A CATALYST COMPOSITION

Abstract

The present disclosure relates to a catalyst composition comprising a first metal complex and optionally a second metal complex dispersed throughout a matrix of an inorganic material. The present disclosure also relates to a method for preparing the catalyst composition, a catalyst comprising the catalyst composition, use of the catalyst composition as a catalyst or the catalyst for converting natural gas to syngas and a method for converting natural gas to syngas using the catalyst composition as a catalyst or the catalyst.

Claims

1. A catalyst composition comprising a first metal complex, and optionally a second metal complex, dispersed throughout a matrix of an inorganic material.

2. The catalyst composition according to claim 1, wherein the first metal complex and the second metal complex is the same or different.

3. The catalyst composition according to claim 1- or 2, wherein the first metal complex and optional second metal complex independently comprise a catalyst metal and a ligand.

4. The catalyst composition according to claim 3, wherein the catalyst metal is selected from the group consisting of Ca, Mg, La, Ni, Pt, Co, Mo, Zr, Sr, Ce, Fe, Zn and any mixture thereof.

5. The catalyst composition according to claim 3, wherein the ligand is selected from the group consisting of ammonia, ethylamine, diethylamine, triethylamine, pyrrolidine, pyrrole, imidazolidine, pyrazolidine, imidazole, pyrazole, oxazolidine, isoxazolidine, oxazole, isoxazole, triazole, furazan, oxadiazole, dioxazole, tretrazole, piperidine, pyridine, diazinane, diazine, morpholine, oxazine, ethylene diamine (en), ethylene triamine, ethylenediaminetetraacetic acid (EDTA), ethyleneglycoltetraacetic acid, ethylendiaminedipropionic acid, hexamethylenediaminetetraacetic acid, dipicolinic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid in their ionic and neutral form and any mixture thereof.

6. The catalyst composition according to claim 1, wherein the inorganic material comprises a compound selected from the group consisting of silicon, a silicon-containing compound, a metallosilicate, a heterometallosilicate, a metal oxide or a combination thereof as the main component.

7. The catalyst composition according to claim 1, wherein the ratio of the first metal complex and second metal complex, when present, to the inorganic material in the matrix is in the range of 1:1 to 1:80 by weight.

8. The catalyst composition according to claim 1, wherein the catalyst composition is in the form of particles with diameters in the range of 1 nm to 20 nm.

9. The catalyst composition according to any one of claim 1, wherein the catalyst composition is impregnated in a support material.

10. The catalyst composition according to claim 9, wherein; a) the support material is selected from the group consisting of silica, alumina, silica-alumina, aluminosilicate mineral, aluminium silicate, titanium silicate, clay, halloysite clay, metal alloy, montmorillonite clay, zeolite, porous glass, support metal oxide, support semi-metal oxide, molecular sieve, silica gel and any mixture thereof; and/or b) the support material is impregnated with the catalyst composition at a ratio in the range of 2:1 to 1:15 by weight.

11. (canceled)

12. The catalyst composition according to claim 1, wherein the first metal complex is [Ni(en).sub.3] (NO.sub.3).sub.2 and the second metal complex, when present, is [Ce(EDTA)] (NO.sub.3).sub.3.

13. A method for preparing a catalyst composition comprising a first metal complex, and optionally a second metal complex, dispersed throughout a matrix of an inorganic material, comprising the steps of: (a) providing a solution of the first metal complex and optionally a solution of the second metal complex; (b) providing a solution of the inorganic material; and (c) mixing the solution of the first metal complex and optionally the solution of the second metal complex with the solution of the inorganic material, to form a dispersion of the first metal complex, and optionally the second metal complex, throughout the matrix of the inorganic material and thereby the catalyst composition.

14. The method according to claim 13, wherein the providing step (a) comprises the step of mixing a first catalyst metal salt with a first ligand in a first solvent to form the first metal complex, wherein the first catalyst metal salt comprises a first catalyst metal cation of a first catalyst metal and a first counteranion, and where the second metal complex is present, the step of mixing a second catalyst metal salt with a second ligand in a second solvent to form the second metal complex, wherein the second catalyst metal salt comprises a second catalyst metal cation of a second catalyst metal and a second counteranion.

15. The method according to claim 14, wherein the first catalyst metal and the first ligand is mixed at a ratio in the range of 1:2 to 1:7 by weight and wherein the second catalyst metal and the second ligand, when present, is mixed at a ratio in the range of 1:2 to 1:7 by weight.

16. The method according to claim 13, wherein the providing step (b) comprises the steps of (b1) mixing an inorganic material precursor with a third solvent, wherein the inorganic material precursor is selected from the group consisting of silane, orthosilicate, tetramethyl orthosilicate, tetraethyl orthosilicate, aluminium chloride, aluminium nitrate, aluminium sulphate, tetrabutylortho titane, tetraethyl titane, tetrapropylortho titane, Na.sub.2HAsO.sub.4.Math.7H.sub.2O, H.sub.3BO.sub.3, BeSO.sub.4.Math.4H.sub.2O, Cr(NO.sub.3).sub.3.Math.9H.sub.2O, In(NO.sub.3).sub.3.Math.xH.sub.2O, Ti[OCH(CH.sub.3).sub.2].sub.4, Zr(NO.sub.3).sub.4, Fe(NO.sub.3).sub.3.Math.9H.sub.2O, Co(NO.sub.3).sub.2.Math.6H.sub.2O, NaVO.sub.3, Ga(NO.sub.3).sub.3.Math.xH.sub.2O, Ge(OCH(CH.sub.3).sub.2).sub.4, KSb(OH).sub.6, Na.sub.2SnO.sub.3.Math.3H.sub.2O, Na.sub.2MoO.sub.4, Mg(NO.sub.3).sub.2.Math.6H.sub.2O, Na.sub.2WO.sub.4.Math.2H.sub.2O and any mixture thereof, wherein the third solvent is water or an aqueous solution; and (b2) hydrolyzing the inorganic material precursor with a base, wherein the base is selected from the group consisting of tetrapropylammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, hexapropyl-1,6-hexanediammonium, N,N,N-trimethyl-1-adamantanammonium hydroxide, and any mixture thereof.

17. (canceled)

18. The method according to claim 13, wherein the mixing step (c) is undertaken at least one of: (i) a temperature in the range of 20 C. to 30 C.; (ii) an ambient pressure in the range of 90 kPa to 110 kPa; (iii) a duration in the range of 15 minutes to 2 hours; (iv) a pH in the range of 8 to 14; or (v) all of (i) to (iv).

19. The method according to claim 13, wherein in the mixing step (c) the solution of the first metal complex and solution of the second metal complex, when present, to the solution of the inorganic material is present at a ratio in the range of 1:5 to 1:260 by weight.

20. The method according to claim 13, further comprising the steps of: (d) impregnating a support material with the catalyst composition after mixing step (c) by mixing the catalyst composition with the support material, or contacting a solution of the catalyst composition with the support material; (e) drying the catalyst composition after the mixing step (c) or the impregnated support material after the impregnating step (d); or (f) calcining the catalyst composition after the mixing step (c), after the drying step (e) or the impregnated support material after the impregnating step (d).

21. A catalyst comprising a catalyst composition comprising a first metal complex, and optionally a second metal complex, dispersed throughout a matrix of an inorganic material, a) a first metal complex, and optionally a second metal complex, dispersed throughout a matrix of an inorganic material; or b) a first metal complex, and optionally a second metal complex, dispersed throughout a matrix of an inorganic material embedded in a support material.

22. (canceled)

23. (canceled)

24. A method for converting natural gas to syngas, the method comprising the step of contacting the catalyst composition according to claim 1 as a catalyst or the catalyst of claim 21 or 22, with natural gas.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0141] The disclosure will be better understood with reference to the detailed description when considered in conjunction with the non-limiting examples and the accompanying drawings, in which:

[0142] FIG. 1 shows a schematic drawing of the silica-protected Ni, Ce complex structure used to prepare the novel Steam Methane Reforming (SMR) catalysts as disclosed herein.

[0143] FIG. 2 shows the X-ray diffraction (XRD) patterns for a commercial Nickel-based catalyst (C0) and the amorphous metal complex-inorganic material hybrid catalysts of the present disclosure (C.sub.1 to C6).

[0144] FIG. 3 shows a schematic diagram showing a simulated steam methane reforming process with natural gas oxidation with air as the reactor heat source.

[0145] FIG. 4 comprises FIGS. 4a to 4f and shows the thermodynamic equilibrium results from a simulation of the catalytic process, varying both steam/carbon (S/C) ratio and reaction temperature simultaneously in a Gibbs reactor with steam methane reforming reaction and side reaction, water gas shift (WGS) reaction, where FIG. 4a shows for methane conversion, FIG. 4b shows for H.sub.2 production, FIG. 4c shows for Total CO.sub.2 production (combining both from WGS reaction and CO.sub.2 produced from natural gas oxidation for heating in flue gas), FIG. 4d shows for CO.sub.2 production from WGS reaction, FIG. 4e shows for total amount of CO.sub.2 per kg of H.sub.2 produced and FIG. 4f shows for energy efficiency (kg H.sub.2 produced per kg of CH.sub.4 used in natural gas heating).

[0146] FIG. 5 refers to a graph that shows the H.sub.2-temperature programmed reduction (H.sub.2-TPR) profile for a commercial Nickel-based catalyst (C0).

[0147] FIG. 6 comprises FIGS. 6a to 6f and refers to graphs that show the H.sub.2-temperature programmed reduction (H.sub.2-TPR) profile for the supported amorphous metal complex-inorganic material hybrid catalysts of the present disclosure, where FIG. 6a shows for clay-based Ni catalyst (C.sub.1), where FIG. 6b shows for amorphous SiO.sub.2Al.sub.2O.sub.3based Ni catalyst (C2), where FIG. 6c shows for amorphous SiO.sub.2Al.sub.2O.sub.3 based Ni,Ce catalyst (C3), where FIG. 6d shows for amorphous SiO.sub.2Al.sub.2O.sub.3based Ni,Ce catalyst (C4), where FIG. 6e shows for amorphous SiO.sub.2Al.sub.2O.sub.3 based Ni,Ce catalyst (C5), and where FIG. 6f shows for amorphous SiO.sub.2Al.sub.2O.sub.3 based Ni,Ce catalyst (C6).

[0148] FIG. 7 comprises FIGS. 7a and 7b and refers to graphs that show the results of the catalytic performance tests for the CO to C6 catalysts at steam/carbon (S/C) ratio=0.3. FIG. 7a shows specific activity normalized to per gram Nickel and FIG. 7b shows comparison of CH.sub.4 conversions against thermodynamic limit conversion (Brown dash-dot line).

[0149] FIG. 8a shows graph of thermogravimetric analysis-differential thermal analysis (TGA-DTA) profiles of spent C.sub.1 catalyst from SMR reactions at S/C=0.3 and nitrogen as diluent. FIG. 8b shows graph of thermogravimetric analysis-differential thermal analysis (TGA-DTA) profiles of spent C2 catalyst from SMR reactions at S/C=0.3 and nitrogen as diluent. FIG. 8c shows graph of thermogravimetric analysis-differential thermal analysis (TGA-DTA) profiles of spent C3 catalyst from SMR reactions at S/C=0.3 and nitrogen as diluent. FIG. 8d shows graph of thermogravimetric analysis-differential thermal analysis (TGA-DTA) profiles of spent C4 catalyst from SMR reactions at S/C=0.3 and nitrogen as diluent. FIG. 8e shows graph of thermogravimetric analysis-differential thermal analysis (TGA-DTA) profiles of spent C5 catalyst from SMR reactions at S/C=0.3 and nitrogen as diluent. FIG. 8f shows graph of thermogravimetric analysis-differential thermal analysis (TGA-DTA) profiles of spent C6 catalyst from SMR reactions at S/C=0.3 and nitrogen as diluent

[0150] FIG. 9 comprises FIGS. 9a to 9c and refers to graphs showing the outcomes of the performance tests on undiluted SMR at S/C=0.3. FIG. 9a shows CH.sub.4 conversions for CO and C4 pelletized catalysts. FIG. 9b shows CH.sub.4 conversions for CO pelletized catalyst. FIG. 9c shows CH.sub.4 conversions for C4 pelletized catalyst C4 catalysts.

EXAMPLES

[0151] Non-limiting examples of the invention will be further described in greater detail by reference to specific examples, which should not be construed as in any way limiting the scope of the invention.

Example 1: Preparation of Catalysts

[0152] A catalyst with high coke resistance and activity was prepared using a silica protected Nickel (and Cerium) metal complex solution. The synthesis was facile and easily scaled up due to its one-pot methodology. Subsequently, a series of different supports (e.g., SiO.sub.2Al.sub.2O.sub.3a typical catalyst support, and clays-a 3D printing viable material) were used to demonstrate versatility, where the metal complex-inorganic material hybrid was shown to be dispersed effectively. Importantly, a stable metal complex-inorganic material hybrid structure was prepared to disperse active metal homogeneously within a silica matrix in which silica was exploited to immobilize these metal complexes electrostatically and to protect the active metal against sintering and coking (FIG. 1). Herein, a total of 6 catalysts (denoted C.sub.1 to C6) were prepared and proven to yield better carbon-resistance and activity for low steam to carbon steam methane reforming against a commercial Nickel-based Catalyst (denoted CO). Metal loadings were quantified in Table 1.

TABLE-US-00001 TABLE 1 Metal Loadings of Novel Catalysts and Commercial Catalyst Ni* Ce* Catalyst (wt %) (wt %) Remarks C0 11.8175 Commercial Nickel-based Catalyst C1 4.605 Impregnated with 1x S0{circumflex over ()} on Clay support C2 0.41775 Impregnated with 1x S0{circumflex over ()} on SiO.sub.2Al.sub.2O.sub.3 support C3 0.37175 1.70575 Impregnated with 1x S1{circumflex over ()} on SiO.sub.2Al.sub.2O.sub.3 support C4 0.62675 1.43025 Impregnated with 1x S2{circumflex over ()} on SiO.sub.2Al.sub.2O.sub.3 support C5 4.355 6.375 Impregnated with 7x S2{circumflex over ()} on 10% Ni/SiO.sub.2Al.sub.2O.sub.3 support C6 2.92 7.1225 Impregnated with 10x S2{circumflex over ()} on SiO.sub.2Al.sub.2O.sub.3 support C7 6.496 Ni impregnated on SiO.sub.2Al.sub.2O.sub.3 support; non-silica protect *Metal loadings were determined using ICP-OES {circumflex over ()}S0-S1 denotes different Silica-protected metal-complex solutions detailed in the materials and methods section.

Pretreatment of Silica-Alumina Support

[0153] Prior to use, an amorphous silica-alumina support (obtained from Sigma-Aldrich, St. Louis, Missouri, USA) was treated at 1000 C. for 20 hours (with 10 hours ramping. 1.6 C./min ramp) in a tube furnace under ambient pressure. The support was denoted SiO.sub.2Al.sub.2O.sub.3.

Preparation of 10% Ni/SiO.sub.2Al.sub.2O.sub.3

[0154] 2.477 g Ni(NO.sub.3).sub.2.Math.6H.sub.2O (98%) (obtained from Sigma-Aldrich, St. Louis, Missouri, USA) was dissolved in 10 mL ethanol (99.5%) and was used for the impregnation on 4.5 g SiO.sub.2Al.sub.2O.sub.3.

Preparation of Silica Protected Nickel Complex Solution

[0155] 7.6 g Tetrapropylammonium hydroxide solution (40% aq.), 3.6 g distilled water, and 8.8 g tetraethylorthosilicate (98%) (obtained from Sigma-Aldrich, St. Louis, Missouri, USA) were mixed under stirring at room temperature for 4 hours in a closed bottle. The initial clear silica solution consisted of a molar composition of (TPA) 20:SiO.sub.2: H.sub.2O:EtOH of 4.5:25:289:100. Then, 5 g of a Ni(NH.sub.2CH.sub.2CH.sub.2NH.sub.2).sub.3 solution (obtained from Sigma-Aldrich, St. Louis, Missouri, USA) which contained 13 wt % Ni(NO.sub.3).sub.2.Math.6H.sub.2O and (NH.sub.2CH.sub.2CH.sub.2NH.sub.2).sub.3/H.sub.2O at a weight ratio of 0.12:1 was added to 20 g of the silica solution. To form the Ni(NH.sub.2CH.sub.2CH.sub.2NH.sub.2).sub.3 solution, 1.8 g NH.sub.2CH.sub.2CH.sub.2NH.sub.2 (99.5%) and 2.5 g Ni(NO.sub.3).sub.2.Math.6H.sub.2O (98%), were mixed in 15 mL of distilled water. The ratio between Ni and NH.sub.2CH.sub.2CH.sub.2NH.sub.2 was 1:3.6 by weight.

[0156] The mixture was continuously stirred at room temperature for 30 minutes to obtain a clear violet solution. The Ni(NH.sub.2CH.sub.2CH.sub.2NH.sub.2).sub.3 and tetraethylorthosilicate was mixed at a ratio of 1:8.6 by weight, and the ratio between Ni(NH.sub.2CH.sub.2CH.sub.2NH.sub.2).sub.3 and SiO.sub.2 in the resultant product was 1:2.5 by weight. The solution was transferred into a closed sample bottle and kept in the fridge overnight. The sample was denoted SO.

Preparation of Silica Protected Nickel, Cerium Complex Solution

[0157] 7.6 g Tetrapropylammonium hydroxide solution (40% aq.), 3.6 g distilled water, and 8.8 g tetraethylorthosilicate (98%) (obtained from Sigma-Aldrich, St. Louis, Missouri, USA) were mixed under stirring at room temperature for 4 hours in a closed bottle. The initial clear solution consisted of a molar composition of (TPA) 20:SiO.sub.2: H.sub.2O:EtOH of 4.5:25:289:100. Then, 5 g or 10 g of a Ni(NH.sub.2CH.sub.2CH.sub.2NH.sub.2).sub.3 (obtained from Sigma-Aldrich, St. Louis, Missouri, USA) solution which contained 13 wt % Ni(NO.sub.3) 2.Math.6H.sub.2O and (NH.sub.2CH.sub.2CH.sub.2NH.sub.2).sub.3/H.sub.2O at a weight ratio of 0.12:1 were added to 20 g of the silica solution. To form the Ni(NH.sub.2CH.sub.2CH.sub.2NH.sub.2).sub.3 solution, 1.8 g NH.sub.2CH.sub.2CH.sub.2NH.sub.2 (99.5%) and 2.5 g Ni(NO.sub.3).sub.2.Math.6H.sub.2O (98%), were mixed in 15 mL of distilled water. The ratio between Ni and NH.sub.2CH.sub.2CH.sub.2NH.sub.2 was 1:3.6 by weight. The mixture was continuously stirred at room temperature for 30 minutes to obtain a clear violet solution. 0.6 g of Ce(EDTA) solution which contained 6 wt % of Ce(NO.sub.3) 3.6H.sub.2O and Na.sub.2EDTA.2H.sub.2O/H.sub.2O at a weight ratio of 0.135:1 was then added. To form the Ce(EDTA) solution, 0.675 g Na.sub.2EDTA.2H.sub.2O and 0.36 g Cc (NO.sub.3) 3.Math.6H.sub.2O (obtained from Sigma-Aldrich, St. Louis, Missouri, USA) were mixed in 5 mL of distilled water. The ratio between Ce and Na.sub.2EDTA.2H.sub.2O was 1:5.8 by weight.

[0158] The obtained dark violet clear solution was transferred into a closed sample bottle and kept in the fridge overnight. The Ni(NH.sub.2CH.sub.2CH.sub.2NH.sub.2).sub.3 and tetraethylorthosilicate (obtained from Sigma-Aldrich, St. Louis, Missouri, USA) was mixed at a ratio of 1/8.6 by weight, and the ratio between Ni(NH.sub.2CH.sub.2CH.sub.2NH.sub.2).sub.3 and SiO.sub.2 in the resultant product was 1/2.5 by weight. The Ce(EDTA) and tetraethylorthosilicate was mixed at a ratio of 1/247.7 by weight, and the ratio between Ce(EDTA) and SiO.sub.2 in the resultant product was 1/71.15 by weight. The sample made with 5 g Ni(NH.sub.2CH.sub.2CH.sub.2NH.sub.2).sub.3 solution was denoted S1 while the sample made with 10 g Ni(NH.sub.2CH.sub.2CH.sub.2NH.sub.2).sub.3 solution was denoted S2.

Preparation of C.SUB.1 .Catalyst

[0159] 1 g SO was impregnated in 50 mg halloysite clay (obtained from Sigma-Aldrich, St. Louis, Missouri, USA) with 7 mg of hydroxypropyl methyl cellulose (obtained from Sigma-Aldrich, St. Louis, Missouri, USA) and the mixture was dried under vacuum. The dried powder was calcined at 650 C. for 2 hours (100 C./h ramp) and sieved (40-60 mesh). The sample was denoted C.sub.1.

Preparation of C2 Catalyst

[0160] 1 g SO was impregnated in 1 g SiO.sub.2Al.sub.2O.sub.3 (obtained from Sigma-Aldrich, St. Louis, Missouri, USA) and the mixture was dried under vacuum. The dried powder was calcined at 650 C. for 2 hours (100 C./h ramp) and sieved (40-60 mesh). The sample was denoted C2.

Preparation of C3 Catalyst

[0161] 1 g S1 was impregnated in 1 g SiO.sub.2Al.sub.2O.sub.3 and the mixture was dried under vacuum. The dried powder was calcined at 650 C. for 2 hours (100 C./h ramp) and sieved (40-60 mesh). The sample was denoted C3.

Preparation of C4 Catalyst

[0162] 1 g S2 was impregnated to 1 g SiO.sub.2Al.sub.2O.sub.3 and the mixture was dried under vacuum. The dried powder was calcined at 650 C. for 2 hours (100 C./h ramp) and sieved (40-60 mesh). The sample was denoted as C4.

Preparation of C5 Catalyst

[0163] 1 g S2 was impregnated in 1 g 10% Ni/SiO.sub.2Al.sub.2O.sub.3 and the mixture was dried under vacuum. The same impregnation procedure was repeated for 6 times. The overall composition comprised of 7 g solution and 1 g support. The dried powder was calcined at 650 C. for 2 hours (100 C./h ramp) and sieved (40-60 mesh). The sample was denoted C5.

Preparation of C6 Catalyst

[0164] 1 g S2 was impregnated in 1 g SiO.sub.2Al.sub.2O.sub.3 and the mixture was dried under vacuum. The same impregnation procedure was repeated for 9 times. The overall composition is 10 g solution and 1 g support. The dried powder was calcined at 650 C. for 2 hours (100 C./h ramp) and sieved (40-60 mesh). The sample was denoted C6.

Preparation of C7 Catalyst

[0165] 1.26 g Ni(NO.sub.3) 2. 6H.sub.2O (98%) was dissolved in 10 mL Ethanol and was used for the impregnation in 4.75 g SiO.sub.2Al.sub.2O.sub.3. The dried powder was calcined at 650 C. for 2 hours (100 C./h ramp). The sample was denoted C7.

Example 2: Characterization Data of Catalysts

XRD Measurement

[0166] A typical catalyst powder was scanned over a 20 range of 10-80 (ramp rate of 2/min) in a Shimadzu XRD-6000 X-ray Diffractometer under the conditions of 1 divergence slit, 1 scattering slit and 0.3 mm receiving slit, Cu K X-ray source (beam voltage 40 kV and current 30 mA).

[0167] The catalysts prepared maintained an amorphous character, and X-ray

[0168] Diffraction (XRD) analysis confirmed the lack of well-defined peaks which indicates the absence of crystallites (FIG. 2). A broad peak from 20 to 30 denoted presence of an amorphous silica character. The diffraction peaks of the commercially obtained CO catalyst (20=44.5, 51.8, and 76.4, PDF- #NO. 04-0850) corresponded to the (111), (200), and (220) crystal faces of Ni. NiO crystal faces were also observed at 20-37.2 and 62.9 (PDF- #NO. 47-1049). The C5 XRD pattern showed much less intense NiO peaks at 20=37.2 and 62.9 and a Ni(111) peak at 2=44.5 which suggested a highly dispersed amorphous nature (and small crystallite sizes) of nickel species on the C5 catalysts. Nickel faces in the other catalysts (C.sub.1 to C.sub.4 and C6) were not observable, due to low nickel loading (Table 1), small particle size and their highly dispersed amorphous nature.

Catalytic Performance Tests

[0169] 50 mg of catalysts was loaded into a quartz tube (O.D. =9 mm, I.D. =7 mm) sandwiched between quartz wool before fixing the quartz tube in a heating furnace. A Gasboard 3100 syngas analyzer was used to analyze product gas in the reaction. A liquid pump with heating belt (set at 250 C.) was used to supply steam, and a water trap with a chiller (set at 2 C.) was affixed before the syngas analyzer.

Thermodynamic Analysis for Low Steam-Carbon Ratio SMR

[0170] Thermodynamic equilibrium of S/C=0.3 SMR at any given temperature at atmospheric pressure was calculated by minimizing Gibbs free energy of a multicomponent system. The total Gibbs free energy was the summation of all chemical potential of the species (i.e., methane, water, carbon monoxide, hydrogen, and carbon dioxide). Peng-Robinson Equation of State was chosen to estimate the fugacity coefficient estimations for non-polar systems. Thermodynamic equilibrium calculations were performed on Aspen Plus V12.1 using RGibbs reactor.

Technoeconomic Analysis for Varying Steam-Carbon Ratio SMR

[0171] Aspen HYSYS V12.1 was used to evaluate the effect of steam to carbon ratio (S/C) and reaction temperature on SMR performance (i.e., methane conversion, CO.sub.2 production (from reverse water gas shift and burning of natural gas to supply heat) and energy efficiency (kg H.sub.2 produced per kg of CH.sub.4 used in natural gas heating). Peng Robison equation of state was used as the fluid package in the simulation. A complete combustion of natural gas supplied at 3 bar and 30 C. (90% v/v CH.sub.4, 5% v/v N.sub.2 and 5% v/v CO.sub.2) was assumed for supplying heat to a reactor. The amount of natural gas required was automatically adjusted and determined to supply enough heat energy for maintaining an isothermal reaction. The reaction was assumed to be operating at thermodynamic limit using a Gibbs reactor with a specified reaction equilibrium (i.e., steam methane reforming and water gas shift reactions). A series of varying S/C ratio (from 0.3 to 5) and reaction temperature (500 C. to 1000 C.) case studies were ran on Aspen HYSYS V12.1 and evaluated using Python script with a surf plot.

[0172] Simulation with Aspen HYSYS V12 of steam methane reforming process with typical natural gas feed (i.e., 90% v/v CH.sub.4 with 5% v/v CO.sub.2 and 5% v/v N.sub.2) was studied (FIG. 3). Considering heating of reactor to be from the exothermic reaction between natural gas feed and air, independent variables of S/C ratio (from 0.3 to 5) and reaction temperature (from 500 C. to 1000 C.) were varied to investigate their combined effect on the steam methane reforming process. A Gibbs reactor was used to evaluate steam methane reforming performance at thermal dynamic equilibrium without limiting catalyst performance.

H.SUB.2.-TPR Measurement

[0173] 50 mg of catalyst was used in each analysis in a Thermo Scientific TPDRO-1100 series equipment. H.sub.2-TPR profile was obtained with 30 mL/min 5 vol % H.sub.2 (balance in N.sub.2) and ramping of 10 C./min from room temperature to 900 C.

[0174] While thermodynamics dictate that higher operating temperature and S/C ratio will result in higher CH.sub.4 conversion (FIG. 4a) and hence higher H.sub.2 production (FIG. 4b), the amount of CO.sub.2 produced both from the competing side reaction (i.e., water gas shift (WGS) reaction; H.sub.2O+COCO.sub.2+H.sub.2) and natural gas oxidation for thermal heating per H.sub.2 produced (henceforth denote as Total CO.sub.2 Production) generally decreases with decreasing S/C ratio at the same operating temperature (FIG. 4e). At low S/C ratio, an optimal temperature between 600 to 750 C. gives the lowest amount of CO.sub.2 per kg of H.sub.2 production. Differential changes in total CO.sub.2 production are more significant with a change in S/C ratio in comparison with changing operating temperature (FIG. 4c), and higher S/C ratio will result in more CO.sub.2 produced in the steam methane reforming process. CO.sub.2 production from only WGS is illustrated in FIG. 4d, where the relationship between CO.sub.2 production from WGS and temperature or S/C ratio is similar to that of total CO.sub.2 production (i.e., comparing FIGS. 4c and 4d). Importantly, low S/C ratio is beneficial for achieving low carbon steam methane reforming process. A performance variable, energy efficiency, defined as the amount of H.sub.2 produced per kg of CH.sub.4 used in natural gas heating is developed and illustrated in FIG. 4f. A high energy efficiency (i.e., more H.sub.2 produced per heating unit; CH.sub.4) is achieved at between 600 C. and 750 C. Subsequently, low-carbon steam methane reforming tests at the lowest S/C ratio (i.e., 0.3) and at 600 C. which are extremely harsh conditions that promote coke formation, were tested for the supported amorphous metal complex-inorganic material hybrid catalysts.

[0175] The catalysts were first reduced at 800 C. for 1 hour (10 C./min ramp rate) for CO catalyst and at 600 C. for 1 hour (10 C./min ramp rate) for C.sub.1 to C.sub.6 catalysts according to the H.sub.2-temperature programmed reduction (H.sub.2-TPR) profiles (FIG. 5 and FIG. 6).

TGA-DTA Measurement

[0176] TGA-DTA was used to investigate coking in spent catalyst. Typically, about 7 mg of spent catalyst was used for the analysis in a Shimadzu DTG-60 equipment. Simultaneous heat flow and weight measurements were performed from room temperature to 950 C. with a ramp rate of 10 C./min under air atmosphere.

[0177] Each catalyst (CO to C6) was pelletized (40-60 mesh) prior to a reaction test. At S/C=0.3, specific activities of supported amorphous metal complex-inorganic material hybrid catalysts were constantly superior over the commercial catalyst (C0) (FIG. 7a), thereby showing that the disclosed method in functionalizing active metals (nickel) onto a catalyst support via silica-protection provided significant improvement in catalyzing low S/C SMR reactions while providing versatility in tuning support materials and active metal compositions.

[0178] FIG. 7b shows that the supported amorphous metal complex-inorganic material hybrid catalysts can achieve close to thermodynamic limit conversions at a S/C=0.3 SMR process. Even despite the harsh low steam conditions that promote carbon formation, thermogravimetric analysis-differential thermal analysis (TGA-DTA) experiment on spent C.sub.1 to C.sub.6 catalysts showed negligible carbon formation (FIG. 8).

[0179] Undiluted (i.e., pure feed of methane and steam) SMR at S/C=0.3 was tested for a selected catalyst (C4) against the commercially obtained catalyst CO(FIG. 9a). The CO catalyst deactivated within 30 minutes with significant coking ( 78% carbon, FIG. 9b), meanwhile at the same condition, the C4 catalyst showed superior anti-coking ability

[0180] (FIG. 9c) while continuing to maintain high reaction activity.

INDUSTRIAL APPLICABILITY

[0181] The disclosed catalyst composition may be used as a catalyst for Steam Methane Reforming (SMR) for the production of hydrogen and syngas from natural gas. This is applicable to industries such as energy, electrical and transportation, where the catalyst composition can be used as a highly active catalyst in low-carbon steam methane reforming.

[0182] It will be apparent that various other modifications and adaptations of the invention will be apparent to the person skilled in the art after reading the foregoing disclosure without departing from the spirit and scope of the invention and it is intended that all such modifications and adaptations come within the scope of the appended claims.