Catalyst and process for thermo-neutral reforming of liquid hydrocarbons

Abstract

The invention relates to a four-component catalyst and a seven-component catalyst and refractory supports for use in the thermoneutral reforming of petroleum-based liquid hydrocarbon fuels.

Claims

1. A thermoneutral reforming process for the production of a hydrogen-rich synthesis gas from liquid hydrocarbon fuels, which comprises: a. providing a mixture of a liquid hydrocarbon fuel, an O.sub.2 rich gas or air and steam to an interior zone of a reactor, said interior zone including a catalyst bed consisting of a NiCe.sub.2O.sub.3PtLa.sub.2O.sub.3 combined combustion and steam and/or CO.sub.2 reforming catalyst supported on magnesium aluminate and containing a potassium compound as a promoter; b. pre-heating the mixture to a temperature of about 350 C. to about 450 C.; and c. bringing the mixture into contact with the catalyst bed at a gas hour space velocity of about 30,000 h.sup.1 to about 70,000 h.sup.1 causing an exothermic combustion reaction raising the reaction temperature to about 800 C. to about 900 C. and also causing an endothermic steam reforming reaction for a period of time sufficient to reform the liquid fuel to yield a hydrogen-rich synthesis gas.

2. The process of claim 1, wherein the liquid hydrocarbon fuel is a petroleum-based fuel.

3. The process of claim 2, wherein the petroleum-based liquid is selected from the group consisting of paraffins, light naphtha, heavy-naphtha, kerosene and diesel.

4. The process of claim 1, wherein the gas hour space velocity is between about 35,000 and about 50,000.sup.h-1.

5. The process of claim 1, wherein the heat generated from the exothermic combustion reaction is neutralized and compensated for by the endothermic reaction on the same catalyst bed.

6. The process of claim 1, wherein the reaction is carried out without the need of an external heat supply.

7. The process of claim 1, wherein coke formation is avoided.

8. The process of claim 3, wherein about 99% of the liquid petroleum based fuels is converted into syngas (H.sub.2/CO/CO.sub.2/CH.sub.4).

9. The process of claim 1, wherein the syngas produced from the process can be further purified to produce highly pure hydrogen.

10. The process of claim 1, wherein the hydrogen rich syngas is used as a feed for on-board reformers in vehicles incorporating a high temperature or low temperature fuel cell.

11. The process of claim 1, wherein the hydrogen-rich syngas is used as a feed for hydrogen enrichment in internal combustion engines.

12. The process of claim 1, wherein the hydrogen-rich syngas is employed in stationary applications.

13. The process of claim 1, wherein the sulfur content of the liquid hydrocarbons fuel is 200 ppm or less.

Description

DESCRIPTION OF THE FIGURES

(1) FIG. 1 is a graph showing the time on stream versus the percentages of the products converted according to the prior art method.

(2) FIG. 2 is a graph showing the time on stream versus the percentages of the products converted when using the four component catalyst of the present invention.

(3) FIG. 3 is a graph showing the time on stream versus the percentages of the products converted when using the seven component catalyst of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

(4) A catalyst of the present invention comprises oxide member(s) of the rare earth group metal oxide(s), such as lanthanum and/or cerium oxide and mixtures thereof, and/may contain a member of Group IV, such as zirconium oxide, a member selected from the group consisting of elemental nickel, a reducible compound of nickel and mixtures thereof, a member of the platinum group of metals, such as elemental platinum or a compound of platinum. Platinum group metals can be used as more than one metal, such as two or three including rhodium or compounds of rhodium and mixtures thereof. In addition, promoters from group VIIB of the periodic table, such as rhenium, can be used to enhance the efficiency of the thermoneutral reforming of the liquid hydrocarbons feedstock. The multi-component catalysts are supported on magnesium aluminate, calcium aluminate or mixtures therefore. Also, an alkaline metal, such as potassium, can be incorporated into the support to enhance the resistance to the buildup of coke on the catalyst.

(5) The composition of the 7-component catalyst of the present invention, along with the weight range of each constituent, is as follows: 0.5-15% Ni, 0.5-10% Ce.sub.2O.sub.3, 0.5-5% La.sub.2O.sub.3, 0.1-2% Pt, 0 a 1% ZrO.sub.2, 0 a 2% Rh, and 0 a 2% Re. The concentration of potassium, when present, is between 0.5 to 3.0%. The remainder of the catalyst is comprised of a refractory support containing alumina, magnesium aluminate or a mixture thereof. A refractory cement based on calcium aluminate, can also be incorporated to increase the mechanical strength of the catalyst. The specific surface area of the catalyst is from about 15 to about 125 square meters per gram, preferably above 50 square meters per gram.

(6) The support can be provided in different shapes such as spheres, extrudates and rings with one or multiple holes and other shaped opening depending on the desired maximum pressure drop in the process. For production of H.sub.2-rich gas for use in fuel cells it is preferable to use refractory supports in the form of spheres, such as those having diameters of 2-3 millimeters, simple extrudate, such as those having 1 to 4 millimeters of diameter, complex extrudates, such as trilobe or quadralobe or rasch ring, such as 10104 (external diameterheightinternal diameter). A preferred form for use in the fuel cells is in the shape of a honeycomb. For large-scale production of H.sub.2-rich gas, defined herein as production units with higher than 100,000 Nm.sup.3/day of hydrogen, it is preferable to use the support in the form of ring with multiple holes.

(7) A catalyst of the present invention can be prepared in accordance with various methods. The seven component catalyst, which is understood as containing Ni, Rh, Re, Pt, Ce.sub.2O.sub.3, La.sub.2O.sub.3 and ZrO.sub.2, is preferably prepared by a multiple step sequence of impregnation, calcination and reduction of the multi-components on the support. The catalyst impregnation is carried out using an aqueous solution of a soluble salt component, preferably nitrates. The preferred order of impregnation is to first impregnate the rhodium and rhenium metal salts which decompose upon subsequent heat treatment to form the corresponding oxides. After the impregnation, the composite material is dried at about 120 C. at a slow rate of heating, preferably at a rate of about 0.5 C. per minute and then maintaining the temperature at 120 C. for about one hour. The temperature is then raised to about 250 C. at the same rate, and the temperature is then maintained at 250 C. for about 1.5 hours. All the heat treatment is done with air or O.sub.2-rich gas. Optionally, after the impregnation the catalyst is treated at 60 C. for 10 to 30 minutes with ammonia-rich gas before the O.sub.2-rich gas heat treatment. The first step in catalyst preparation ends with a O.sub.2-rich gas reduction at a temperature from 400 C. to 450 C. for 2 hours. The second step is carried out in a manner similar to the first step with the use of salts of Pt and Zr. The third step is carried out similarly to the first and second stages with the use of salts of Ni, Ce and La. Optionally, the reduction step in the third step is conducted between 400 and 1100 C., preferably 700 C. to 800 C.

(8) A preferred embodiment of the invention is a four component catalyst, which is understood as containing multi-components Ni, Pt, Ce.sub.2O.sub.3, La.sub.2O.sub.3. The four component catalyst is preferably prepared by a single step impregnation, calcination and optionally reduction. The refractory support is impregnated with an aqueous solution containing a soluble salt, preferably nitrates, of Ni, Ce, La and Pt. After the impregnation, the composite material is dried at about 120 C. at a slow rate of heating, preferably at a rate of about 0.5 C. per minute and then maintaining the temperature at 120 C. for about one hour. The temperature is then raised to about 250 C. at the same rate, and the temperature is then maintained at 250 C. for about 1.5 hours. The heat treatment is done with air or O.sub.2-rich gas. Optionally, after impregnation the catalyst is treated at 60 C. for 10 to 30 minutes with ammonia-rich gas before the O.sub.2-rich gas heat treatment. The final catalyst preparation step is calcination at 400 to 450 C. in air or O.sub.2-rich gas. Optionally, the final stage of preparation may be a reduction while flowing H.sub.2 or gas rich in H.sub.2 with 400 C. to 1100 C., preferably from 400 to 500 C., for 2 hours. Depending on the volume of the pores in the support, it may be necessary to perform more than one step of impregnation, drying and calcination to obtain the desired content of all the components.

(9) The present invention provides a significantly improved multi-component catalyst that is employed in a process for the production of hydrogen-rich gas from liquid petroleum fractions, such as light naphtha, kerosene and diesel while reacting with water vapor and oxygen-rich gas in a fixed bed reactor. The catalysts perform simultaneously the catalytic functions of endothermic steam reforming and exothermic combustion with high efficiency of the thermoneutral reforming and with low detectable deactivation. The heat produced from catalytic combustion induces the endothermic steam reforming of hydrocarbons on the same catalysts surface leading to ultra-rapid reforming.

(10) The catalyst prepared in accordance with the present invention has the desired properties of: (1) being capable of complete oxidation of the hydrocarbon feedstock by consuming all the oxygen supplied, and generating a high heat of combustion reaction; (2) being very active for the steam reforming reaction which is endothermic, consuming the heat generated by the oxidation reaction and providing true thermoneutral reforming; (3) having a very long active life without any or low detectable deactivation, and (4) being able to process liquid hydrocarbons ranging from light naphtha to diesel at a very high rate of conversion to syngas. The good performance of the catalyst is believed to be associated with the occurrence of oxygen and hydrogen spillover by active phases on the surface of the catalyst associated with a support of high thermal and hydrothermal resistance and properties of low coke deposition.

(11) In accordance with another embodiment of the present invention, there is also provided a process for the production of hydrogen-rich syngas consisting of hydrogen and carbon monoxide with less than 1.5 vol % methane and carbon dioxide. The process comprises contacting vaporized liquid hydrocarbons, air/oxygen and steam over the multi-component catalyst. The process of the present invention can be carried out over a wide range of operating conditions. The level of the operating conditions are dictated by the feedstock used and the level of conversion required. The process of the present invention is used to produce hydrogen-rich gas from low sulfur middle distillate petroleum fractions (e.g., heavy naphtha, kerosene, and diesel) without the need for prior desulfurization at high gaseous hourly space velocity, while still maintaining full liquid hydrocarbon conversion under these conditions.

(12) The heat transfer between the exothermic and endothermic reaction performed directly on the same catalyst bed associated with high activity and stability of the catalyst in accordance with the present invention, allows the required catalytic reactor volume for liquid hydrocarbon reforming in this invention to be less than 1/20 the size of a conventional steam reforming reactor, and less than 1/10 the size of an auto thermal reformer. Moreover, the large furnace needed to heat the reactor, as required in conventional hydrocarbon steam reforming can be eliminated.

(13) In accordance with the present invention, the use of the magnesium aluminate support yields a thermo-neutral catalyst with higher activity, a reduced tendency to accumulate coke and a higher level of durability than the prior art based on alumina type supports. The excellent properties of the support allows for the simplification of the procedure for preparing the catalyst, reducing the content of noble metal, preferably Rh and Re are not used in the catalyst formulation, which is of benefit in reducing the production cost of the catalyst.

(14) In general, the subject invention provides the following advantages: 1. Simplified and/or less catalyst preparation steps 2. Lower catalyst cost 3. Higher liquid hydrocarbon conversion which is important for intended application 4. Required crystallite size was achieved with simplified and/or less catalyst preparation steps 5. Higher Surface area which gives indication on better catalyst performance 6. Higher pore volume and pore diameter which enhances heavy hydrocarbon conversion 7. Higher rate of dehydrogenation activity which gives indication on better catalyst performance 8. Higher methane conversion which gives indication on better catalyst performance

(15) Each of the inventions will now be described in greater detail in the examples, including specific embodiments and versions, but the inventions are not limited to these embodiments, versions or examples, which are included to enable a person having ordinary skill in the art to make and use the present inventions.

(16) The following examples are presented to illustrate the nature of the present invention and the manner of practicing the same, without, however, may be considered limiting, of its contents. Two examples are given along with one example from the prior art to demonstrate the present invention. For each example, the details of the catalyst preparation method, catalyst hydrogenation activity test, catalyst steam reforming activity test, crystallite size measurement, physical properties measurement and catalyst performance evaluation with heavy naphtha feed are given.

Example 1 (Prior Art Method)

(17) Catalyst Preparation Method:

(18) This example describes the preparation of a seven multi-component catalyst for use in the Thermo-Neutral process reformed in accordance with the prior art (U.S. Pat. No. 7,700,005).

(19) The catalyst was prepared by impregnating alumina spheres of diameter in the range of about 2 to about 4 millimeters and surface area of the support is from about 85 square meters per gram. One hundred and thirty-one grams of support-type alumina were impregnated with 75.6 ml of aqueous solution containing 0.84 grams of rhodium nitrate III (CAS 10139-58-9Sigma Aldrich, product code 83750) and 0.59 grams of rhenium oxide VII (CAS 1314-68-7Sigma Aldrich product code 1314-68-7). The catalyst was dried from ambient temperature to 60 C. at a rate of 0.5 C./min and then exposed to 60 C. for 10 minutes at an NH3-rich atmosphere. Then the catalyst was thermally treated for 60 C. up to 120 C. at a rate of 1 C./min and after for 120 C. up to 350 C. at a rate of 1.4 C./min. The catalyst was then reduced in flowing H.sub.2 at 430 C., cooled to 30 C. to 60 C. and exposed to a flow of air to passivation to obtain RhRe/alumina sample.

(20) A small amount of this sample was taken for process control. One hundred and eleven grams of the sample RhRe/alumina was impregnated with 70.3 ml of aqueous solution containing 2.53 grams of zirconium oxynitrate hydrate (CAS 12985-18-3 Sigma Aldrich product code 380679) and 1.82 grams of tetraaminoplatino chloride (II) monohydrate (CAS 13933-33-0 Alfa Aesar product code 10836). The steps of drying, calcination and hydrogen reduction were carried out similarly to the preparation of RhRe/Alumina sample to obtain the PtZrO.sub.2/RhRe/alumina sample.

(21) A small amount of this sample was taken for process control again. One hundred grams of the PtZrO.sub.2/RhRe/alumina sample was impregnated with 63.3 ml aqueous solution containing 2.97 grams of lanthanum nitrate hexahydrate (CAS 10277-43-7 Alfa Aesar, product code 44346), 8.87 grains of cerium (III) nitrate (CAS 10294-41-4, Sigma Aldrich, product code 392219) and 33.23 grams of nickel nitrate hexahydrate (CAS 0277-43-7, Sigma Aldrich, code product 203874). The steps of drying and calcination were carried out similarly to the preparation of PtZrO.sub.2/RhRe/alumina.

(22) The catalyst was then reduced in flowing H.sub.2 at 430 C. and them from 430 C. to 1160 C., cooled to 30 C. and exposed to a flow of air to passivation to obtain the multi-component catalyst NiCe.sub.2O.sub.3La.sub.2O.sub.3/PtZrO.sub.2/RhRe/alumina sample. The final catalyst had a nominal composition of (% w/w):0.2% Rh; 0.3% Re, 0.8% Pt, 1.0 ZrO.sub.2, 1.0 La.sub.2O.sub.3, 6% Ni, 3% Ce.sub.2O.sub.3 supported on stable alumina.

(23) TABLE-US-00001 Catalyst Prep. Steps Examples Catalyst Components (Summary) Prior art NiCe.sub.2O.sub.3La.sub.2O.sub.3PtZrO.sub.2RhRe 1. Three supported on alumina impregnation steps and final reduction at 1160 C. 2. Ammonia treatment is needed
Catalyst Hydrogenation Activity Test

(24) The purpose of this experiment is to assess the metal functionality through measuring the metallic area of the catalysts. It was estimated by the activity measurement in the reaction of dehydrogenation of cyclohexane. The conversion of cyclohexane was carried out in unit microactivity using the following conditions: mass of catalyst of 0.1 grains at a particle size 60-270 mesh; H.sub.2 flow between 40 to 80 ml/min; cyclohexane fed via saturator maintained at 10 C.; atmospheric pressure and reaction temperature between 330 C. to 390 C. Before the reaction the catalysts were pretreated in flow (40 ml/min) for 2 hours at 550 C. The reactants and products were analyzed by gas chromatography (HP 5890) using Plot Al2O3/KCl column operating at 150 C. The activity was expressed as total conversion of cyclohexane and as the dehydrogenation reaction rate, given by the expression R=X Fao/W, where X=conversion to benzene, W=mass of catalyst (g) and flow Fao=molar cyclohexane (mol/s).

(25) TABLE-US-00002 Examples Rate of Dehydrogenation Activity Prior art 16.4
Catalyst Steam Reforming Activity Test

(26) The purpose of this experiment is to assess the steam reforming functionality of catalyst using methane. The experiments were conducted in commercial equipment (AutoChem II, Micromeritcs). The tests were conducted using 200 mg of crushed catalyst in the range smaller than 170 mesh. The catalysts were pretreated in the temperature of 650 C. and atmospheric pressure by passing 40 ml/min of a gas containing hydrogen and 10% saturated with water vapor at 50 C. The activity of steam reforming of methane measurement was performed at 500 C. atmospheric pressure and steam/carbon ratio of 2.3 mol/mol. The effluent gases from the reactor were analyzed by gas chromatography and the activity measured by the degree of conversion of methane (X %).

(27) TABLE-US-00003 Examples Steam Reforming Conversion (%) Prior art 26
Crystallite Size Measurement

(28) This is to illustrate that the catalyst in accordance with the present invention prepared using magnesium aluminate, as disclosed in Examples 2 and 3, provides a nickel with reduced dimensions in the crystallite size that is not higher than the nickel obtained using the prior art with the most expensive support alumina. The metallic nickel crystal size was estimated by (peak: 200) DRX diffraction lines. It is believed that small size in particular of metallic nickel contributes to have a lower deactivation by coke formation.

(29) TABLE-US-00004 Examples Crystallite Size (nm) Prior art 17
Physical Properties

(30) This is to illustrate high metal BET surface area, pore volume and pore size in accordance with the present invention

(31) TABLE-US-00005 Pore Volume Examples Surface Area (m.sup.2/g) (cm.sup.3/g) Pore Diameter () Prior art 45.2 0.24 106 Notes: Sbet = specific surface area by N.sub.2 adsorption; Vp = pore volume by N2 desorption (BJH distribution); dm = pore average diameter (by 4 V/A)
Catalyst Performance Evaluation with Heavy Naphtha

(32) Catalyst performance evaluation was conducted with heavy naphtha fuel at micro-reactor unit. The properties of the heavy naphtha feed are as follow:

(33) TABLE-US-00006 Fuel Name Heavy Naphtha Heating Value (BTU/lb) 19606 Density @ 60 F. (g/cc) 0.7543 Sulfur @ 77 F. <2 ppm Viscosity (cSt) @ 104 F. PIONA (vol %) SIMIDIS ( F.) Aromatics 8.317 IBP 188 Naphthenes 38.163 05% 194 Oxygenates 0.000 10% 201 Paraffins 8.000 20% 220 i-Paraffins 41.503 30% 235 Olefins 3.025 40% 246 Unidentified 0.992 50% 257 % Recovered 100 60% 273 % Residue 0 70% 285 80% 295 90% 314 95% 324 FBP 340

(34) Catalyst evaluation was carried out in a fixed-bed flow reactor system. The reaction system consisted of gas and liquid feed sections, a preheating section, a reactor section and a product collection section. Gases were fed through mass flow controllers; liquid feeds were pumped by precision HPLC pumps. The reactor tube was 17.5 mm in diameter and was made of Haynes 230 alloy. A three-zone electric furnace, whose temperatures were monitored and controlled by temperature controllers, heated the reactor system. Thermocouples were provided to measure the inner temperature of the reactor. Water and heavy naphtha were vaporized in pre-heaters and were mixed with air in a static mixer before entering the reactor. The product collection section consisted of a pressure control valve, a gas-liquid separator, a liquid level controller and a product tank. 6 ml of the catalyst was loaded and positioned at the center of the reactor tube, between layers of inert silicon carbide. The top portion of silicon carbide layer also served as a preheating zone.

(35) The feed mixture was heated up to 350 C. in the preheating zone. The reactor was heated up to the starting temperature of 410 C. under nitrogen flow of 20 l/h. Water was pumped into the pre-heater and vaporized, and steam was sent in at a flow rate corresponding to a steam-to-hydrocarbon feed (H.sub.2O/C) molar ratio of 2.1. The hydrocarbon feed was pumped with O.sub.2/C ratio of 0.5. The total gas hour space velocity (GHSV) was about 45000 hr.sup.1. The reactor temperature increased to about 800-820 C. in a few seconds without external heating. A gas sample was collected and analyzed in two gas chromatographs, one equipped with TCD and the other with FID. The experiment was conducted for more than 60 hours and the graph shown in FIG. 1 and Table 1 demonstrates overall results.

(36) TABLE-US-00007 TABLE 1 Example 1 Prior art Experimental Results Run ID 1 2 3 4 5 6 Time on Stream, hour 7.0 19.0 30.9 41.2 51.6 64.1 Conditions GHSV, h1 45941 46096 46527 47052 48054 46767 Oxygen/Carbon ratio 0.5 0.5 0.5 0.5 0.5 0.5 Steam/Carbon ratio 2.3 2.2 2.2 2.2 2.2 2.2 Steady State Reaction T, C. 800 800 800 800 805 803 Results HC Conversion, % 100 100 100 100 100 100 H.sub.2O Conversion, % 27.9 27.5 26.5 26.0 24.4 24.2 H.sub.2/(CO + CO.sub.2) 1.7 1.7 1.7 1.7 1.7 1.7 Product Composition (l/h) H.sub.2 108.1 105.9 106.8 101.8 103.0 99.1 CO 27.2 27.1 28.9 28.5 28.4 28.9 CO.sub.2 35.2 33.8 33.0 31.3 32.9 30.8 CH.sub.4 1.3 1.1 1.2 1.1 0.9 1.1 N2 111 109 113 114 121 110 Dry Gas (without N.sub.2) (mole %) H.sub.2 62.9 63.1 62.9 62.6 62.3 62.0 CO 15.8 16.1 17.0 17.5 17.2 18.1 CO.sub.2 20.5 20.1 19.4 19.2 19.9 19.3 CH.sub.4 0.8 0.7 0.7 0.7 0.6 0.7 Product Gas (mole %) H.sub.2 38.2 38.3 37.7 36.8 36.0 36.7 CO 9.6 9.8 10.2 10.3 9.9 10.7 CO.sub.2 12.5 12.2 11.7 11.3 11.5 11.4 CH.sub.4 0.5 0.4 0.4 0.4 0.3 0.4 N.sub.2 39.3 39.3 40.0 41.2 42.3 40.8

Example 2 (Present Invention with 7-Component Catalyst A))

(37) Catalyst Preparation Method:

(38) This example is in accordance with the present invention describes the preparation of seven multi-component catalyst using magnesium aluminate as a support. The magnesium aluminate, was prepared by calcination a commercial hydrotalcite (SudChemie, product code T-2701 1/16 inch, with 30% w/w of MgO in alumina balance) at 1050 C. in air for 4 hours. The support had a surface area 67.6 m2/g, pore volume of 0.35 cm3/g by N.sub.2 adsorption and 0.9 cm.sup.3/g by water absorption and standard X-ray diffraction characteristic of the magnesium aluminate. The catalyst was prepared in a manner identical to Example 1 except final reduction step was conducted at 730 C. instead of 1160 C. The final catalysts had a nominal composition of (% w/w): 0.2% Rh; 0.3% Re, 0.8% Pt, 1.0 ZrO.sub.2, 1.%) La.sub.2O.sub.3, 6% Ni, 3% Ce.sub.2O.sub.3 supported on magnesium aluminate.

(39) TABLE-US-00008 Catalyst Prep. Steps Examples Catalyst Components (summary) A NiCe.sub.2O.sub.3La.sub.2O.sub.3PtZrO.sub.2RhRe 1. Three supported on Magnesium Aluminate impregnation steps and final reduction at 730 C. 2. Ammonia treatment is needed
Catalyst Hydrogenation Activity Test:

(40) The purpose of this experiment is to assess the metal functionality measuring the metallic area of the catalysts. It was estimated by the activity measurement in the reaction of dehydrogenation of cyclohexane. The conversion of cyclohexane was carried out in unit microactivity using the following conditions: mass of catalyst of 0.1 grams at a particle size 60-270 mesh; H.sub.2 flow between 40 to 80 ml/min; cyclohexane fed via saturator maintained at 10 C.; atmospheric pressure and reaction temperature between 330 C. to 390 C. Before the reaction the catalysts were pretreated in H.sub.2 flow (40 ml/min) for 2 hours at 550 C. The reactants and products were analyzed by gas chromatography (HP 5890) using Plot Al.sub.2O.sub.3/KCl column operating at 150 C. The activity was expressed as total conversion of cyclohexane and as the dehydrogenation reaction rate, given by the expression R=X Fao/W, where X=conversion to benzene, W=mass of catalyst (g) and flow Fao=molar cyclohexane (mol/s).

(41) TABLE-US-00009 Examples Rate of Dehydrogenation Activity A 31
Catalyst Steam Reforming Activity Test

(42) The purpose of this experiment is to assess the steam reforming functionality of catalyst using methane. The experiments were conducted in commercial equipment (AutoChem II, Micromeritcs). The tests were conducted using 200 mg of crushed catalyst in the range smaller than 170 mesh. The catalysts were pretreated in the temperature of 650 C. and atmospheric pressure by passing 40 ml/min of a gas containing hydrogen and 10% saturated with water vapor at 50 C. The activity of steam reforming of methane measurement was performed at 500 C. atmospheric pressure and steam/carbon ratio of 2.3 mol/mol. The effluent gases from the reactor were analyzed by gas chromatography and the activity measured by the degree of conversion of methane (X %).

(43) TABLE-US-00010 Examples Steam Reforming Conversion (%) A 31
Crystallite Size Measurement

(44) This is to illustrate that the catalyst in accordance with the present invention prepared using the magnesium aluminate provides a nickel with reduced dimensions in the crystallite size that is not higher than the nickel obtained using the prior art with the most expensive support alumina. The metallic nickel crystal size was estimated by (peak: 200) DRX diffraction lines. It is believed that small size in particular of metallic nickel contributes to have a lower deactivation by coke formation.

(45) TABLE-US-00011 Examples Crystallite Size (nm) A 16
Physical Properties

(46) This is to illustrate high metal BET surface area, pore volume and pore size in accordance with the present invention.

(47) TABLE-US-00012 Surface Area Examples (m.sup.2/g) Pore Volume (cm.sup.3/g) Pore Diameter () A 66.7 0.28 169 Notes: Sbet = specific surface area by N2 adsorption; Vp = pore volume by N2 desorption (BJH distribution); dm = pore average diameter (by 4 V/A)
Catalyst Evaluation with Heavy Naphtha

(48) Catalyst evaluation was tested with heavy naphtha fuel at micro reactor unit. Heavy naphtha feed properties as follow:

(49) TABLE-US-00013 Fuel Name Heavy Naphtha Heating Value (BTU/lb) 19606 Density @ 60 F. (g/cc) 0.7543 Sulfur @ 77 F. <2 ppm Viscosity (cSt) @ 104 F. PIONA (vol %) SIMIDIS ( F.) Aromatics 8.317 IBP 188 Naphthenes 38.163 05% 194 Oxygenates 0.000 10% 201 Paraffins 8.000 20% 220 i-Paraffins 41.503 30% 235 Olefins 3.025 40% 246 Unidentified 0.992 50% 257 % Recovered 100 60% 273 % Residue 0 70% 285 80% 295 90% 314 95% 324 FBP 340

(50) Catalyst evaluation was carried out in a fixed-bed flow reactor system. The reaction system consisted of gas and liquid feed sections, a preheating section, a reactor section and a product collection section. Gases were fed through mass flow controllers; liquid feeds were pumped by precision HPLC pumps. The reactor tube was 17.5 mm in diameter and was made of Haynes 230 alloy. A three-zone electric furnace, whose temperatures were monitored and controlled by temperature controllers, heated the reactor system. Thermocouples were provided to measure the inner temperature of the reactor. Water and heavy naphtha were vaporized in pre-heaters and were mixed with air in a static mixer before entering the reactor. The product collection section consisted of a pressure control valve, a gas-liquid separator, a liquid level controller and a product tank. 6 ml of the catalyst was loaded and positioned at the center of the reactor tube, between layers of inert silicon carbide. The top portion of silicon carbide layer also served as a preheating zone. The feed mixture was heated up to 350 C. in the preheating zone. The reactor was heated up to the starting temperature of 410 C. under nitrogen flow of 20 l/h, Water was pumped into the pre-heater and vaporized, and steam was sent in at a flow rate corresponding to a steam-to-hydrocarbon feed (H.sub.2O/C) molar ratio of 2.1. The hydrocarbon feed was pumped with O2/C ratio of 0.5. The total gas hour space velocity (GHSV) was about 4500 hr.sup.1. The reactor temperature increased to about 800-820 C. in a few seconds without external heating. A gas sample was collected and analyzed in two gas chromatographs, one equipped with TCD and the other with FID. The experiment was conducted for more than 60 hours and the following graph in FIG. 2 and Table 2 demonstrate the overall results.

(51) TABLE-US-00014 TABLE 2 Example 2 Prior art Experimental Results Run ID 1 2 3 Time on Stream, hour 22.0 46.7 76.1 Conditions GHSV, h-1 43539 43504 43606 Oxygen/Carbon ratio 0.5 0.5 0.5 Steam/Carbon ratio 2.2 2.2 2.2 Steady State Reaction T, C. 800 800 800 Results HC Conversion, % 100 100 100 H.sub.2O Conversion, % 29.7 29.7 30.2 H.sub.2/(CO + CO.sub.2) 1.6 1.6 1.6 Product Composition (l/h) H.sub.2 112.3 106.1 105.5 CO 28.2 28.2 28.6 CO.sub.2 40.1 37.3 36.8 CH.sub.4 1.5 1.5 1.8 N.sub.2 144.9 136.7 136 Dry Gas (without N.sub.2) (mole %) H.sub.2 61.7 61.3 61.1 CO 15.5 16.3 16.6 CO.sub.2 22.0 21.6 21.3 CH.sub.4 0.8 0.9 1.0 Product Gas (mole %) H.sub.2 34.3 34.2 34.2 CO 9.4 10.0 10.2 CO.sub.2 12.3 12.0 11.9 CH.sub.4 0.5 0.5 0.6 N.sub.2 44.3 44.1 44.1

Example 3 (Present Invention with 4-Component Catalyst B)

(52) Catalyst Preparation Method:

(53) This example, which is in accordance with the present invention describes the preparation of multi-component catalyst having four components using magnesium aluminate, promoted with K as a support. The support of magnesium aluminate was prepared as: 200 grams of commercial hydrotalcite (SudChemie, product code T-2701 1/16 inch, with 30% w/w of MgO in alumina balance) were impregnated with 180 ml of an aqueous solution containing 7.37 g of potassium hydroxide. The material was dried overnight at 100 C. and then calcined at 1050 C. in air for 4 hours. The support had a surface area 85.7 m.sup.2/g and pore volume of 0.70 cm.sup.3/g. 174 grams of the prepared support was impregnated with 140 ml of aqueous solution containing 0.70 g of tetraaminoplatino chloride (II) monohydrate (CAS 13933-33-0 Alfa Aesar product code 10836), 5.14 grams of lanthanum nitrate hexahydrate (CAS 10277-43-7 Alfa Aesar, product code 44346), 15.36 grams of cerium (III) nitrate (CAS 102.94-41-4, Sigma Aldrich, product code 392219) and 57.51 grams of nickel nitrate hexahydrate (CAS 10277-43-7, Sigma Aldrich, code product 203874). The catalyst was dried from ambient temperature to 120 C. at a rate of 1 C./min and after for 120 C. up to 350 C. at a rate of 1.4 C./min. The catalyst was then reduced in flowing H.sub.2 at 730 C., cooled to 30 C. and exposed to a flow of air to passivation to obtain PtNiCe.sub.2O.sub.3La.sub.2O.sub.3/K-magnesium aluminate catalyst. The final catalysts had a nominal composition of (% w/w): 1.0% Pt, 1.0 La.sub.2O.sub.3, 6% Ni, 3% Ce.sub.2O.sub.3, 2.7% K.sub.2O, supported in magnesium aluminate,

(54) TABLE-US-00015 Catalyst Prep. Steps Examples Catalyst Components (summary) B PtNiLa.sub.2O.sub.3Ce.sub.2O.sub.3 supported 1. One impregnation K promoted Magnesium step and final Aluminate reduction at 730 C. 2. No Ammonia treatment 3. Promoter (such as K) is added
Catalyst Hydrogenation Activity Test:

(55) The purpose of this experiment is to assess the metal functionality through measuring the metallic area of the catalysts. It was estimated by the activity measurement in the reaction of dehydrogenation of cyclohexane. The conversion of cyclohexane was carried out in unit microactivity using the following conditions: mass of catalyst of 0.1 grams at a particle size 60-270 mesh; H.sub.2 flow between 40 to 80 ml/min; cyclohexane fed via saturator maintained at 10 C.; atmospheric pressure and reaction temperature between 330 C. to 390 C. Before the reaction the catalysts were pretreated in H.sub.2 flow (40 ml/min) for 2 hours at 550 C. The reactants and products were analyzed by gas chromatography (HP 5890) using Plot Al.sub.2O.sub.3/KCl column operating at 150 C. The activity was expressed as total conversion of cyclohexane and as the dehydrogenation reaction rate, given by the expression R=X Fao/W, where X=conversion to benzene, W=mass of catalyst (g) and flow Fao=molar cyclohexane (mol/s).

(56) TABLE-US-00016 Examples Rate of Dehydrogenation Activity B 18
Catalyst Steam Reforming Activity Test

(57) The purpose of this experiment is to assess the steam reforming functionality of catalyst using methane. The experiments were conducted in commercial equipment (AutoChem II, Micromerites). The tests were conducted using 200 mg of crushed catalyst in the range smaller than 170 mesh. The catalysts were pretreated in the temperature of 650 C. and atmospheric pressure by passing 40 ml/min of a gas containing hydrogen and 10% saturated with water vapor at 50 C. The activity of steam reforming of methane measurement was performed at 500 C. atmospheric pressure and steam/carbon ratio of 2.3 mol/mol. The effluent gases from the reactor were analyzed by gas chromatography and the activity measured by the degree of conversion of methane (X %).

(58) TABLE-US-00017 Examples Steam Reforming Conversion (%) A (New Invention) 36
Crystallite Size Measurement

(59) This is to illustrate that the catalyst in accordance with the present invention prepared using the magnesium aluminate provides a nickel with reduced dimensions in the crystallite size that is not higher than the nickel obtained using the prior art with the most expensive support alumina. The metallic nickel crystal size was estimated by (peak: 200) DRX diffraction lines. It is believed that small size in particular of metallic nickel contributes to have a lower deactivation by coke formation.

(60) TABLE-US-00018 Examples Crystallite Size (nm) B 14
Physical Properties

(61) This is to illustrate high metal BET surface area, pore volume and pore size in accordance with the present invention.

(62) TABLE-US-00019 Surface Area Examples (m.sup.2/g) Pore Volume (cm.sup.3/g) Pore Diameter () B 77.5 0.38 170 Notes: Sbet = specific surface area by N2 adsorption; Vp = pore volume by N2 desorption (BJH distribution); dm = pore average diameter (by 4 V/A)
Catalyst Evaluation with Heavy Naphtha

(63) Catalyst evaluation was tested with heavy naphtha fuel at micro-reactor unit. Heavy naphtha feed properties as follow:

(64) TABLE-US-00020 Fuel Name Heavy Naphtha Heating Value (BTU/lb) 19606 Density @ 60 F. (g/cc) 0.7543 Sulfur @ 77 F. <2 ppm Viscosity (cSt) @ 104 F. PIONA (vol %) SIMIDIS ( F.) Aromatics 8.317 IBP 188 Naphthenes 38.163 05% 194 Oxygenates 0.000 10% 201 Paraffins 8.000 20% 220 i-Paraffins 41.503 30% 235 Olefins 3.025 40% 246 Unidentified 0.992 50% 257 % Recovered 100 60% 273 % Residue 0 70% 285 80% 295 90% 314 95% 324 FBP 340 Catalyst evaluation was carried out in a fixed-bed flow reactor system. The reaction system consisted of gas and liquid feed sections, a preheating section, a reactor section and a product collection section.

(65) Gases were fed through mass flow controllers; liquid feeds were pumped by precision HPLC pumps. The reactor tube was 17.5 mm in diameter and was made of Haynes 230 alloy. A three-zone electric furnace, whose temperatures were monitored and controlled by temperature controllers, heated the reactor system. Thermocouples were provided to measure the inner temperature of the reactor. Water and heavy naphtha were vaporized in pre-heaters and were mixed with air in a static mixer before entering the reactor. The product collection section consisted of a pressure control valve, a gas-liquid separator, a liquid level controller and a product tank 6 ml of the catalyst was loaded and positioned at the center of the reactor tube, between layers of inert silicon carbide. The top portion of silicon carbide layer also served as a preheating zone. The feed mixture was heated up to 350 C. in the preheating zone. The reactor was heated up to the starting temperature of 410 C. under nitrogen flow of 20 l/h. Water was pumped into the pre-heater and vaporized, and steam was sent in at a flow rate corresponding to a steam-to-hydrocarbon feed (H.sub.2O/C) molar ratio of 2.1. The hydrocarbon feed was pumped with O.sub.2/C ratio of 0.5. The total gas hour space velocity (GHSV) was about 45000 hr-1. The reactor temperature increased to about 800-820 C. in a few seconds without external heating. A gas sample was collected and analyzed in two gas chromatographs, one equipped with TCD and the other with FID. The experiment was conducted for more than 60 hours and the following graph in FIG. 3 and Table 3 demonstrate the overall results.

(66) TABLE-US-00021 TABLE 3 Example 3 Prior art Experimental Results Run ID 1 2 3 Time on Stream, hour 20.1 46.3 67.3 Conditions GHSV, h-1 42974 42968 43047 Oxygen/Carbon ratio 0.5 0.5 0.5 Steam/Carbon ratio 2.2 2.1 2.1 Steady State Reaction T, C. 840 830 832 Results HC Conversion, % 100 99 99 H.sub.2O Conversion, % 21.7 21.8 21.9 H.sub.2/(CO + CO.sub.2) 1.5 1.6 1.5 Product Composition (l/h) H.sub.2 91.8 91.0 90.7 CO 22.6 22.0 23.4 CO.sub.2 36.7 36.4 35.9 CH.sub.4 2.5 2.4 2.5 N.sub.2 140 138 141 Dry Gas (without N.sub.2) (mole %) H.sub.2 59.8 59.9 59.5 CO 14.7 14.5 15.3 CO.sub.2 23.9 24.0 23.5 CH.sub.4 1.6 1.6 1.6 Product Gas (mole %) H.sub.2 31.3 31.4 30.9 CO 8.3 8.2 8.7 CO.sub.2 12.5 12.6 12.3 CH.sub.4 0.8 0.8 0.9 N.sub.2 47.7 47.6 48.0

(67) Set forth in Table 4 below is a comparison of the properties of the catalyst of the prior art and of the present invention, as well as certain process parameters of the prior art and the present invention.

(68) TABLE-US-00022 TABLE 4 Liquid Steam Hydro- Crys- Pore Rate of Re- carbon tallite Surface Pore Di- dehydro- forming Exam- Catalyst Catalyst Con- size Area Volume ameter genation Cconver- ples Components Prep. Steps Cost version (nm) (m.sup.2/g) (cm.sup.3/g) () activity sion (%) Prior art NiCe.sub.2O.sub.3La.sub.2O.sub.3PtZrO.sub.2RhRe 1. Three High 100% 17 45.2 0.24 106 16.4 26 supported on impregnation alumina steps and final reduction at 1160 C. 2. Ammonia treatment is needed A NiCe.sub.2O.sub.3La.sub.2O.sub.3PtZrO.sub.2RhRe 1. Three Low 100% 16 66.7 0.28 169 31 31 (New supported on impregnation invention) Magnesium steps and Aluminate final reduction at 730 C. 2. Ammonia treatment is needed B PtNiLa.sub.2O.sub.3Ce.sub.2O.sub.3 4. One Very 100% 14 77.5 0.38 170 18 36 (New Supported K impregnation Low invention) promoted step and Magnesium final Aluminate reduction at 730 C. 5. No Ammonia treatment 6. Promoter (such as K) is added