CATALYSTS FOR HYDROGEN PRODUCTION

Abstract

It is provided solid, heterogeneous catalysts and a method for producing H.sub.2 by steam reforming. More particularly, the catalyst comprises at least one metal element of Cu, Ni, Fe, Co, Mo, Mn, Mg, Zr, La, Ce, Ti, Zn and W, having a formula Cu.sub.aNi.sub.bFe.sub.c-Co.sub.dMO.sub.eMn.sub.fMg.sub.gZr.sub.hLa.sub.iCe.sub.jTi.sub.kZn.sub.lW.sub.mO.sub.x, wherein a, b, c, d, e, f, g, h, i, j, k, I and m are molar ratios for the respective elements, wherein a, b, c, d, e, f, g and m are >0, h, I, j, k and I are >0 or a, b, c, d, e, f, g, i, and j are ≥0, h, k, I and m are >0 and x is such that the catalyst is electrically neutral. The produced H.sub.2 can be used to powered vehicle as described herein.

Claims

1: A catalyst for producing H.sub.2 by steam reforming of a carbonaceous material, comprising at least six metal element of Cu, Ni, Fe, Co, Mo, Mn, Mg, Zr, La, Ce, Ti, Zn and W, having a formula Cu.sub.aNi.sub.bFe.sub.cCo.sub.dMo.sub.eMn.sub.fMg.sub.gZr.sub.hLa.sub.iCe.sub.jTi.sub.kZn.sub.lW.sub.mO.sub.x, wherein a, b, c, d, e, f, g, h, i, j, k, l and m are molar ratios for the respective elements, wherein a, b, c, d, e, f, g and m are ≥0, a+b+c+d+e+f+g>0, h, i, j, k and l are >0 and x is such that the catalyst is electrically neutral; or a, b, c, d, e, f, g, h, i, j, k, l and m are molar ratios for the respective elements, wherein a, b, c, d, e, f, g, i, and j are ≥0, a+b+c+d+e+f+g>0, h, k, l and m are >0 and x is such that the catalyst is electrically neutral.

2: The catalyst of claim 1, wherein a+b+c+d+e+f+g+h+i+j+k+l=1.

3: The catalyst of claim 1, wherein 0≤a≤0.32, 0≤b≤0.19, 0≤c≤0.29, 0≤d≤0.16, 0≤e≤0.11, 0≤f≤0.21, 0≤g≤0.32, 0.23≤h≤0.42, 0.01≤i≤0.02, 0.03≤j≤0.10, 0.11≤k≤0.20, 0.11≤l≤0.19 and 0≤m≤0.04; or 0≤a≤0.32, 0≤b≤0.19, 0≤c≤0.29, 0≤d≤0.16, 0≤e≤0.11, 0≤f≤0.21, 0≤g≤0.32, 0.23≤h≤0.42, 0≤i≤0.02, 0≤j≤0.10, 0.11≤k≤0.20, 0.11≤l≤0.19 and 0<m≤0.04.

4: The catalyst of claim 1, wherein the metal oxidation state is Cu 0, +1 or +2; Ni 0 or +2; Co 0 or +2; Mo 0 or +2; Mn 0, +2, +3 or +4; Mg 0 or +2; Mn+5, +6 or +7; Fe 0, +2 or +3; Ti 0, +2, +3 or +4; Zn0, +1 or +2; Zr 0 or +4; La 0 or +3; Ce 0, +3 or +4; W 0 or +3, or combination thereof.

5: The catalyst of claim 1, wherein the catalyst is one of: Cu.sub.0.17Fe.sub.0.09Zr.sub.0.35La.sub.0.02Ce.sub.0.05Ti.sub.0.16Zn.sub.0.16O.sub.x; Cu.sub.0.08Ni.sub.0.08Fe.sub.0.06Co.sub.0.12Zr.sub.0.31La.sub.0.01Ce.sub.0.04Ti.sub.0.15Zn.sub.0.14O.sub.x; Cu.sub.0.19Zr.sub.0.38La.sub.0.02Ce.sub.0.05Ti.sub.0.18Zn.sub.0.18 O.sub.x; Ni.sub.0.19Zr.sub.0.38La.sub.0.02Ce.sub.0.05Ti.sub.0.18Zn.sub.0.17O.sub.x; Cu.sub.0.18Ni.sub.0.07Zr.sub.0.36La.sub.0.02Ce.sub.0.05Ti.sub.0.17Zn.sub.0.16O.sub.x; Cu.sub.0.07Ni.sub.0.18Zr.sub.0.36La.sub.0.02Ce.sub.0.05Ti.sub.0.17Zn.sub.0.16O.sub.x; Cu.sub.0.32Zr.sub.0.32La.sub.0.01Ce.sub.0.05Ti.sub.0.15Zn.sub.0.15O.sub.x; Cu.sub.0.27Ni.sub.0.04Fe.sub.0.10Zr.sub.0.28La.sub.0.01Ce.sub.0.04Ti.sub.0.13Zn.sub.0.13O.sub.x; Fe.sub.0.15Zr.sub.0.04La.sub.0.02Ce.sub.0.06Ti.sub.0.19Zn.sub.0.19O.sub.x; Cu.sub.0.15CO.sub.0.16Zr.sub.0.32La.sub.0.01Ce.sub.0.05Ti.sub.0.15Zn.sub.0.15O.sub.x; Cu.sub.0.26Fe.sub.0.15Zr.sub.0.28La.sub.0.01Ce.sub.0.04Ti.sub.0.13Zn.sub.0.13O.sub.x; Cu.sub.0.23Fe.sub.0.26Zr.sub.0.24La.sub.0.01 Ce.sub.0.03Ti.sub.0.11Zn.sub.0.11O.sub.x; Cu.sub.0.13Fe.sub.0.29Zr.sub.0.27La.sub.0.01 Ce.sub.0.04Ti.sub.0.13Zn.sub.0.13O.sub.x; Cu.sub.0.15Mn.sub.0.17Zr.sub.0.32La.sub.0.01Ce.sub.0.05Ti.sub.0.15Zn.sub.0.15O.sub.x; Cu.sub.0.16Mo.sub.0.11Zr.sub.0.34La.sub.0.02Ce.sub.0.05Ti.sub.0.16Zn.sub.0.16O.sub.x; Cu.sub.0.12Mg.sub.0.32Zr.sub.0.26La.sub.0.01 Ce.sub.0.04Ti.sub.0.12Zn.sub.0.12O.sub.x; Cu.sub.0.09Fe.sub.0.09Co.sub.0.09Zr.sub.0.35La.sub.0.02Ce.sub.0.05Ti.sub.0.16Zn.sub.0.16O.sub.x; Cu.sub.0.15Fe.sub.0.17Zr.sub.0.32La.sub.0.01Ce.sub.0.05Ti.sub.0.15Zn.sub.0.15O.sub.x; Ni.sub.0.17 Fe.sub.0.13Mn.sub.0.19Zr.sub.0.33La.sub.0.01Ce.sub.0.05Ti.sub.0.16Zn.sub.0.15O.sub.x; Fe.sub.0.19Zr.sub.0.38La.sub.0.02Ce.sub.0.05Ti.sub.0.18Zn.sub.0.18O.sub.x; Mn.sub.0.21Zr.sub.0.38La.sub.0.02Ce.sub.0.05Ti.sub.0.18Zn.sub.0.17O.sub.x; Cu.sub.0.08Co.sub.0.09Mn.sub.0.09Zr.sub.0.35La.sub.0.02Ce.sub.0.05Ti.sub.0.16Zn.sub.0.16O.sub.x; Ni.sub.0.10Mn.sub.0.10Zr.sub.0.38La.sub.0.02Ce.sub.0.05Ti.sub.0.18Zn.sub.0.17O.sub.x; Co.sub.0.11Zr.sub.0.42La.sub.0.02Ce.sub.0.06Ti.sub.0.20Zn.sub.0.19O.sub.x; Fe.sub.0.1Co.sub.0.10Zr.sub.0.38La.sub.0.02Ce.sub.0.05Ti.sub.0.18Zn.sub.0.17O.sub.x; Co.sub.0.10Zr.sub.0.40La.sub.0.02Ce.sub.0.10Ti.sub.0.19Zn.sub.0.19O.sub.x; Ni.sub.0.1Co.sub.0.10Zr.sub.0.38La.sub.0.02Ce.sub.0.05Ti.sub.0.18Zn.sub.0.17O.sub.x; Co.sub.0.10Mn.sub.0.10Zr.sub.0.37La.sub.0.02Ce.sub.0.05Ti.sub.0.18Zn.sub.0.17O.sub.x; or Cu.sub.0.13Ni.sub.0.09Zr.sub.0.39Ti.sub.0.18Zn.sub.0.18W.sub.0.04O.sub.x.

6: The catalyst of claim 1, wherein the catalyst has a surface area between about 10 m.sup.2/g and about 500 m.sup.2, and/or a total pore volume between 1.01 mL/g and about 1 mL/g.

7. (canceled)

8: The catalyst of claim 1, wherein the catalyst is in powdered, pelleted, extruded form or coated on a metal or any suitable surface with or without an added binder.

9-20. (canceled)

21: A method for producing H.sub.2 by steam reforming of a carbonaceous material, comprising contacting and reacting said carbonaceous material and water with a solid catalyst as defined in claim 1, producing hydrogen.

22: The method of claim 21, wherein the carbonaceous material and water are in a gas phase.

23. (canceled)

24: The method of claim 21, wherein the carbonaceous material comprises methanol, ethanol, propanol, butanol, diethyl ether, dimethyl ether, glycerol, glycol, methane, ethane, butane, gasoline, diesel, a light distillate, naphtha, kerosene, or a combination thereof.

25. (canceled)

26: The method of claim 22, wherein the gas phase further comprise oxygen or air diluted with an inert gas.

27: The method of claim 26, wherein the inert gas is nitrogen or argon.

28: The method of claim 21, wherein hydrogen is produced by a methanol decomposition reaction, by a water gas shift reaction, by a methanol steam reforming reaction, by an ethanol steam reforming reaction, or by a oxidative methanol, oxidative ethanol reforming and/or ethanol steam reforming reaction.

29-32. (canceled)

33: The method of claim 21, further producing carbon monoxide, carbon dioxide, and/or low molecular weight hydrocarbons.

34-35. (canceled)

36: The method of claim 21, wherein the reaction is conducted at temperatures between 150° C. and 1000° C., between 200° C. and 450° C. for methanol reforming or between 300° C. and 1000° C. for ethanol reforming.

37-38. (canceled)

39: The method of claim 21, wherein the reaction is conducted at atmospheric pressure or higher pressure.

40-42. (canceled)

43: The method of claim 21, wherein the reaction is conducted with H.sub.2O to methanol ratio in the gas phase equal to or greater than 1; or is conducted with H.sub.2O to ethanol ratio in the gas phase equal to or greater than 3.

44: The method of claim 21, wherein the reaction is conducted in a fixed bed reactor or on a catalyst coated surface.

45: The method of claim 21, wherein the reaction is conducted in one stage or two or more successive stages.

46: The method of claim 21, wherein the reaction is conducted with a WHSV of methanol between about 0.1 hr.sup.−1 and about 30 hr.sup.−1, with a WHSV of methanol between about 1 hr.sup.−1 and about 15 hr.sup.−1, with a WHSV of ethanol between about 1 hr.sup.−1, or with a WHSV of about 150 hr.sup.−1, with a WHSV of ethanol between about 2.5 hr.sup.−1 and about 100 hr.sup.−1 or with a WHSV of ethanol between about 5 hr.sup.−1 and about 80 hr.sup.−1.

47-62. (canceled)

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0095] Reference will now be made to the accompanying drawings.

[0096] FIG. 1 illustrates a system of methanol reforming for screening solid, heterogeneous catalysts in a single reactor in accordance with one embodiment.

[0097] FIG. 2 shows a system for methanol reforming for screening solid, heterogeneous catalysts in two connected reactors in accordance with one embodiment.

[0098] FIG. 3 shows a plot of temperature vs. methanol conversion, carbon monoxide content, methane content and hydrogen production rate in the product stream for methanol steam reforming in the system of FIG. 1, in accordance with one embodiment.

[0099] FIG. 4 shows a plot of weight hour space velocity (WHSV) vs. methanol conversion, carbon monoxide content, methane content and hydrogen production rate in the product stream for methanol steam reforming in the system of FIG. 1, in accordance with one embodiment.

[0100] FIG. 5 shows a plot of water/methanol ratio vs. methanol conversion, carbon monoxide content, methane content and hydrogen production rate in the product stream for methanol steam reforming in the system of FIG. 1, in accordance with one embodiment.

[0101] FIG. 6 shows a system for ethanol steam reforming for screening solid, heterogeneous catalysts in two connected reactors in accordance with one embodiment.

[0102] FIG. 7 illustrates an Ethanol Reforming Process Flow Diagram (PFD) for Hydrogen Production using Stationary Units in accordance with one embodiment.

[0103] FIG. 8 illustrates a Ethanol Reforming Process Flow Diagram (PFD) for supplying hydrogen to a Fuel Cell Mobile Unit to be used for fuel cell powered vehicles, flying equipment+ or ships in accordance with one embodiment.

[0104] FIG. 9 shows a plot of temperature vs. carbon monoxide content, methane content and hydrogen production rate in the product stream for ethanol steam reforming in the system of FIG. 6, in accordance with one embodiment.

[0105] FIG. 10 shows a plot of weight hour space velocity (WHSV) vs. carbon monoxide content, methane content and hydrogen production rate in the product stream for ethanol steam reforming in the system of FIG. 6, in accordance with one embodiment.

[0106] FIG. 11 shows a plot of water/ethanol ratio vs. carbon monoxide content, methane content and hydrogen production rate in the product stream for ethanol steam reforming in the system of FIG. 6, in accordance with one embodiment.

DETAILED DESCRIPTION

[0107] It is provided solid, heterogeneous catalyst preparation for producing H.sub.2 via methanol reforming in accordance with the following reactions:

CH.sub.3OH.fwdarw.CO+2H.sub.2  (Equation 1)

CO+H.sub.2O.fwdarw.CO.sub.2+H.sub.2  (Equation 2)

CH.sub.3OH+H.sub.2O.fwdarw.CO.sub.2+3H.sub.2  (Equation 3)

CH.sub.3OH+0.5H.sub.2O+0.25O.sub.2.fwdarw.CO.sub.2+2.5H.sub.2  (Equation 4)

[0108] And ethanol steam reforming in accordance with the following reaction:

CH.sub.3CH.sub.2OH.fwdarw.CO+CH.sub.4+H.sub.2  (Equation 5)

CH.sub.4+H.sub.2O.fwdarw.CO+3H.sub.2  (Equation 6)

CO+H.sub.2O.fwdarw.CO.sub.2+H.sub.2  (Equation 7)

C.sub.2H.sub.5OH+3H.sub.2.fwdarw.2CO.sub.2+6H.sub.2  (Equation 8)

CH.sub.3CH.sub.2OH+0.5H.sub.2O+0.250.sub.2.fwdarw.2CO.sub.2+3.5H.sub.2  (Equation 9)

[0109] The solid, heterogeneous catalysts of the present disclosure may be used in methanol or ethanol reforming reaction, which may include methanol decomposition (Equation 1), water gas shift (Equation 2), methanol steam reforming (Equation 3), oxidative methanol and ethanol steam reforming (Equation 4 and Equation 9) and ethanol steam reforming (Equations 5-8) to produce hydrogen which may be used as a fuel or in other chemical transformations requiring added hydrogen.

[0110] The term “heterogeneous” as used herein with respect to solid catalysts refers to any solid physical form of suitable catalyst, whether a catalyst is calcined or otherwise hardened, whether provided in powder, pellet, balled, or extruded form or anchored to a solid structure such as a metal surface, ceramics, molecular sieve of natural or synthetic solid-state composition. Such catalysts are generally not solubilized during the reaction and recoverable from the reaction products by simple filtration.

[0111] In one embodiment, the catalyst comprises at least one metal element of Cu, Ni, Fe, Co, Mo, Mn, Mg, Zr, La, Ce, Ti, Zn and W, having a formula Cu.sub.aNi.sub.bFe.sub.cCo.sub.dMo.sub.eMn.sub.fMg.sub.gZr.sub.hLa.sub.iCe.sub.jTi.sub.kZn.sub.lW.sub.mO.sub.x, wherein a, b, c, d, e, f, g, h, i, j, k, l and m are molar ratios for the respective elements, wherein a, b, c, d, e, f, g and m are ≥0, h, i, j, k and l are >0 and x is such that the catalyst is electrically neutral; wherein a+b+c+d+e+f+g+h+i+j+k+l+m=1 and 0≤a≤0.32, 0≤b≤0.19, 0≤c≤0.29, 0≤d≤0.16, 0≤e≤0.11, 0≤f≤0.21, 0≤g≤0.32, 0.23≤h≤0.42, 0.01≤i≤0.02, 0.03≤j≤0.10, 0.11≤k≤0.20, 0.11≤l≤0.19 and 0≤m≤0.04, x is such that the catalyst is electrically neutral.

[0112] one embodiment, the catalyst comprises at least one metal element of Cu, Ni, Fe, Co, Mo, Mn, Mg, Zr, La, Ce, Ti, Zn and W, having a formula Cu.sub.aNi.sub.bFe.sub.cCo.sub.dMo.sub.eMn.sub.fMg.sub.gZr.sub.hLa.sub.iCe.sub.jTi.sub.kZn.sub.lW.sub.mO.sub.x, wherein a, b, c, d, e, f, g, h, i, j, k, l and m are molar ratios for the respective elements, wherein a, b, c, d, e, f, g, i, and j are 0, h, k, l and m are ≥0 and x is such that the catalyst is electrically neutral; wherein a+b+c+d+e+f+g+h+i+j+k+l+m=1 and 0≤a≤0.32, 0≤b≤0.19, 0≤c≤0.29, 0≤d≤0.16, 0≤e≤0.11, 0≤f≤0.21, 0≤g≤0.32, 0.23≤h≤0.42, 0≤i≤0.02, 0≤j≤0.10, 0.11≤k≤0.20, 0.11≤l≤0.19 and 0<m≤0.04, x is such that the catalyst is electrically neutral.

[0113] In a non-limiting embodiment, the metal oxidation state may be as follows: Cu.sup.0, Cu.sup.+1, Cu.sup.+2, Ni.sup.0, Ni.sup.+2, Co.sup.0, Co.sup.+2, Mo.sup.0, Mo.sup.+2, Mn.sup.0, Mn.sup.+2, Mn.sup.+3, Mn.sup.+4, Mg.sup.0, Mg.sup.+2 Mn.sup.+5, Mn.sup.+6, Mn.sup.+7, Fe.sup.0, Fe.sup.+2, Fe.sup.+3, Ti.sup.0, Ti.sup.+2, Ti.sup.+3, Ti.sup.+4, Zn.sup.0, Zn.sup.+1, Zn.sup.+2, Zr.sup.0, Zr.sup.+4, La.sup.0, La.sup.+3 Ce.sup.0, Ce.sup.+3, Ce.sup.+4, W.sup.0 or W.sup.+3.

[0114] In an embodiment, the solid, heterogeneous catalyst comprising at least one metal element of Cu, Ni, Fe, Co, Mo, Mn, Mg, Zr, La, Ce, Ti, Zn and W, having a formula Cu.sub.aNi.sub.bFe.sub.cCo.sub.dMo.sub.eMn.sub.fMg.sub.gZr.sub.hLa.sub.iCe.sub.jTi.sub.kZn.sub.lW.sub.mO.sub.x may be prepared using a variety of known methods, including but not limited to, impregnation, ion-exchange, co-precipitation and or physical mixing. While several methods are discussed below, it is appreciated that other suitable methods may be readily apparent to those skilled in the art to obtain the desired composition, shape, surface area and total pore volume of the solid, heterogeneous catalyst.

[0115] In an example, the solid, heterogeneous catalyst comprising at least one metal element of Cu, Ni, Fe, Co, Mo, Mn, Mg, Zr, La, Ce, Ti, Zn and W, having a formula Cu.sub.aNi.sub.bFe.sub.cCo.sub.dMo.sub.eMn.sub.fMg.sub.gZr.sub.hLa.sub.iCe.sub.jTi.sub.kZn.sub.lW.sub.mO.sub.x may be prepared/obtained from any suitable source of its relevant elemental constituents (i.e., the relevant metal(s)) in presence or in absence of a structure directing agent. Suitable sources of the elemental constituents of the at least one metal composition may be compounds such as halides, nitrates, formates, oxalates, citrates, acetates, carbonates, amine complexes, ammonium salts and/or hydroxides and hydrates of the above-mentioned metals (from Group IIA, IB, IIB, IIIB, IVB, VIB, VIIB and VIIIB from the periodic table). A structure directing agent as used herein refers to any structural template that may be used for synthesizing structured materials, such as but not limited to a zeolite with a desired micro, meso or macro pore size.

[0116] In an embodiment, the catalyst composition prepared/obtained from the relevant source of elemental constituents may be calcined before and/or after particle aggregation with or without concomitant use of a shaping aid, via an extruding or a pelletizing process, at a temperature between about 200° C. and about 1000° C., preferably at a temperature between about 300° C. and about 900° C., and more preferably at a temperature between about 450° C. and about 750° C. The calcination may be carried out either in the presence of an inert gas, under an oxidizing atmosphere such as air (or another suitable mixture of inert gas and molecular oxygen), under a reducing atmosphere (e.g., a mixture of inert gas, NH.sub.3, CO, and/or H.sub.2) or under a reduced pressure. The calcination time may be between about 30 mins and about 10 hours, preferably between about 1 hour and about 8 hours, and more preferably between about 2 and about 6 hours, wherein the calcination time generally decreasing with increasing calcination temperature. The calcination time may be further reduced by using certain types of calcination equipment or furnaces and/or by selecting a suitable temperature ramping program.

[0117] In an embodiment, the catalyst comprising at least one metal element of Cu, Ni, Fe, Co, Mo, Mn, Mg, Zr, La, Ce, Ti, Zn and W, having a formula Cu.sub.aNi.sub.bFe.sub.cCo.sub.dMo.sub.eMn.sub.fMg.sub.gZr.sub.hLa.sub.iCe.sub.jTi.sub.kZn.sub.lW.sub.mO.sub.x has an average surface area of for example between about 10 m.sup.2/g and about 500 m.sup.2/g and an average pore volume of for example between about 0.01 mL/g and about 1 mL/g. It is appreciated that the catalyst may also exhibit any other suitable average surface area and/or average pore volume in other embodiments.

[0118] The process for producing H.sub.2 by steam reforming of a carbonaceous material, comprising contacting and reacting the carbonaceous material and water with a solid catalyst, wherein the solid catalyst comprises at least one metal element of Cu, Ni, Fe, Co, Mo, Mn, Mg, Zr, La, Ce, Ti, Zn and W, having a formula Cu.sub.aNi.sub.bFe.sub.cCo.sub.dMo.sub.eMn.sub.fMg.sub.gZr.sub.hLa.sub.iCe.sub.jTi.sub.kZn.sub.lW.sub.mO.sub.x, wherein a, b, c, d, e, f, g, h, i, j, k, l and m are molar ratios for the respective elements, wherein a, b, c, d, e, f, g and m are ≥0, h, i, j, k and l are >0 and x is such that the catalyst is electrically neutral; wherein a+b+c+d+e+f+g+h+i+j+k+l+m=1 and 0≤a≤0.32, 0≤b≤0.19, 0≤c≤0.29, 0≤d≤0.16, 0≤e≤0.11, 0≤f≤0.21, 0≤g≤0.32, 0.23≤h≤0.42, 0.01≤i≤0.02, 0.03≤j≤0.10, 0.11≤k≤0.20, 0.11≤l≤0.19 and 0≤m≤0.04, x is such that the catalyst is electrically neutral; wherein the metal oxidation state may be Cu.sup.0, Cu.sup.+1, Cu.sup.+2, Ni.sup.0, Ni.sup.+2 Co.sup.0, Co.sup.+2, Mo.sup.0, Mo.sup.+2, Mn.sup.0, Mn.sup.+2, Mn.sup.+3, Mn.sup.+4, Mg.sup.0, Mg.sup.+2, Mn.sup.+5, Mn.sup.+6, Mn.sup.+7, Fe.sup.0, Fe.sup.+2, Fe.sup.+3, Ti.sup.0, Ti.sup.+2, Ti.sup.+3, Ti.sup.+4, Zn.sup.0, Zn.sup.+1, Zn.sup.+2, Zr.sup.0, Zr.sup.+4, La.sup.0, La.sup.+3, Ce.sup.0, Ce.sup.+3, Ce.sup.+4, W.sup.0 or W.sup.+3.

[0119] The process for producing H.sub.2 by steam reforming of a carbonaceous material, comprising contacting and reacting the carbonaceous material and water with a solid catalyst, wherein the solid catalyst comprises at least one metal element of Cu, Ni, Fe, Co, Mo, Mn, Mg, Zr, La, Ce, Ti, Zn and W, having a formula Cu.sub.aNi.sub.bFe.sub.cCo.sub.dMo.sub.eMn.sub.fMg.sub.gZr.sub.hLa.sub.iCe.sub.jTi.sub.kZn.sub.lW.sub.mO.sub.x, wherein a, b, c, d, e, f, g, h, i, j, k, l and m are molar ratios for the respective elements, wherein a, b, c, d, e, f, g, i, and j are ≥0, h, k, l and m are >0 and x is such that the catalyst is electrically neutral; wherein a+b+c+d+e+f+g+h+i+j+k+l+m=1 and 0≤a≤0.32, 0≤b≤0.19, 0≤c≤0.29, 0≤d≤0.16, 0≤e≤0.11, 0≤f≤0.21, 0≤g≤0.32, 0.23≤h≤0.42, 0≤i≤0.02, 0≤j≤0.10, 0.11≤k≤0.20, 0.11≤l≤0.19 and 0<m≤0.04, x is such that the catalyst is electrically neutral; wherein the metal oxidation state may be Cu.sup.0, Cu.sup.+1, Cu.sup.+2, Ni.sup.0, Ni.sup.+2 Co.sup.0, Co.sup.+2, Mo.sup.0, Mo.sup.+2, Mn.sup.0, Mn.sup.+2, Mn.sup.+3, Mn.sup.+4, Mg.sup.0, Mg.sup.+2, Mn.sup.+5, Mn.sup.+6, Mn.sup.+7, Fe.sup.0, Fe.sup.+2, Fe.sup.+3, Ti.sup.0, Ti.sup.+2, Ti.sup.+3, Ti.sup.+4, Zn.sup.0, Zn.sup.+1, Zn.sup.+2, Zr.sup.0, Zr.sup.+4, La.sup.0, La.sup.+3. Ce.sup.0, Ce.sup.+3, Ce.sup.+4, W.sup.0 or W.sup.+3.

[0120] In an embodiment, the starting material is in a gas phase. Preferably, the gas phase of starting material may or may not comprise other gases, such as, but not limited to, ethanol, propanol, butanol, diethyl ether, glycerol, glycol, methane, ethane, propane, butane, in addition to the methanol and steam. The gas phase may further comprise oxygen or air further diluted with an inert gas, e.g. nitrogen or argon, which could be present as a carrier gas. Blending oxygen or air into the gas phase may encourage combustion and may also balance the total thermodynamic requirements of the reforming system.

[0121] It is thus provided a method for producing H.sub.2 by steam reforming of a carbonaceous material, comprising contacting and reacting the carbonaceous material and water with a solid catalyst as defined herein producing hydrogen.

[0122] The starting material is a carbonaceous material comprising for example, and not limited to, methanol, ethanol or carbon monoxide, and water, oxygen, or a combination thereof.

[0123] In a further embodiment, the carbonaceous material comprises ethanol, propanol, butanol, diethyl ether, dimethyl ether, glycerol, glycol, methane, ethane, butane, methanol, gasoline, diesel, a light distillate, naphtha, kerosene, or a combination thereof.

[0124] The process produces a gas fraction containing the hydrogen that may be separated from liquid fraction containing unreacted starting material. The gas fraction may include hydrogen, carbon monoxide, carbon dioxide, methane and trace amount of other hydrocarbons.

[0125] In a non-limiting example, the process is conducted at temperatures between 150° C. and 1000° C. Specifically, the process for methanol reforming may be conducted at temperatures between about 150° C. and about 450° C., preferably between about 200° C. and about 400° C., and more preferably between about 250° C. and about 350° C.; The process for ethanol reforming may be conducted at temperatures between about 300° C. and about 1000° C., preferably between about 400° C. and about 900° C., and more preferably between about 450° C. and about 850° C. In general, at higher process temperature alcohol conversion rate increases.

[0126] The process may be conducted at atmospheric pressure or higher pressure. In general, at the elevated pressures hydrogen production rate decreases.

[0127] The process is conducted with H.sub.2O to alcohol molar ratio in the gas phase equal to or greater than 1. For example, the process for methanol reforming may be conducted with H.sub.2O to methanol molar ratio in said gas phase equal to or greater than 1. In some embodiments however the molar ratio of H.sub.2O to methanol in said gas phase is between 1 and 3, preferably between 1 and 2, and more preferably between 1 and 1.5. The process for ethanol reforming may be conducted with H.sub.2O to methanol ratio in said gas phase equal to or greater than 3. In some embodiments however the molar ratio of H.sub.2O to ethanol in said gas phase is between 3 and 9, preferably between 3 and 7, and more preferably between 3 and 6. In general, higher water to alcohol molar ratio mainly affects reactions by shifting the equilibrium towards the products and, thus, reduces CO and CH.sub.4 content in the product stream.

[0128] In a fixed bed reactor, the process may be conducted at a WHSV of feed alcohol between about 0.1 h.sup.−1 and about 150 h.sup.−1. In general, at higher WHSV hydrogen production rate increases.

[0129] Control of the temperature, WHSV of carbonaceous material and water/carbonaceous material ratio in the process may be used to affect the process efficiency (i.e., conversion efficiency (%)), carbon monoxide content (molar percentage of carbon monoxide in the gas phase of product stream, %), methane content (molar percentage of methane in the gas phase of product stream, %) and hydrogen production rate (the volume of produced hydrogen per gram catalyst per hour, Lg.sup.−1h.sup.−1). The conversion efficiency is calculated according to equation (9) below:

[00001]$\begin{array}{cc}\mathrm{Conversion}=\frac{\mathrm{mols}.\mathrm{of}\mathrm{consumed}\mathrm{carbon}}{\mathrm{mols}.\mathrm{of}\mathrm{injected}\mathrm{carbon}}\times 100,& \mathrm{Equation}\left(9\right)\end{array}$

where, mols. of consumed carbon=combined mols of CO+CO.sub.2+CH.sub.4.

[0130] In case where, methanol is a carbonaceous feed stock, mols. of injected carbon=mols of injected methanol.

[0131] In case where, ethanol is a carbonaceous feed stock, mols. of injected carbon=2×mols of injected ethanol.

[0132] All reagents used in the following examples were of technical grade. Zirconium hydroxide and doped zirconium hydroxide (may contain a trace amount of hafnium) were purchased from Mel Chemicals UK. All other materials were purchased from Aldrich Chemical Co. Reactions were monitored by gas chromatography (GC). conversion (%), carbon monoxide content (%), methane content (%) and hydrogen production rate (Lg.sup.−1h.sup.−1) were calculated based on gas chromatography (GC) by using standard calibration methods.

Example I

General Method of Catalyst Preparation

[0133] To prepare a catalyst composition, the relevant mixture of metal oxides or metal oxide precursors obtained from any suitable source of elemental constituents was prepared by either one of the following methods: sol gel, impregnation, ion exchange, coprecipitation, physical mixing and/or a combination thereof, and was subsequently extruded, pelleted or pressed into tablets with tablet pressing machine and then calcined in static or flowing air in a programmable furnace. The calcined pellets were crushed and sieved between 10 and 20 mesh sizes. The coated catalyst was made by standard method such as but not limited to sol gel, Physical Vapor Deposition (PVD) or Chemical Vapor Deposition (CVD) on a metal or any suitable surface and then calcined at 550° C. for 4 hours in static or flowing air. Prior to testing, the calcined Catalyst may or may not be pre-reduced using Temperature Programmed Reduction (TPR) from room temperature to 500° C. under H.sub.2 gas stream or 2% H.sub.2 diluted with an inert gas for 5 hours. Non-limiting examples of catalyst preparation are provided in Table 1.

Representative Examples of Catalyst Preparation

[0134] Catalyst 8: The solution of Cu(NO.sub.3).sub.2.2.5H.sub.2O (9.22 g) and Ni(NO.sub.3).sub.2.6H.sub.2O (32.21 g) in distilled water (25 mL) was impregnated on the mixture of Ce(OH).sub.4 (equivalent to 17 wt % CeO.sub.2) and La(OH).sub.3 (equivalent to 5 wt % La.sub.2O.sub.3) doped Zirconium hydroxide (40.59 g), TiO.sub.2 (8.12 g) and ZnO (8.12 g). The impregnated powder was dried in air for 5 h and at 120° C. overnight and then was pressed into pellets and then calcined at 200° C. for 2 hours and then at 550° C. for 4 hours in static air in a programmable furnace. The calcined pellets were crushed and sieved between 10 and 20 mesh sizes. The catalyst obtained has a surface area of about 71.11 m.sup.2/g, a total pore volume of about 0.25 mL/g and a pore size of about 133.39 Å.

[0135] Catalyst 12: The solution of Cu(NO.sub.3).sub.2.2.5H.sub.2O (23.79 g) and Co(NO.sub.3).sub.2.6H.sub.2O (32.10 g) in distilled water (25 mL) was impregnated on the mixture of Ce(OH).sub.4 (equivalent to 17 wt % CeO.sub.2) and La(OH).sub.3 (equivalent to 5 wt % La.sub.2O.sub.3) doped Zirconium hydroxide (40.59 g), TiO.sub.2 (8.12 g) and ZnO (8.12 g). The impregnated powder was dried in air for 5 h and at 120° C. overnight and then was pressed into pellets and then calcined at 200° C. for 2 hours and then at 550° C. for 4 hours in static air in a programmable furnace. The calcined pellets were crushed and sieved between 10 and 20 mesh sizes. The catalyst obtained has a surface area of about 75.62 m.sup.2 g, a total pore volume of about 0.17 mL/g and a pore size of about 95.91Å.

TABLE-US-00001 TABLE 1 Catalyst Preparation Raw materials used Catalyst Cu(NO.sub.3).sub.2•2.5H.sub.2O Ni(NO.sub.3).sub.2•6H.sub.2O Fe(NO.sub.3).sub.3•9H.sub.2O Co(NO.sub.3).sub.2•6H.sub.2O (NH.sub.4).sub.6Mo.sub.7O.sub.24•4H.sub.2O Number (g) (g) (g) (g) (g) 1 25 32.21 0 0 0 2 37.58 48.1 48.84* 0 0 3 25 0 23.58 0 0 4 12.48 16.15 16.49 25 0 5 25 0 0 0 0 6 0 32.21 0 0 0 7 25 12.5 0 0 0 8 9.22 32.21 0 0 0 9 50 0 0 0 0 10 50 8 32.99 0 0 11 0 0 24.24* 0 0 12 23.79 0 0 32.1 0 13 47.02 0 47.58 0 0 14 47.02 0 94.05 0 0 15 23.79 0 94.05 0 0 16 23.79 0 0 0 0 17 23.79 0 0 0 11.96 18 23.79 0 0 0 0 19 12.48 0 23.58 16.37 0 20 23.79 0 47.02 0 0 21 0 0 32.99 0 0 22 0 0 38.00 0 0 23 0 0 0 0 0 24 11.89 0 0 16.05 0 25 0 16.10 0 0 0 26 0 0 0 16.05 0 27 0 0 23.58 16.05 0 28 0 0 0 16.05 0 29 0 16.10 0 16.05 0 30 0 0 0 16.05 0 31 1.83 1.49 0 0 0 Raw materials used La and Ce Doped Zirconium Catalyst Mn(NO.sub.3).sub.2•4H.sub.2O MgOAc•4H.sub.2O (NH.sub.4).sub.2Ce(NO.sub.3).sub.6 hydroxide TiO.sub.2 ZnO Number (g) (g) (g) (g) (g) (g) 1 0 0 0 40.59 8.12 8.12 2 0 0 0 61.01 12.2 12.2 3 0 0 0 40.59 8.12 8.12 4 0 0 0 40.59 8.12 8.12 5 0 0 0 40.59 8.12 8.12 6 0 0 0 40.59 8.12 8.12 7 0 0 0 40.59 8.12 8.12 8 0 0 0 40.59 8.12 8.12 9 0 0 0 40.59 8.12 8.12 10 0 0 0 40.59 8.12 8.12 11 0 0 0 35.71 7.14 7.14 12 0 0 0 40.59 8.12 8.12 13 0 0 0 40.59 8.12 8.12 14 0 0 0 40.59 8.12 8.12 15 0 0 0 40.59 8.12 8.12 16 29.7 0 0 40.59 8.12 8.12 17 0 0 0 40.59 8.12 8.12 18 0 57.34 0 40.59 8.12 8.12 19 0 0 0 40.59 8.12 8.12 20 0 0 0 40.59 8.12 8.12 21 32.30 0 0 40.59 8.12 8.12 22 0 0 0 35.71 7.14 7.14 23 29.70 0 0 40.59 8.12 8.12 24 14.85 0 0 40.59 8.12 8.12 25 14.85 0 0 40.59 8.12 8.12 26 0 0 0 40.59 8.12 8.12 27 0 0 0 40.59 8.12 8.12 28 0 0 12.72 40.59 8.12 8.12 29 0 0 0 40.59 8.12 8.12 30 14.85 0 0 40.59 8.12 8.12 31 0 0 0 3.31** 0.84 0.84 *FeCl.sub.2•6H.sub.2O; **W Doped Zirconium hydroxide

Example II

Catalyst Evaluation

[0136] catalysts Screening

[0137] The solid, heterogeneous catalyst compositions from table 1 were screened by using a fixed bed reactor system (see FIGS. 1 and 2). The effect of various elements (i.e., the effect of the composition of the heterogeneous catalysts) on the methanol decomposition, water gas shift and steam reforming reactions was determined.

Methanol Decomposition

[0138]
CH.sub.3OH.fwdarw.CO+2H.sub.2

[0139] Determination of catalytic activity in methanol decomposition reaction was carried out in a fixed bed reactor system (FIG. 1). A mixture of 12.5 g catalyst and 16.5 g silicon carbide 10 was placed between glass wool, metal wool, metal frit or metal screen plugs in a ¾-inch diameter stainless-steel reactor 12, fitted with a thermocouple. Reactor 12 is heated with a temperature-programmable furnace 14. Prior to testing, the calcined Catalyst may or may not be pre-reduced using Temperature Programmed Reduction (TPR) from room temperature to 500° C. under H.sub.2 gas stream or 2% H.sub.2 in N.sub.2 at 100 ml/min for 5 hours. Afterwards, methanol 16 was fed using a HPLC pump. Methanol passes through a evaporation zone 20 located at the bottom ⅓ of reactor 12 that is maintained at 300-350° C. where the liquid is converted to vapors before reaching the heated catalyst bed 10 above the preheating zone 20. Hot gaseous effluent existing from the reactor 12 is cooled by passing through a cooling condenser 24 to separate unreacted methanol and/or water, the product gas stream was analyzed on a connected Agilent 7879B gas chromatography 26 equipped with Reformed Gas Analysis (RGA) system. Thus, the H.sub.2, CO, CO.sub.2 and CH.sub.4 gas levels could be quantified directly. Data relating to the methanol conversion on various catalyst compositions, as well as hydrogen production rate, carbon monoxide content and methane content (molar %) in the gas product stream are shown in Table 2.

TABLE-US-00002 TABLE 2 Methanol decomposition without water H.sub.2 WHSV of Methanol CO CH.sub.4 Production Catalyst Temperature MeOH Conversion Content Content Rate Number (° C.) (h.sup.−1) (%) (%) (%) (Lg.sup.−1 h.sup.−1) 1 300 0.95 53 26.3 0.5 0.51 350 1.90 82.9 28.5 0.7 2.28 350 3.79 97.7 29.5 0.8 5.17 350 5.69 77.9 27.7 0.6 6.25 2 300 0.47 94 25.7 1.2 0.6 350 0.47 100 2.9 19.5 0.25 3 287 3.79 55 24.3 1.1 3.13 300 0.95 98 29.9 1.3 1.24 300 3.79 30 21.8 1.4 1.93 350 3.79 97 23.5 3.9 5.26 4 285 3.79 56 23.1 0.4 2.89 5 350 3.79 100 26.1 1.8 5.62 6 300 0.95 71 26.4 0.4 0.79 7 350 1.90 100 29 0.9 3.16 8 300 3.79 42 27 0.4 2.69 350 3.79 100 26.6 7 5.34 9 350 0.95 97 25.7 1.5 1.43 350 1.90 51 20.6 1.7 1.64 10 300 0.95 100 2.2 1.1 1.60 300 1.90 81 1.8 0.8 2.51 11 400 0.95 99 18.1 8.6 1.19 490 0.95 94 4.8 25.3 0.57 14 350 0.95 92 21.9 4.6 1.18 16 300 0.47 45 23.2 1 0.41 17 300 0.95 38 7.6 10.5 0.56 18 250 0.47 7 12.8 0 0.09 300 0.47 49 25.6 0.3 0.42 350 0.47 100 27.2 0.7 0.94 19 300 0.95 44 26.3 0.9 0.72 350 0.95 59 10.2 10.6 0.86

Water Gas Shift (WGS)

[0140]
CO+H.sub.2O.fwdarw.CO.sub.2+H.sub.2

[0141] Determination of catalytic activity in water gas shift reaction was carried out in a fixed bed reactor system (FIG. 2). A mixture of 12.5 g catalyst and 16.5 g silicon carbide 10 was placed between glass wool, metal wool, metal frit or metal screen plugs in a ¾-inch diameter stainless-steel reactor 12, fitted with a thermocouple. Reactor 12 is heated with a temperature-programmable furnace 14. Prior to testing, the calcined Catalyst may or may not be pre-reduced using Temperature Programmed Reduction (TPR) from room temperature to 500° C. under H.sub.2 gas stream or 2% H.sub.2 in N.sub.2 at 100 ml/min for 5 hours. The mixture of off-gas containing CO and H.sub.2, from methanol 16 decomposition reactor loaded with Catalyst 1 (see Table 1) and water 18 which was fed at a certain flow rate generated from an HPLC pump passed through a evaporation zone 21 located at the bottom ⅓ of reactor 30 that is maintained at 300-350° C. where the liquid was converted to vapors before reaching the heated catalyst bed 22 above the preheating zone 20. In addition to the process described in FIG. 1, the mixture of off-gas exiting the reactor 12 then goes through a water gas shift reactor 30 before the hot gaseous effluent existing from the water gas shift reactor 30 was cooled by passing through a cooling condenser 24 to separate unreacted methanol and/or water, the product gas stream was analyzed on a connected Agilent 7879B gas chromatography 26 equipped with Reformed Gas Analysis (RGA) system. Thus, the H.sub.2, CO, CO.sub.2 and CH.sub.4 gas levels could be quantified directly. Data relating to the methanol conversion with various catalyst compositions, as well as hydrogen production rate, carbon monoxide content and methane content (molar %) in the gas product stream are shown in Table 3.

TABLE-US-00003 TABLE 3 Water Gas Shift (WGS) reaction WHSV H.sub.2O/MeOH H.sub.2 of Ratio Methanol CO CH.sub.4 Production Catalyst Temperature MeOH (molar/ Conversion Content Content Rate Number (° C.) (h.sup.−1) molar) (%) (%) (%) (Lg.sup.−1 h.sup.−1) 1 350 0.47 1.53 100 4.2 3.1 0.92 350 0.95 0.68 100 15.1 0.8 1.77 2 300 0.47 1.53 82 10.1 2.3 0.72 350 0.47 1.53 93 7 7.3 0.64 3 300 0.47 1.53 74 2.8 0.9 0.85 300 0.95 1.22 89 6.2 0.8 2.05 300 1.90 1.51 73 6.8 0.5 3.30 300 3.79 1.20 91 13.6 0.8 7.57 4 300 0.95 1.22 100 4.1 2.2 1.65 5 350 0.95 1.22 88 3.1 0.7 1.64 350 1.90 1.13 96 7 0 3.40 6 350 0.95 1.22 97 22.1 1.2 1.50 350 1.90 1.22 100 7 16.1 2.09 7 350 0.95 1.22 100 6.3 0.9 2.00 350 1.90 1.22 100 8.6 1.1 3.94 8 350 0.95 1.22 100 9 2 1.70 350 1.90 1.22 100 5.9 19.2 1.83 9 350 0.95 1.22 88 5.7 0.6 1.89 350 1.90 1.22 59 15.8 0.6 3.63 10 300 0.95 1.22 100 3.9 1 2.03 300 1.90 1.22 100 5.4 1.3 3.85 11 300 0.95 1.22 87 28.3 0.8 1.53 350 0.95 1.22 95 16.2 0.8 1.66 400 0.95 1.22 100 9.1 0.8 1.96 400 1.90 1.22 100 11.2 0.9 3.80

Methanol Steam Reforming

[0142]
CH.sub.3OH+H.sub.2O.fwdarw.CO.sub.2+3H.sub.2

[0143] Determination of catalytic activity in methanol steam reforming reaction was carried out in a fixed bed reactor system as described previously (FIG. 1). A mixture of 12.5 g of catalyst and 16.5 g silicon carbide 10 was placed between glass wool, metal wool, metal frit or metal screen plugs in a ¾-inch diameter stainless-steel tubular reactor 12 equipped with a thermocouple. A temperature-programmable furnace 14 was used to heat the reactor. Prior to testing, the calcined Catalyst may or may not be pre-reduced using a temperature programmed furnace, ramping temperatures from room 20° C. to 500° C. under H.sub.2 gas stream or 2% H.sub.2 in N.sub.2 at 100 ml/min for 5 hours. A liquid mixture of methanol 16 and water 18 in ratios presented in Table 4 were injected at the bottom of the reactor using a HPLC pumps. Reactants were evaporated in the bottom preheating zone of the reactor prior to reaching the catalyst bed 10 located in the middle of the reactor as described previously. Hot gaseous effluents from the reactor 12 were cooled down by passing through a cooling condenser 24. The liquid product was separated from the gases and collected and analyzed. Data relating to the methanol conversion with various catalyst compositions, as well as hydrogen production rate, carbon monoxide content and methane content (molar %) in the gas product stream are shown in Table 4.

TABLE-US-00004 TABLE 4 Methanol Steam Reforming Reaction WHSV H.sub.2O/MeOH H.sub.2 of Ratio Methanol CO CH.sub.4 Production Catalyst Temperature MeOH (molar/ Conversion Content Content Rate Number (° C.) (h.sup.−1) molar) (%) (%) (%) (Lg.sup.−1 h.sup.−1) 1 300 0.47 1.53 88 7.20 0.10 1.11 350 1.08 1.46 81 6.60 0.10 2.51 350 0.95 1.22 100 14.00 0.20 2.30 350 1.90 1.22 87 11.30 0.30 4.06 350 3.79 1.20 89 14.50 0.70 8.04 2 300 0.47 1.53 100 12.50 1.30 0.89 300 1.61 1.46 89 16.40 0.50 2.64 3 300 0.95 1.22 91 3.50 0.20 2.05 300 1.90 1.19 73 1.70 0.10 3.43 300 3.79 1.76 100 3.30 0.10 8.81 300 4.74 1.76 80 3.60 0.80 8.71 4 285 1.90 1.19 80 11.70 0.20 3.41 300 0.95 1.22 100 7.60 0.80 2.15 5 350 1.90 1.22 97 6.00 0.00 4.48 350 2.84 1.20 100 6.90 0.00 6.61 6 350 1.90 1.22 100 3.40 19.90 1.71 7 350 1.90 1.22 100 12.20 0.20 4.26 350 0.95 1.22 97 9.60 0.20 2.08 8 350 0.95 1.22 100 3.70 22.20 0.82 300 1.90 1.22 88 16.70 3.00 3.13 9 350 0.95 1.22 100 5.60 0.00 2.20 350 1.90 1.22 99 6.40 0.00 4.37 350 3.79 1.20 98 10.40 0.00 8.40 10 300 1.90 1.22 100 9.60 2.60 3.95 300 3.79 1.20 96 13.70 1.20 7.75 11 350 0.95 1.22 67 1.80 1.10 1.48 400 0.95 1.22 95 8.80 2.40 1.82 400 2.40 0.96 100 7.50 1.80 3.86 12 300 0.95 1.17 100 4.60 0.70 1.83 300 1.90 1.22 94 7.30 0.50 3.86 300 3.79 1.22 100 5.40 0.10 8.50 300 7.58 1.20 93 5.50 0.10 16.13 300 11.38 1.20 88 6.10 0.10 23.41 13 300 0.95 1.17 75 0.70 0.00 1.76 350 0.95 1.17 100 3.60 0.10 2.24 300 1.90 1.22 55 0.50 0.10 2.72 300 3.79 1.22 56 0.50 0.00 5.40 300 7.58 1.20 54 0.60 0.00 9.95 14 300 0.95 1.17 86 1.70 0.10 2.05 350 0.95 1.17 100 7.90 0.10 2.23 300 3.79 1.22 72 1.00 0.20 6.93 300 7.58 1.20 73 1.10 0.20 13.71 300 11.38 1.20 73 1.80 0.30 19.25 300 15.17 1.20 68 2.40 0.40 25.54 15 300 0.95 1.17 82 1.30 0.10 2.02 350 0.95 1.17 100 5.00 0.50 2.30 300 1.90 1.22 64 0.50 0.10 3.26 300 3.79 1.22 52 0.50 0.10 5.08 300 7.58 1.20 33 0.60 0.20 6.62 300 11.38 1.20 32 0.70 0.30 10.04 350 15.17 1.20 41 3.50 0.60 15.15 16 300 0.95 1.17 100 4.40 0.00 2.39 350 0.95 1.17 98 7.70 0.00 2.35 300 1.90 1.22 97 6.80 0.00 5.34 300 3.79 1.22 90 4.90 0.00 8.64 300 7.58 1.20 86 3.50 0.00 16.84 300 11.38 1.20 73 1.90 0.00 23.94 300 15.17 1.20 71 2.40 0.00 29.70 17 275 0.95 1.17 22 0.20 1.10 2.02 300 0.95 1.17 57 0.20 1.40 5.05 350 0.95 1.17 100 1.00 2.60 8.02 300 7.58 1.20 63 0.80 6.20 4.00 350 7.58 1.20 95 0.90 7.00 5.89 18 300 0.95 1.17 69 1.00 0.00 7.12 350 0.95 1.17 95 4.50 0.00 8.82 300 1.90 1.22 59 0.70 0.00 6.36 350 1.90 1.22 95 4.50 0.00 8.99 300 3.79 1.22 61 0.90 0.00 6.05 19 350 3.79 1.22 100 3.80 0.00 9.36 300 0.95 1.17 70 10.00 2.50 5.21 350 0.95 1.17 91 2.30 9.80 5.02 300 3.79 1.22 68 3.70 1.90 5.22 350 3.79 1.22 100 8.70 22.60 3.23 20 300 1.90 1.20 74 1.30 0.10 3.36 350 1.90 1.20 100 6.80 0.20 4.14

Ethanol Steam Reforming

[0144]
C.sub.2H.sub.5OH+3H.sub.2O.fwdarw.2CO.sub.2+6H.sub.2

[0145] Determination of catalytic activity in ethanol steam reforming, reaction was carried out in a fixed bed reactor system similar to what has been described before (FIG. 6). A mixture of 1 g of catalyst and 14 g silicon carbide 10 was placed between glass wool, metal wool, metal frit or metal screen plugs in a ¾-inch diameter stainless-steel tubular reactor 12 equipped with a thermocouple. A temperature-programmable furnace 14 was used to heat the reactor 12. Prior to testing, the calcined Catalyst may or may not be pre-reduced using a temperature programmed furnace, ramping temperatures from room 20° C. to 500° C. under H.sub.2 gas stream or H.sub.2 gas stream diluted with nitrogen or an inert gas at 100 ml/min for 5 hours. A liquid mixture of ethanol and water 36 in 1:5 molar ratio (40% vol % of ethanol) were injected at the bottom of the reactor using a HPLC pump. Reactants were evaporated in the bottom preheating zone 20 of the reactor prior to reaching the catalyst bed 10 located in the middle of the reactor. Hot gaseous effluents from the reactor 12 were cooled down by passing through a cooling condenser 24 after passage by the water gas shift reactor 30. The liquid product was separated from the gases and collected and analyzed. Gas stream was analyzed using an Agilent 7879B gas chromatography 26 equipped with Reformed Gas Analysis (RGA) system equipped with detectors to detect and quantify H.sub.2, CO, CO.sub.2 and CH.sub.4 and low molecular weight gaseous hydrocarbons. Thus, the H.sub.2, CO, CO.sub.2 and CH.sub.4 gas levels could be quantified directly. Data relating to the ethanol conversion with various catalyst compositions, as well as hydrogen production rate, carbon monoxide content and methane content (molar %) in the gas product stream are shown in Table 5.

TABLE-US-00005 TABLE 5 Ethanol Steam Reforming Reaction WHSV H.sub.2O/EtOH H.sub.2 of Ratio Ethanol CO CH.sub.4 Production Catalyst Temperature EtOH (molar/ Conversion Content Content Rate Number (° C.) (h.sup.−1) molar) (%) (%) (%) (Lg.sup.−1 h.sup.−1) 12 300 0.4 5 26 11.7 7.3 0.3 350 0.4 5 64 7.6 7 0.5 400 0.4 5 87 2.5 8.7 0.7 500 0.4 5 98 4.5 9.7 0.8 600 0.4 5 100 5.4 6.5 0.9 700 0.4 5 100 10.7 2.7 1 800 0.4 5 100 14.1 5.2 0.8 6 650 4.8 9 85 23.7 9.1 7.3 700 5 9 100 24.3 10.2 9 850 5 9 99 7.2 0.1 10.6 850 10 9 83 9.6 0.3 21.5 850 20 9 88 10.1 0.7 47.1 850 40 9 100 10.7 2.1 107.8 900 5 9 100 10.8 0.3 13 25 700 20 5 100 12.9 6.2 43.5 800 20 5 100 14.8 5 43.9 900 20 5 100 18.8 0.1 53.9 26 600 20 5 77 12.5 6.8 29.3 700 20 5 100 13.6 4.2 41.8 800 20 5 100 13.4 3.4 41.9 900 20 5 100 16.6 3.9 39.5 700 40 5 100 27.3 6.1 65.6 700 80 5 100 27 10.5 113.9 850 20 4 100 16.6 5.1 37.8 850 20 5 100 15.3 3.9 41.7 850 20 6.5 100 13.4 3.3 43.9 850 20 10 100 10.6 2.6 47.5 27 600 20 5 100 11 5.8 41.5 700 20 5 100 12.3 7.1 37.9 800 20 5 100 13.2 7.1 38.2 900 20 5 100 16.2 4.5 44.5 28 600 20 5 98 9 8.6 36.9 700 20 5 100 19.5 5.3 39.9 800 20 5 100 13.3 6.1 39.6 900 20 5 100 16.8 3.5 45.3 29 600 20 5 100 16.5 9.1 34.2 700 20 5 100 23.6 8 55.8 800 20 5 100 15.2 2.8 56.3 900 20 5 100 18.7 0 56.1 700 80 5 100 22.3 14.5 96.1 800 80 5 100 18.1 4.1 167.9 30 600 20 5 100 10.6 4.5 42.2 700 20 5 100 13.8 3.6 46.6 800 20 5 100 14.6 5.3 43.4 900 20 5 97 15.5 6.5 42 31 350 2.5 7 100 19.4 27.4 2.08 400 2.5 7 100 1.4 25.5 2.54

Process Flow Diagram (PFD)

[0146] Alcohol Reforming Process Flow Diagram (PFD) for a Stationary Hydrogen Production Unit

[0147] With reference to FIG. 7, alcohol from feed tank T-1 40 and water from feed tank T-2 42 are fed into heat exchanger/evaporator E-1 44, using pumps P-1 and P-2, heated by mixed hot gas flow exiting from reactor R-2 48. Vaporized feed stream is further heated in makeup heater F-1 50 to reaction temperature before entering reactor R-1 46, where the alcohol and water vapors are converted into H.sub.2, CO.sub.2, CO, CH.sub.4 and in trace amounts of low molecular weight hydrocarbons. Product stream including unreacted water vapors from R-1 46 enters reactor R-2 48 where CO is further converted into H.sub.2 and CO.sub.2 by water gas shift reaction. After exiting R-2 48 the product stream passes through E-1 44 and then through gas-liquid separator V-1 52. Gas phase from top of the separator V-1 52 enters hydrogen purification column V-2 54. After H.sub.2 is separated, remaining combustible gases are combusted as fuel to generate heat in heater F-1 50. Water from bottom of separator V-1 52 return back to water tank 42.

[0148] Alcohol Reforming Process Flow Diagram (PFD) for On-Board Hydrogen Production for Fuel Cell Powered Electric Vehicles, Flying Equipment and/or Ships

[0149] With reference to FIG. 8, alcohol from feed tank T-1 60 and water from feed tank T-2 62 are fed into heat exchanger/evaporator E-1 64, using pumps P-1 and P-2, heated by mixed hot gas flow exiting from reactor R-2 68. Vaporized feed stream is further heated in makeup heater F-1 66 to reaction temperature before entering reactor R-1 70, where the alcohol and water vapors are converted into H.sub.2, CO.sub.2, CO, CH.sub.4 and in trace amounts of low molecular weight hydrocarbons. Product stream, including unreacted water vapors, from R-1 70 enters reactor R-2 68 where CO is further converted into H.sub.2 and CO.sub.2 by water gas shift reaction. After exiting R-2 68 the product stream passes through E-1 64 and gas-liquid separator V-2 72. Gas phase from top of the separator V-2 72 enters directly into the fuel cell FC-1 74, if the fuel cell can tolerate presence of CO and CO.sub.2 in the incoming hydrogen stream. Optionally, in case fuel cell is sensitive to the presence of non-hydrogen gases, then hydrogen stream can be pretreated by passing through hydrogen purification column V-3 76 to eliminate non-hydrogen gases from hydrogen stream prior to feeding into the fuel cell 74. After H.sub.2 is separated, remaining combustible gases are mixed with unreacted hydrogen from fuel cell tail gas separator V-1 78 and combusted as fuel to generate heat in heater F-1 66. Water from separator V-1 78 and separator V-2 72 returns back to feed water tank 62.

Example III

Process Conditions

[0150] With reference to FIG. 1, the process conditions including temperature, flow rate (specifically, weight hourly space velocity (WHSV)) as well as water/methanol ratio were evaluated by using catalysts from Table 1 at atmosphere pressure.

[0151] The impact of the process temperature was assessed by using catalyst 17 under atmospheric pressure, while keeping the WHSV and water/methanol ratios constant. The results are presented in Table 6 and FIG. 3.

TABLE-US-00006 TABLE 6 Temperature Effect WHSV H.sub.2 of Methanol CO CH.sub.4 Production Temperature MeOH H.sub.2O/MeOH Conversion Content Content Rate (° C.) (h.sup.−1) Ratio (%) (%) (%) (Lg.sup.−1 h.sup.−1) 275 0.95 1.17 22 0.20 1.10 2.02 300 0.95 1.17 57 0.20 1.40 5.05 350 0.95 1.17 100 1.00 2.60 8.02

[0152] The impact of the WHSV of methanol was further evaluated by using catalyst 16 under atmospheric pressure, while keeping the temperature constant at and water/methanol ratios constant. The results are presented in Table 7 and FIG. 4.

TABLE-US-00007 TABLE 7 Methanol WHSV Effect WHSV H.sub.2 of Methanol CO CH.sub.4 Production MeOH Temperature H.sub.2O/MeOH Conversion Content Content Rate (h.sup.−1) (° C.) Ratio (%) (%) (%) (Lg.sup.−1 h.sup.−1) 0.95 300 1.2 100 4.4 0 2.39 1.90 300 1.2 97 6.8 0 5.34 3.79 300 1.2 90 4.9 0 8.64 7.58 300 1.2 86 3.5 0 16.84 11.38 300 1.2 73 1.9 0 23.94 15.17 300 1.2 71 2.4 0 29.70

[0153] The impact of the water/methanol ratio was also investigated by using catalyst 1 under atmospheric pressure, while keeping the temperature and WHSV of methanol constant. The results are presented in Table 8 and FIG. 5.

TABLE-US-00008 TABLE 8 H.sub.2O/MeOH Ratio Effect WHSV H.sub.2 of Methanol CO CH.sub.4 Production H.sub.2O/MeOH Temperature MeOH Conversion Content Content Rate Ratio (° C.) (h.sup.−1) (%) (%) (%) (Lg.sup.−1 h.sup.−1) 1 300 0.48 90 9.7 0.1 1.07 1.5 300 0.48 92 7.2 0.1 1.13 1.75 300 0.48 100 6.2 0.1 1.12 2 300 0.48 100 3.4 0.1 1.12

Example IV

Ethanol Steam Reforming

[0154] With reference to FIG. 6, the process conditions including temperature, flow rate (specifically, weight hourly space velocity (WHSV)) as well as water/methanol ratio were evaluated by using catalysts from table 1.

[0155] The impact of the process temperature was assessed by using catalyst 26 under atmospheric pressure, while keeping the WHSV and the water/ethanol ratios constant. The results are presented in Table 9 and FIG. 9.

TABLE-US-00009 TABLE 9 Temperature Effect WHSV H.sub.2 of Ethanol CO CH.sub.4 Production Temperature Ethanol H.sub.2O/Ethanol Conversion Content Content Rate (° C.) (h.sup.−1) Ratio (%) (%) (%) (Lg.sup.−1 h.sup.−1) 600 20 5 78 12.5 6.81 29.32 700 20 5 100 13.6 4.25 41.81 800 20 5 99 13.4 3.45 41.93 850 20 5 100 15.3 3.92 41.7 900 20 5 99 16.6 3.88 39.52

[0156] The impact of the WHSV of ethanol was further evaluated by using catalyst 28 under atmospheric pressure, while keeping the temperature and the water/ethanol ratios constant The results are presented in Table 10 and FIG. 10.

TABLE-US-00010 TABLE 10 Ethanol WHSV Effect WHSV H.sub.2 of Ethanol CO CH.sub.4 Production Ethanol Temperature H.sub.2O/Ethanol Conversion Content Content Rate (h.sup.−1) (° C.) Ratio (%) (%) (%) (Lg.sup.−1 h.sup.−1) 80 700 5 100 22.3 14.5 96.1 40 700 5 98 25.9 10.1 57.4 20 700 5 100 23.6 8.2 33.2 10 700 5 100 22.1 8.4 17.9

[0157] The impact of the changing water/ethanol ratio was also investigated by using catalyst 26 under atmospheric pressure, while keeping the temperature and WHSV of ethanol. The results are presented in Table 11 and FIG. 11.

TABLE-US-00011 TABLE 11 H.sub.2O/Ethanol Ratio Effect WHSV H.sub.2 of Ethanol CO CH.sub.4 Production H.sub.2O/Ethanol Temperature Ethanol Conversion Content Content Rate Ratio (° C.) (h.sup.−1) (%) (%) (%) (Lg.sup.−1 h.sup.−1) 4 850 20 100 16.6 5.09 37.80 4.7 850 20 100 15.3 3.92 41.70 6.5 850 20 100 13.4 3.3 43.91 10 850 20 100 10.6 2.58 47.53

[0158] The impact of reaction pressure on reaction performance was investigated by keeping the temperature and WHSV of ethanol constant. The results are presented in Table 12.

TABLE-US-00012 TABLE 12 Reaction Pressure Effect H.sub.2 Ethanol CO CH.sub.4 Production Catalyst Conversion Content Content Rate Number Pressure (%) (%) (%) (Lg.sup.−1 h.sup.−1)  12* 20 100 1.2 2.9 1.4 500 99 0.6 4.4 1.2 1000 75 4 9.8 0.79 25 20 100 12.9 6.2 43.5 500 100 7.20 20.3 24.5 26 20 100 13.6 4.2 41.8 500 81 8.80 14.4 22.0 27 20 100 12.3 7.1 37.9 500 99 8.10 14.7 26.5 28 20 100 19.5 5.3 39.9 500 95 12.60 12.1 27.6 29 20 100 23.6 8.0 55.8 500 94 8.20 16.0 25.0 30 20 100 13.8 3.6 46.6 500 98 8.70 15.1 33.0 *Reaction conditions: Temperature - 850° C., WHSV of ethanol 0.4 h.sup.−1.

[0159] While the present disclosure has been described in connection with specific embodiments thereof, it will be understood that it is capable of further modifications and this application is intended to cover any variations, uses, or adaptations, including such departures from the present disclosure as come within known or customary practice within the art and as may be applied to the essential features hereinbefore set forth, and as follows in the scope of the appended claims.