and carbon dioxide feed mixed is between about 1000 h −1  to 10000 h −1 . Still in other embodiments, the composition includes at least one component selected from the group consisting of: Fe 2 O 3 , Al 2 O 3 , SiO 2 , Na 2 O, CaO, and TiO 2 . In some embodiments, a majority of the particles of the composition have a particle size of less than about 70 μm. In other embodiments, the nickel oxide is present at between about 10 wt. % to about 30 wt. % of the modified red mud catalyst composition. Still in other embodiments, the nickel oxide is present at between about 15 wt. % to about 25 wt. % of the modified red mud catalyst composition. In certain embodiments, the nickel oxide is present at about 20 wt. % of the modified red mud catalyst composition. 
     In some embodiments, conversion percentage of methane reaches up to about 40%. Still in other embodiments, a molar ratio of methane:carbon dioxide:steam is about 3:1:2. In certain embodiments, produced H 2  is at least about 10 mol. % of produced products from the reaction for at least about 5 hours. In certain embodiments, the Brunauer-Emmett-Teller (BET) surface area of the modified red mud catalyst composition is between about 50 m 2 /g and about 90 m 2 /g. Still in other embodiments, the composition includes between about 5 wt. % and about 20 wt. % Al 2 O 3 , between about 2 wt. % and about 10 wt. % CaO, between about 20 wt. % and about 40 wt. % Fe 2 O 3 , between about 5 wt. % and about 20 wt. % SiO 2 , and between about 10 wt. % and about 20 wt. % TiO 2 . 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       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&#39;s scope as it can admit to other equally effective embodiments. 
         FIG. 1  is a graph showing conversion percentage for CH 4  in a bi-reforming process for unmodified red mud (RM) used as a catalyst and for acid nickel-modified red mud (ANMRM) used as a catalyst. 
         FIG. 2  is a graph showing mol. % of H 2  out of the total products produced from bi-reforming of CH 4  for unmodified red mud used as a catalyst and for ANMRM used as a catalyst. 
     
    
    
     DETAILED DESCRIPTION 
     So that the manner in which the features and advantages of the embodiments of compositions of nickel-modified red mud along with systems and methods for bi-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&#39;s scope, as it may include other effective embodiments as well. 
     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. 
     
       
         
           
               
             
               
                 TABLE 1 
               
             
            
               
                   
               
               
                 Example composition ranges for global red mud. 
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Component 
                 Fe 2 O 3   
                 Al 2 O 3   
                 SiO 2   
                 Na 2 O 
                 CaO 
                 TiO 2   
               
               
                   
               
               
                 Approx. 
                 30-60% 
                 10-20% 
                 3-50% 
                 2-10% 
                 2-8% 
                 10% 
               
               
                 Weight 
                   
                   
                   
                   
                   
                   
               
               
                 Percentage 
               
               
                   
               
            
           
         
       
     
     Red mud was modified with nickel to be utilized and tested as a catalyst for bi-reforming as follows. The unmodified red mud used as a catalyst precursor contained no detectable nickel. Saudi Arabian red mud from Ma&#39;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. 
     
       
         
           
               
             
               
                 TABLE 2 
               
             
            
               
                   
               
               
                 Certain component weight percentages in unmodified Saudi  
               
               
                 Arabian red mud (RM) catalyst/catalyst support composition. 
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Component 
                 Fe 2 O 3   
                 Al 2 O 3   
                 SiO 2   
                 Na 2 O 
                 CaO 
                 TiO 2   
               
               
                   
               
               
                 Weight 
                 18.75% 
                 25.22% 
                 18.88% 
                 11.77% 
                 7.97% 
                 6.89% 
               
               
                 Percentage 
               
               
                   
               
            
           
         
       
     
     The untreated red mud exhibited a Brunauer-Emmett-Teller (BET) surface area of about 16 m 2 /g. 
     Table 3 shows an example composition for one embodiment of produced ANMRM for use as a modified catalyst. 
     
       
         
           
               
             
               
                 TABLE 3 
               
             
            
               
                   
               
               
                 Example composition for a produced ANMRM used as a catalyst. 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 Component 
                 Fe 2 O 3   
                 Al 2 O 3   
                 SiO 2   
                 Na 2 O 
                 CaO 
                 TiO 2   
                 NiO 
               
               
                   
               
               
                 Weight 
                 32% 
                 12.4% 
                 8.5% 
                 0.08% 
                 3.8% 
                 15% 
                 24% 
               
               
                 Percentage 
               
               
                   
               
            
           
         
       
     
     Because red mud is a highly variable waste material, elemental composition will vary between samples and test results. 
     Catalyst Preparation. An acid nickel-modified red mud (ANMRM) catalyst with 18.6 wt. % nickel metal was prepared using a homogeneous precipitation process. Using an unmodified red mud catalyst precursor, 20 wt. % of nickel was targeted to be loaded in the red mud to enhance bi-reforming activity, and 18.6 wt. % of nickel was confirmed by X-ray fluorescence (XRF) analysis (about 24% nickel oxide, also referred to as NiO). Depending on the catalyst application, nickel oxide can be loaded to a red mud precursor from between about 1 wt. % to about 50 wt. %. Nickel can be combined with red mud to result in nickel(II) oxide, NiO, in addition to or alternative to nickel(III) oxide, Ni 2 O 3 . 
     BET surface area analysis showed unmodified red mud surface area was about 16 m 2 /g. BET surface area for acid modified red mud was about 170 m 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 2 /g and about 90 m 2 /g, for example about 63 m 2 /g or about 89 m 2 /g. 
     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. The two solutions were mixed, and the final solution was precipitated by slowly adding between about 20 mL to about 30 mL aqueous ammonia with stirring until pH reached 8. Then, the mixed solution was filtered, dried in an oven at 105° C., and calcined at 600° C. for 4 hours. The final ANMRM product was ground to have a particle size of less than about 70 μm. The step of drying in an oven can last from about 2 to about 24 hours. 
     Other nickel-containing compounds can be used in addition to or alternative to nickel nitrate, including any nickel-containing compounds soluble in ethanol or other organic or inorganic alcohols, or in aqueous ammonia. Nickel can be combined with red mud to result in nickel(II) oxide, NiO, in addition to or alternative to nickel(III) oxide, Ni 2 O 3 . 
     Catalyst testing. Several tests on red mud catalytic activity and ANMRM catalytic activity for bi-reforming were experimentally conducted. Red mud was tested as received without any modifications. It was placed in in a Micromeritics® PID Eng &amp; Tech brand microactivity reactor designed for catalyst activity and selectivity analysis, and the same was done for the prepared ANMRM catalyst. The results are compared, for example, in  FIGS. 1 and 2 . Results show that ANMRM catalytic activity for bi-reforming is advantageously improved over non-modified red mud catalytic activity for bi-reforming. 
       FIG. 1  is a graph showing conversion percentage for CH 4  in a bi-reforming process for unmodified red mud (RM) used as a catalyst and for ANMRM used as a catalyst. Effects of nickel addition to red mud were studied. Experimental conditions in the bi-reforming reactor included temperature at about 750° C., pressure at about 14 bar, and gas hourly space velocity (GHSV) at about 7362 h −1 . The test was conducted for 6 hours. The feed was 50 mol. % methane, 17 mol. % CO 2 , and 33 mol. % steam 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. For bi-reforming, the feed composition can comprise, consist essentially of, or consist of CH 4 , CO 2 , and steam. Based in part on thermodynamics, a suitable molar ratio of methane:carbon dioxide:steam is about 3:1:2. 
     Methane conversion illustrated in  FIG. 1  shows ANMRM catalyst outperformed its counterpart, the untreated red mud. Methane conversion by ANMRM reached up to about 40%. On the other hand, unmodified red mud was not effective as a catalyst for conversion of methane. The conversion rate of ANMRM can be attributed to the addition of nickel and synergies of the nickel with the existing transition metals in the red mud. 
       FIG. 2  is a graph showing mol. % of H 2  out of the total products produced from bi-reforming of CH 4  for unmodified red mud used as a catalyst and for ANMRM used as a catalyst. Hydrogen production illustrated in  FIG. 2  shows that untreated red mud produced low amounts of hydrogen, whereas ANMRM catalyst produced up to about 45 mol. % hydrogen. Nickel modification of red mud has enhanced the performance significantly. 
     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. 
     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.