WO2021154864A1 - Catalyst compositions having enhanced acidity for dry reforming processes - Google Patents

Catalyst compositions having enhanced acidity for dry reforming processes Download PDF

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Publication number
WO2021154864A1
WO2021154864A1 PCT/US2021/015303 US2021015303W WO2021154864A1 WO 2021154864 A1 WO2021154864 A1 WO 2021154864A1 US 2021015303 W US2021015303 W US 2021015303W WO 2021154864 A1 WO2021154864 A1 WO 2021154864A1
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Prior art keywords
red mud
catalyst composition
composition
modified red
mud catalyst
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French (fr)
Inventor
Bandar ALSOLAMI
Bandar FADHEL
Rami BAMAGAIN
Mohammed Albuali
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Saudi Arabian Oil Co
Aramco Services Co
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Saudi Arabian Oil Co
Aramco Services Co
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    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts
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    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/883—Molybdenum and nickel
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    • B01J35/613—10-100 m2/g
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01J35/615—100-500 m2/g
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    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C—CHEMISTRY; METALLURGY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
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    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
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    • C01B2203/1082—Composition of support materials
    • C—CHEMISTRY; METALLURGY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • Embodiments of the disclosure relate to catalyst compositions for use in reforming processes.
  • certain embodiments of the disclosure relate to Periodic Table Group VIB metal oxide containing catalyst compositions for and methods of dry reforming.
  • Dry reforming simultaneously utilizes two greenhouse gases, CH4 and CO2, to produce synthesis (syn) gas (CO and 3 ⁇ 4).
  • CH4 and CO2 greenhouse gases
  • Syn synthesis gas
  • 3 ⁇ 4 synthesis gas
  • one challenge of dry reforming is the lack of available, durable, and cost-effective catalyst.
  • Dry reforming generally applies a catalyst, increased temperature, and increased pressure in a process generally according to Equation 1.
  • Dry reforming generally is not as common as steam reforming, and one use is in processes that require a high proportion of CO versus 3 ⁇ 4 in the produced synthesis gas.
  • the thermodynamics of dry reforming are similar to those of steam reforming.
  • One difference of dry reforming from steam reforming is dry reforming’s tendency for coking, increased by a lack of steam to remove carbon deposits.
  • steam is added for effective reduction or removal of coke. Since coking can quickly deactivate Ni catalysts, Rh and Ru catalysts are used in some dry reforming applications.
  • compositions of Periodic Table Group VIB Group VIB
  • Enhanced-acidity Group VIB catalyst compositions are disclosed, in some embodiments further including nickel.
  • the enhanced-acidity Group VIB catalysts also contain in some embodiments Fe, Al, Si, Na, Ca, and Ti oxides from red mud.
  • red mud acts as a catalyst in addition to or alternative to a catalyst carrier.
  • Disclosed compositions are useful as a catalyst in dry reforming processes for the conversion of methane to syngas, according to Equation 1. Utilization of red mud in dry reforming processes provides the concurrent advantages of utilizing a waste material (red mud), converting CO2 (a greenhouse gas), and producing 3 ⁇ 4.
  • Red mud is a caustic waste material produced from bauxite ore processing for alumina extraction, and is utilized here as a catalyst for a dry reforming process. 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. Dry reforming is considered to be a green method for the production of syngas (3 ⁇ 4 and CO), since it utilizes as reactants two greenhouse gases, CH4 and CO2. Despite that, widespread adoption of dry reforming processes has been stymied due in part to the lack of commercially-available durable and efficient catalysts. Red mud generally includes a mixture of transition metals such as Ti, Fe, and Al, which make it an advantageous catalyst for dry reforming processes, for example once modified with nickel and molybdenum.
  • Embodiments disclosed here apply red mud as an active catalyst support, promotor, in addition to or alternative to catalyst to produce hydrogen through dry reforming of methane.
  • a modified red mud catalyst 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.
  • the Group VIB metal oxide comprises at least one metal selected from the group consisting of: chromium, molybdenum, and tungsten.
  • the composition includes at least one component selected from the group consisting of: FeiCb, AI2O3, S1O2, Na 2 0, CaO, and T1O2. Still in other embodiments, a majority of the particles of the composition have a particle size of less than about 70 pm.
  • 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 some embodiments, the nickel oxide is present at about 23 wt.% of the modified red mud catalyst composition.
  • the Group VIB metal oxide is present at between about 1 wt.% to about 20 wt.% of the modified red mud catalyst composition. In some embodiments, the Group VIB metal oxide is present at between about 1 wt.% to about 10 wt.% of the modified red mud catalyst composition. Still in other embodiments, the Group VIB metal oxide is present at about 5 wt.% of the modified red mud catalyst composition. In yet other embodiments, the Bmnauer-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.
  • BET Bmnauer-Emmett-Teller
  • the modified red mud catalyst compositions include dissolving red mud material produced from an alumina extraction process from bauxite ore in water to produce a red mud solution; neutralizing the pH of the red mud solution using an acid; preparing a nickel-containing solution; preparing a Periodic Table Group VIB metal oxide-containing solution; 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 calcining the modified red mud catalyst composition.
  • the Group VIB metal oxide comprises at least one metal selected from the group consisting of: chromium, molybdenum, and tungsten.
  • the water comprises deionized water.
  • the acid comprises hydrochloric acid.
  • the nickel-containing solution comprises nickel nitrate dissolved in ethanol. Still in other embodiments, the Group VIB metal oxide- containing solution comprises ammonium molybdate dissolved in ethanol.
  • the method includes filtering the modified red mud catalyst composition and drying the modified red mud catalyst composition before the step of calcining. In some embodiments, the step of drying occurs at about 100 °C. Still in other embodiments, the step of calcining takes place for about 4 hours at between about 500 °C to about 700 °C. In yet other embodiments, the step of calcining takes place for about 4 hours at about 600 °C.
  • the method includes the step of grinding the modified red mud catalyst composition to a particle size of less than about 70 pm.
  • the BET surface area of the modified red mud catalyst composition is between about 50 m 2 /g and about 90 m 2 /g.
  • a method for dry reforming over a modified red mud catalyst composition including providing a methane feed and carbon dioxide feed to react over the modified red mud catalyst composition at increased temperature and increased pressure to produce synthesis gas comprising 3 ⁇ 4 and CO, the composition comprising: 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.
  • the Group VIB metal oxide comprises at least one metal selected from the group consisting of: chromium, molybdenum, and tungsten. Still in other embodiments, the increased temperature is between about 500 °C to about 1000 °C. In some embodiments, the increased temperature is between about 600 °C to about 800 °C. 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 other embodiments, the increased pressure is between about 10 bar and about 15 bar. Still in other embodiments, the increased pressure is about 14 bar. In yet other embodiments, the methane conversion rate is at least about 14% for at least about 6 hours.
  • gas hourly space velocity of the methane feed and carbon dioxide feed mixed is between about 1000 h 1 to 10000 h 1 .
  • the composition includes at least one component selected from the group consisting of: Fe 2 0 3 , AI2O3, S1O2, Na 2 0, CaO, and T1O2.
  • a majority of the particles of the composition have a particle size of less than about 70 pm.
  • the nickel oxide is present at between about 10 wt.% to about 30 wt.% of the modified red mud catalyst composition.
  • 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 23 wt.% of the modified red mud catalyst composition. In some embodiments, the Group VIB metal oxide is present at between about 1 wt.% to about 20 wt.% of the modified red mud catalyst composition. Still in other embodiments, the Group VIB metal oxide is present at between about 1 wt.% to about 10 wt.% of the modified red mud catalyst composition. In certain embodiments, the Group VIB metal oxide is present at about 5 wt.% of the modified red mud catalyst composition.
  • a molar ratio of the methane feed to the carbon dioxide feed is between about 1 : 1 and about 1 : 1.75.
  • produced 3 ⁇ 4 is at least about 9 mol.% of produced products from the reaction.
  • the BET surface area of the modified red mud catalyst composition is between about 50 m 2 /g and about 90 m 2 /g.
  • modified red mud catalyst compositions with nickel in addition to or alternative to molybdenum or other metals include between about 15 wt.% and about 30 wt.% AI2O3, between about 1 wt.% and about 5 wt.% CaO, between about 10 wt.% and about 30 wt.% Fe 2 0 3 , between about 1 wt.% and about 5 wt.% Na20, between about 10 wt.% and about 25 wt.% S1O2, and between about 1 wt.% and about 10 wt.% T1O2.
  • FIG. 1 is a graph showing conversion percentage for CFU 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.
  • RM unmodified red mud
  • ANMoMRM acid nickel-molybdenum-modified red mud
  • FIG. 2 is a graph showing mol.% of Fh out of the total products produced from dry reforming of CFU in a dry reforming process for unmodified red mud used as a catalyst and for ANMoMRM used as a catalyst.
  • 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.
  • Example composition ranges for global red mud.
  • Red mud was modified with nickel and molybdenum to be utilized and tested as a catalyst for dry reforming as follows.
  • nickel is not required.
  • 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 A1 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 Saudi Arabian red mud (RM) catalyst/catalyst support composition.
  • the untreated red mud exhibited a Brunauer-Emmett-Teller (BET) surface area of about 16 m 2 /g.
  • BET Brunauer-Emmett-Teller
  • 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.
  • Example composition for a produced ANMoMRM used as a catalyst was not limited.
  • red mud is a highly variable waste material, elemental composition will vary between samples and test results.
  • 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.
  • XRF X-ray fluorescence
  • molybdenum oxide also referred to as MoO
  • nickel oxide can be loaded to a red mud precursor from between about 1 wt.% to about 50 wt.%
  • 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.%.
  • 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 pm.
  • the step of drying in an oven can last from about 2 to about 24 hours.
  • 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, NLCL.
  • Molybdenum can be combined with red mud to result in (molybdenum dioxide, M0O2) or Molybdenum(VI) oxide (molybdenum trioxide, M0O3).
  • 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.
  • FIG. 1 is a graph showing conversion percentage for C3 ⁇ 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 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.% CO2 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.
  • GHSV gas hourly space velocity
  • the feed composition will include CH4 and CO2.
  • a feed will consist essentially of or consist of CH4 and CO2.
  • the molar ratio of the feed for CH4 to CO2 can be about 1:1.
  • some other embodiments showed that greater CO2 concentrations up to 1:1.75 (mole CH4 to mole CO2) surprisingly and unexpectedly enhanced 3 ⁇ 4 production.
  • 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.
  • FIG. 2 is a graph showing mol.% of 3 ⁇ 4 out of the total products produced from dry reforming of CH4 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.

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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.

Description

CATALYST COMPOSITIONS HAVING ENHANCED ACIDITY
FOR DRY REFORMING PROCESSES
BACKGROUND
Field
[0001] Embodiments of the disclosure relate to catalyst compositions for use in reforming processes. In particular, certain embodiments of the disclosure relate to Periodic Table Group VIB metal oxide containing catalyst compositions for and methods of dry reforming.
Description of the Related Art
[0002] Dry reforming simultaneously utilizes two greenhouse gases, CH4 and CO2, to produce synthesis (syn) gas (CO and ¾). However, one challenge of dry reforming is the lack of available, durable, and cost-effective catalyst. Dry reforming generally applies a catalyst, increased temperature, and increased pressure in a process generally according to Equation 1.
CH4 + C02 2H2 + 2CO Eq. 1
[0003] Dry reforming generally is not as common as steam reforming, and one use is in processes that require a high proportion of CO versus ¾ in the produced synthesis gas. The thermodynamics of dry reforming are similar to those of steam reforming. One difference of dry reforming from steam reforming is dry reforming’s tendency for coking, increased by a lack of steam to remove carbon deposits. In some applications like mixed reforming or bi-reforming (a combination of steam and dry reforming), steam is added for effective reduction or removal of coke. Since coking can quickly deactivate Ni catalysts, Rh and Ru catalysts are used in some dry reforming applications.
[0004] Present catalyst technology is insufficient in some processes to provide cost-effective means for dry reforming.
SUMMARY OF THE INVENTION
[0005] Applicant has recognized a need for compositions of Periodic Table Group VIB (Group VIB) metal oxide containing modified red mud to be applied in systems and processes for dry reforming. Enhanced-acidity Group VIB catalyst compositions are disclosed, in some embodiments further including nickel. The enhanced-acidity Group VIB catalysts also contain 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 dry reforming processes for the conversion of methane to syngas, according to Equation 1. Utilization of red mud in dry reforming processes provides the concurrent advantages of utilizing a waste material (red mud), converting CO2 (a greenhouse gas), and producing ¾.
[0006] Red mud is a caustic waste material produced from bauxite ore processing for alumina extraction, and is utilized here as a catalyst for a dry reforming process. 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. Dry reforming is considered to be a green method for the production of syngas (¾ and CO), since it utilizes as reactants two greenhouse gases, CH4 and CO2. Despite that, widespread adoption of dry reforming processes has been stymied due in part to the lack of commercially-available durable and efficient catalysts. Red mud generally includes a mixture of transition metals such as Ti, Fe, and Al, which make it an advantageous catalyst for dry reforming processes, for example once modified with nickel and molybdenum.
[0007] Embodiments disclosed here apply red mud as an active catalyst support, promotor, in addition to or alternative to catalyst to produce hydrogen through dry reforming of methane.
[0008] Therefore, disclosed here is a modified red mud catalyst 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. In some embodiments, the Group VIB metal oxide comprises at least one metal selected from the group consisting of: chromium, molybdenum, and tungsten. In other embodiments, the composition includes at least one component selected from the group consisting of: FeiCb, AI2O3, S1O2, Na20, CaO, and T1O2. Still in other embodiments, a majority of the particles of the composition have a particle size of less than about 70 pm. In certain 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 some embodiments, the nickel oxide is present at about 23 wt.% of the modified red mud catalyst composition.
[0009] In other embodiments of the composition, the Group VIB metal oxide is present at between about 1 wt.% to about 20 wt.% of the modified red mud catalyst composition. In some embodiments, the Group VIB metal oxide is present at between about 1 wt.% to about 10 wt.% of the modified red mud catalyst composition. Still in other embodiments, the Group VIB metal oxide is present at about 5 wt.% of the modified red mud catalyst composition. In yet other embodiments, the Bmnauer-Emmett-Teller (BET) surface area of the modified red mud catalyst composition is between about 50 m2/g and about 90 m2/g.
[0010] Additionally disclosed here are methods for producing the modified red mud catalyst compositions, one method including dissolving red mud material produced from an alumina extraction process from bauxite ore in water to produce a red mud solution; neutralizing the pH of the red mud solution using an acid; preparing a nickel-containing solution; preparing a Periodic Table Group VIB metal oxide-containing solution; 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 calcining the modified red mud catalyst composition. In some embodiments, the Group VIB metal oxide comprises at least one metal selected from the group consisting of: chromium, molybdenum, and tungsten. Still in other embodiments, the water comprises deionized water. In certain embodiments, the acid comprises hydrochloric acid.
[0011] In some other embodiments of the methods, the nickel-containing solution comprises nickel nitrate dissolved in ethanol. Still in other embodiments, the Group VIB metal oxide- containing solution comprises ammonium molybdate dissolved in ethanol. In yet other embodiments, the method includes filtering the modified red mud catalyst composition and drying the modified red mud catalyst composition before the step of calcining. In some embodiments, the step of drying occurs at about 100 °C. Still in other embodiments, the step of calcining takes place for about 4 hours at between about 500 °C to about 700 °C. In yet other embodiments, the step of calcining takes place for about 4 hours at about 600 °C. Still in yet other embodiments, the method includes the step of grinding the modified red mud catalyst composition to a particle size of less than about 70 pm. In some embodiments, the BET surface area of the modified red mud catalyst composition is between about 50 m2/g and about 90 m2/g.
[0012] Additionally disclosed here is a method for dry reforming over a modified red mud catalyst composition, the method including providing a methane feed and carbon dioxide feed to react over the modified red mud catalyst composition at increased temperature and increased pressure to produce synthesis gas comprising ¾ and CO, the composition comprising: 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.
[0013] In some embodiments, the Group VIB metal oxide comprises at least one metal selected from the group consisting of: chromium, molybdenum, and tungsten. Still in other embodiments, the increased temperature is between about 500 °C to about 1000 °C. In some embodiments, the increased temperature is between about 600 °C to about 800 °C. 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 other embodiments, the increased pressure is between about 10 bar and about 15 bar. Still in other embodiments, the increased pressure is about 14 bar. In yet other embodiments, the methane conversion rate is at least about 14% for at least about 6 hours. In yet 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: Fe203, AI2O3, S1O2, Na20, CaO, and T1O2. In certain embodiments, a majority of the particles of the composition have a particle size of less than about 70 pm. And in other embodiments, the nickel oxide is present at between about 10 wt.% to about 30 wt.% of the modified red mud catalyst composition.
[0014] 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 23 wt.% of the modified red mud catalyst composition. In some embodiments, the Group VIB metal oxide is present at between about 1 wt.% to about 20 wt.% of the modified red mud catalyst composition. Still in other embodiments, the Group VIB metal oxide is present at between about 1 wt.% to about 10 wt.% of the modified red mud catalyst composition. In certain embodiments, the Group VIB metal oxide is present at about 5 wt.% of the modified red mud catalyst composition. In certain other embodiments, a molar ratio of the methane feed to the carbon dioxide feed is between about 1 : 1 and about 1 : 1.75. In some embodiments, produced ¾ is at least about 9 mol.% of produced products from the reaction. And in other embodiments, the BET surface area of the modified red mud catalyst composition is between about 50 m2/g and about 90 m2/g.
[0015] In some embodiments of the compositions and methods described, modified red mud catalyst compositions with nickel in addition to or alternative to molybdenum or other metals include between about 15 wt.% and about 30 wt.% AI2O3, between about 1 wt.% and about 5 wt.% CaO, between about 10 wt.% and about 30 wt.% Fe203, between about 1 wt.% and about 5 wt.% Na20, between about 10 wt.% and about 25 wt.% S1O2, and between about 1 wt.% and about 10 wt.% T1O2.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] 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.
[0017] FIG. 1 is a graph showing conversion percentage for CFU 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.
[0018] FIG. 2 is a graph showing mol.% of Fh out of the total products produced from dry reforming of CFU in a dry reforming process for unmodified red mud used as a catalyst and for ANMoMRM used as a catalyst.
DETAILED DESCRIPTION OF THE INVENTION
[0019] 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.
[0020] 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.
Figure imgf000010_0001
[0021] 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 A1 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 Saudi Arabian red mud (RM) catalyst/catalyst support composition.
Figure imgf000011_0001
[0022] The untreated red mud exhibited a Brunauer-Emmett-Teller (BET) surface area of about 16 m2/g.
[0023] 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.
Table 3. Example composition for a produced ANMoMRM used as a catalyst.
Figure imgf000011_0002
[0024] Because red mud is a highly variable waste material, elemental composition will vary between samples and test results.
[0025] 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.%.
[0026] First, 10 g of Saudi Arabian red mud from Ma'aden Aluminium Company, based at Ras A1 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 pm. The step of drying in an oven can last from about 2 to about 24 hours.
[0027] 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, NLCL. Molybdenum can be combined with red mud to result in (molybdenum dioxide, M0O2) or Molybdenum(VI) oxide (molybdenum trioxide, M0O3).
[0028] BET surface area analysis showed unmodified red mud surface area was about 16 m2/g. BET surface area for acid modified red mud was about 170 m2/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 m2/g and about 90 m2/g, for example about 63 m2/g or about 89 m2/g.
[0029] 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.
[0030] FIG. 1 is a graph showing conversion percentage for C¾ 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 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.% CO2 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.
[0031] For dry reforming, the feed composition will include CH4 and CO2. In some embodiments for dry reforming, a feed will consist essentially of or consist of CH4 and CO2. Based on thermodynamics, the molar ratio of the feed for CH4 to CO2 can be about 1:1. However, some other embodiments showed that greater CO2 concentrations up to 1:1.75 (mole CH4 to mole CO2) surprisingly and unexpectedly enhanced ¾ production.
[0032] 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.
[0033] FIG. 2 is a graph showing mol.% of ¾ out of the total products produced from dry reforming of CH4 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.
[0034] 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.
[0035] 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.

Claims

CLAIMS That claimed is:
1. A modified red mud catalyst composition, the composition comprising: red mud material produced from an alumina extraction process from bauxite ore; nickel oxide, the nickel oxide present at between 5 wt.% to 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 1 wt.% and 30 wt. % of the modified red mud catalyst composition.
2. The composition according to claim 1, where the Group VIB metal oxide comprises at least one metal selected from the group consisting of: chromium, molybdenum, and tungsten.
3. The composition according to claim 1 or claim 2, further comprising at least one component selected from the group consisting of: Fe203, AI2O3, S1O2, Na20, CaO, and T1O2.
4. The composition according to any one of claims 1 to 3, where a majority of the particles of the composition have a particle size of less than 70 pm.
5. The composition according to any one of claims 1 to 4, where the nickel oxide is present at between 10 wt.% to 30 wt.% of the modified red mud catalyst composition.
6. The composition according to any one of claims 1 to 4, where the nickel oxide is present at between 15 wt.% to 25 wt.% of the modified red mud catalyst composition.
7. The composition according to any one of claims 1 to 4, where the nickel oxide is present at 23 wt.% of the modified red mud catalyst composition.
8. The composition according to any one of claims 1 to 7, where the Group VIB metal oxide is present at between 1 wt.% to 20 wt.% of the modified red mud catalyst composition.
9. The composition according to any one of claims 1 to 7, where the Group VIB metal oxide is present at between 1 wt.% to 10 wt.% of the modified red mud catalyst composition.
10. The composition according to any one of claims 1 to 7, where the Group VIB metal oxide is present at 5 wt.% of the modified red mud catalyst composition.
11. The composition according to any one of claims 1 to 10, where the Brunauer-Emmett- Teller (BET) surface area of the modified red mud catalyst composition is between 50 m2/g and 90 m2/g.
12. The composition according to any one of claims 1 to 11, where the composition includes between 15 wt.% and 30 wt.% AI2O3, between 1 wt.% and 5 wt.% CaO, between 10 wt.% and 30 wt.% Fe203, between 1 wt.% and 5 wt.% Na20, between 10 wt.% and 25 wt.% S1O2, and between 1 wt.% and 10 wt.% T1O2.
13. A method for producing the modified red mud catalyst composition of claim 1, the method comprising the steps of: dissolving red mud material produced from an alumina extraction process from bauxite ore in water to produce a red mud solution; neutralizing the pH of the red mud solution using an acid; preparing a nickel-containing solution; preparing a Periodic Table Group VIB metal oxide-containing solution; 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 calcining the modified red mud catalyst composition.
14. The method according to claim 13, where the Group VIB metal oxide comprises at least one metal selected from the group consisting of: chromium, molybdenum, and tungsten.
15. The method according to claim 13 or claim 14, where the water comprises deionized water.
16. The method according to any one of claims 13 to 15, where the acid comprises hydrochloric acid.
17. The method according to any one of claims 13 to 16, where the nickel-containing solution comprises nickel nitrate dissolved in ethanol.
18. The method according to any one of claims 13 to 17, where the Group VIB metal oxide- containing solution comprises ammonium molybdate dissolved in ethanol.
19. The method according to any one of claims 13 to 18, further comprising filtering the modified red mud catalyst composition and drying the modified red mud catalyst composition before the step of calcining.
20. The method according to claim 19, where the step of drying occurs at 100 °C.
21. The method according to any one of claims 13 to 20, where the step of calcining takes place for 4 hours at between 500 °C to 700 °C.
22. The method according to any one of claims 13 to 20, where the step of calcining takes place for 4 hours at 600 °C.
23. The method according to any one of claims 13 to 22, further comprising the step of grinding the modified red mud catalyst composition to a particle size of less than 70 pm.
24. The method according to any one of claims 13 to 23, where the Bmnauer-Emmett-Teller (BET) surface area of the modified red mud catalyst composition is between 50 m2/g and 90 m2/g.
25. The method according to any one of claims 13 to 24, where the composition includes between 15 wt.% and 30 wt.% AI2O3, between 1 wt.% and 5 wt.% CaO, between 10 wt.% and 30 wt.% Fe203, between 1 wt.% and 5 wt.% Na20, between 10 wt.% and 25 wt.% S1O2, and between 1 wt.% and 10 wt.% T1O2.
26. 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 increased temperature and increased pressure to produce synthesis gas comprising ¾ and CO, the composition comprising: red mud material produced from an alumina extraction process from bauxite ore; nickel oxide, the nickel oxide present at between 5 wt.% to 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 1 wt.% and 30 wt. % of the modified red mud catalyst composition.
27. The method according to claim 26, where the Group VIB metal oxide comprises at least one metal selected from the group consisting of: chromium, molybdenum, and tungsten.
28. The method according to claim 26 or claim 27, where the increased temperature is between 500 °C to 1000 °C.
29. The method according to claim 26 or claim 27, where the increased temperature is between 600 °C to 800 °C.
30. The method according to claim 26 or claim 27, where the increased temperature is 750 °C.
31. The method according to any one of claims 26 to 30, where the increased pressure is between 5 bar and 20 bar.
32. The method according to any one of claims 26 to 30, where the increased pressure is between 10 bar and 15 bar.
33. The method according to any one of claims 26 to 30, where the increased pressure is 14 bar.
34. The method according to any one of claims 26 to 33, where the methane conversion rate is at least 14% for at least 6 hours.
35. The method according to any one of claims 26 to 34, where gas hourly space velocity of the methane feed and carbon dioxide feed mixed is between 1000 h 1 to 10000 h 1.
36. The method according to any one of claims 26 to 35, where the composition includes at least one component selected from the group consisting of: FeiCb, AI2O3, S1O2, Na20, CaO, and T1O2.
37. The method according to any one of claims 26 to 36, where a majority of the particles of the composition have a particle size of less than 70 pm.
38. The method according to any one of claims 26 to 37, where the nickel oxide is present at between 10 wt.% to 30 wt.% of the modified red mud catalyst composition.
39. The method according to any one of claims 26 to 37, where the nickel oxide is present at between 15 wt.% to 25 wt.% of the modified red mud catalyst composition.
40. The method according to any one of claims 26 to 37, where the nickel oxide is present at 23 wt.% of the modified red mud catalyst composition.
41. The method according to any one of claims 26 to 40, where the Group VIB metal oxide is present at between 1 wt.% to 20 wt.% of the modified red mud catalyst composition.
42. The method according to any one of claims 26 to 40, where the Group VIB metal oxide is present at between 1 wt.% to 10 wt.% of the modified red mud catalyst composition.
43. The method according to any one of claims 26 to 40, where the Group VIB metal oxide is present at 5 wt.% of the modified red mud catalyst composition.
44. The method according to any one of claims 26 to 43, where a molar ratio of the methane feed to the carbon dioxide feed is between 1:1 and 1:1.75.
45. The method according to any one of claims 26 to 44, where produced ¾ is at least 9 mol.% of produced products from the reaction.
46. The method according to any one of claims 26 to 45, where the Bmnauer-Emmett-Teller (BET) surface area of the modified red mud catalyst composition is between 50 m2/g and 90 m2/g.
47. The method according to any one of claims 26 to 46, where the composition includes between 15 wt.% and 30 wt.% AI2O3, between 1 wt.% and 5 wt.% CaO, between 10 wt.% and 30 wt.% Fe203, between 1 wt.% and 5 wt.% Na20, between 10 wt.% and 25 wt.% S1O2, and between 1 wt.% and 10 wt.% T1O2.
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