Title

Catalyst for Production of Hydrogen and Synthesis Gas

Background

The present development is a high efficiency catalyst for use in a catalytic partial oxidation process for the production of hydrogen or syngas gas from hydrocarbons. The catalyst comprises rhenium in combination with a second metal

selected from the group consisting of platinum, iridium, ruthenium, rhodium, and palladium at an atomic ratio of rhenium to second metal from 25:1 to 1 : 1. The process comprises reacting a feed containing hydrocarbons with an oxygen source at a C/O

ratio of 0.9 to 1.1 in the presence of the catalyst, and wherein the gas hourly space

velocity of the feed over the catalyst ranges from 1,000 hr ^"1 to 2,000,000 hr ^"1 . In the process, the catalyst is maintained at a temperature from 500 ⁰ C to 1 ,500 ⁰ C as the feed makes contact with the catalyst.

Large volumes of hydrogen or synthesis gas, a mixture of hydrogen and carbon monoxide, are needed for a number of important chemical reactions. One process for producing hydrogen or synthesis gas is through catalytic partial oxidation (CPOx)

processes. In catalytic partial oxidation processes the gaseous hydrocarbon feedstock is mixed with air, oxygen-enriched air, or oxygen, in the presence of a catalyst. The partial oxidation of methane yields a syngas mixture with a H ₂ :CO ratio of 2:1, as shown in Equation 1 :

CH ₄ + V ₂ O ₂ <→ CO + 2 H ₂ (1)

This product ratio is especially desirable for downstream applications such as the

Fischer-Tropsch Synthesis.

In a catalytic partial oxidation process, the following side-reactions may occur:

CH ₄ + 2O ₂ <→ CO ₂ + 2H ₂ O (2)

CO + H ₂ O <→ CO ₂ + H ₂ (3)

The reaction shown in Equation 2 reduces the selectivity of both hydrogen and carbon monoxide. When the reaction occurs, CO ₂ and H ₂ O are formed. The system then favors the reaction shown in Equation 3, which alters the H ₂ /C0 ratio (the ratio is greater than 2:1 in the forward direction and less than 2:1 in the reverse direction). Catalysts for partial oxidation processes reported in the prior art tend to favor production of gases with a H ₂ /CO ratio of less than 2: 1 because the catalyst has <100% selectivity toward Equation 1 and high reaction temperatures needed for efficient methane conversion favor the reverse reaction of Equation 3. With a high efficiency catalyst, the reactions of Equation 2 and Equation 3 can be minimized or even totally eliminated.

In catalytic partial oxidation processes, the feedstock is normally introduced to the catalyst at elevated temperature and pressure. For example, in a typical catalytic partial oxidation process, the feedstock is preheated to a temperature of 450 ⁰ C, the gas hourly space velocity of the feed over the catalyst ranges from 1,000 hr ^'1 to 2,000,000 hr ^"1 , the pressure in the reactor can be up to 300 atms, and the catalyst is maintained at a temperature from 500 ⁰ C to 1,500 ⁰ C as the feed makes contact with the catalyst. The reaction generally proceeds at a relatively fast rate, and shorter catalyst contact times are needed to accomplish partial oxidation of a hydrocarbon feedstock as compared to prior art steam reforming processes.

The selectivity of catalytic partial oxidation to produce carbon monoxide and hydrogen is controlled by several factors - one of the most important being the choice of catalyst composition. Typically, the best catalyst compositions include precious metals. Rhodium, for example, has been found to be effective in CPOx processes, but rhodium also tends to have a lower stability than desired for commercial applications.

Rhodium loading at concentrations from 3 wt% to 10 wt% has been found to reduce the catalyst deactivation rate. In addition, to achieve high selectivity to the target products, carbon monoxide and hydrogen, and to produce synthesis gas with a H ₂ /CO ratio as close to 2.0 as possible, a temperature higher than 1000 ⁰ C is general required for a rhodium catalyst.

U.S. Patent 5,648,582 (issued to Schmidt, et al. on July 15, 1997) teaches a CPOx process having a very short residence time (120,000 to 12,000,000 hr ^'1 at atmospheric pressure) that uses a ceramic monolith supporting a metal catalyst selected from rhodium, nickel or platinum. U.S. Patent 6,458,334 (issued to Tamhankar, et al on October 1, 2002) teaches a CPOx process initiated at temperatures below 200 ⁰ C and having a relatively short residence time (50,000 hr ^"1 to 12,000,000 hr ^*1 at a pressure of 1 to 20 atmospheres) that uses a ceria monolith supporting a metal catalyst selected from nickel, cobalt, iron, platinum, palladium, iridium, rhenium, ruthenium, rhodium, osmium and combinations thereof. The difficulty with using a monolith support is that the catalyst must be engineered to fit the reactor, which is operated at an elevated temperature. Because of the difference in expansion characteristics between the monolith and the reactor, it is possible for feed to bypass the catalyst. In addition, it can be difficult to find coating materials with the stability and durability needed for high temperature processes in large-scale applications. For the CPOX process to be of commercial interest, it is necessary that the catalyst used in the process is able to achieve a high conversion of the methane feedstock at high gas hourly space velocities (GHSV) for a long period of time, and that the selectivity of the process to the desired products, carbon monoxide and hydrogen, must be as high as possible. Moreover, the catalyst preferably should comprise metals that are readily available at reasonable costs.

Summary of the Present Development

The present development is a high efficiency activated catalyst for use in a catalytic partial oxidation (CPOx) process for the production of hydrogen or syngas gas from hydrocarbons. The CPOx process comprises reacting a feed containing hydrocarbons with an oxygen source at a C/O ratio from 0.9 to 1.1 in the presence of the activated catalyst, wherein the gas hourly space velocity of the feed over the catalyst ranges from 1000 hr ^"1 to 2,000,000 hr ^"1 , the catalyst is maintained at a temperature from 500 ⁰ C to l,500°C as the feed makes contact with the catalyst, and the pressure in the reactor is maintained from 1 atm to 300 atms. The preferred catalyst for use in the process consists essentially of an alumina support impregnated with rhenium and a second metal selected from the group consisting of platinum, rhodium, iridium, ruthenium and palladium, wherein the atomic ratio of rhenium to second metal is from 25:1 to 1 :1 and the second metal is dispersed and maintained as finely distributed particles of 10 nanometers in diameter under the process conditions. Unlike the catalysts of the prior art, the present catalyst does not include iron, nickel or cobalt. During preparation of the catalyst, the catalyst must not be exposed to an oxidizing

environment at a temperature higher than 360 ⁰ C after rhenium is loaded onto the

support, and the catalyst must be activated in a reducing environment at temperatures

higher than 35O ⁰ C before using in a CPOx process.

Brief Description of the Figures

Figure IA is a TEM image of a freshly reduced sample of a Re-Pt catalyst made according to the invention;

Figure IB is a TEM image of the catalyst of Figure IA at a higher magnification;

Figure 1C is a TEM image of the catalyst of Figure IB after being subjected to a methane and steam feedstream and an oxygen feedstream wherein the CHVO ₂ = 2 and the H2O/CH4 = 0 for 235 hours, and the reactor is heated to a temperature of 900 ⁰ C;

Figures 2A - 2D show graphically the relative performance of a catalyst prepared according to the invention comprising about a 4:1 Re:Pt as compared to a traditional CPOx catalyst comprising about 4% Rh and to a traditional CPOx catalyst comprising 2% Rh, with:

Figure 2A comparing methane conversion versus time on stream; Figure 2B comparing hydrogen selectivity versus time on stream; Figure 2C comparing CO selectivity versus time on stream; and

Figure 2D comparing H ₂ /CO ratio versus time on stream.

Detailed Description of the Present Development

The present development is a high efficiency activated catalyst for use in a catalytic partial oxidation process for the production of hydrogen or syngas gas from hydrocarbons. The present process provides high yields of hydrogen or synthesis gas.

The feed gas for the present process will typically contain light hydrocarbons (CH _x ) and oxygen. Optionally, steam, carbon dioxide, recycle gas and combinations thereof, may be present. The molar ratio of CH _x : O ₂ may range from 1 :1 to 4:1. If steam and carbon dioxide are not present in the feedstock, it is desirable that the CH _X :O ₂ ratio be 2: 1. As is known in the art, the feed ratio may be adjusted as necessary based on the availability of the feedstock and the H ₂ :CO ratio required in any subsequent processes. Natural gas, certain refinery off gases containing methane or higher hydrocarbons, and other fuel sources that can be converted to hydrocarbon- containing gases may also be used. The oxygen source for the process is typically air, but can include air enriched with oxygen, oxygen mixed with other gases, or pure

oxygen. Optionally, steam, carbon dioxide, carbon monoxide, and hydrogen may come from a recycled gas stream.

The ratio of hydrocarbon to oxygen in the feed gas may vary, with the mixture dependent on the particular hydrocarbons chosen and the amount of oxygen necessary to conduct the particular partial oxidation reaction, as is known in the art. For the production of synthesis gas from methane, it is preferred that the carbon in the hydrocarbon to oxygen ratio (CH _x O ₂ ) ranges from 1 : 1 to 4: 1 , and that the carbon in the hydrocarbon to steam ratio (CH _X :H ₂ O) ranges from no steam present up to 1:5, and that the carbon in the hydrocarbon to carbon dioxide ratio (CH _x : CO ₂ ) ranges from no carbon dioxide present to 1:5.

The catalysts employed in the present invention comprise rhenium and a second metal on a refractory oxide support. The second metal is selected from the group consisting of platinum, rhodium, iridium, ruthenium and palladium. The refractory oxide is selected from the group consisting of alumina or rare earth promoted alumina or alkaline earth modified alumina, with a surface area greater than 0.5 m ² /g, and preferably greater than 1 m /g, and more preferably greater than 2 m /g. In an exemplary embodiment, the refractory oxide is a pure alumina with a surface area greater than 0.5 m ² /g. The refractory oxide is typically provided as particles in the shape of rings with one or more holes, tabs, granules, spheres, powders ranging in size up to 30 micrometers, or is wash-coated onto a monolith substrate. The rhenium concentration ranges from 0.1 wt % to 10 wt %, preferably from 0.5 wt% to 5 wt%, and the second metal concentration ranges from 0.05 wt % to 5 wt %, preferably from 0.1 wt% to 2.5 wt%, with the concentrations of rhenium to second metal adjusted as necessary to maintain a rhenium to second metal atomic ratio from 25:1 to 1 :1. The balance of the catalyst is the support. In a preferred embodiment, the catalyst

comprises rhenium and platinum with the metals present such that the Re: Pt is equal to 4:1.

The rhenium and the second metal are impregnated on the support using a conventional incipient wetness method. The metals may be impregnated either sequentially or simultaneously. After the rhenium is added to the support, care must be taken to not expose the rhenium-impregnated support to temperatures in excess of

36O ⁰ C in an oxidizing environment. Rather, the catalyst must be thermally treated at

temperatures below 36O ⁰ C, and preferably at temperatures below 150 ⁰ C, to remove any

moisture and decomposition components. Before use in the CPOx process, the catalyst must be placed in a reducing environmental at relatively low temperatures, such as

temperatures of less than 100 ⁰ C, and activated by increasing the temperature in a

hydrogen-containing gas stream until the temperature is higher than 300 ⁰ C, and

preferably is as high as 700 ⁰ C to 1000 ⁰ C. The catalyst can be pre-reduced or reduced

in-situ. The precursors for the rhenium and the second metals used in this development can be nitrates, chlorides, ammonium complexes, organometallic compounds and combinations thereof.

The partial oxidation process is conducted by contacting the hydrocarbon feed gas and the oxygen source with the catalyst at predetermined contact times which will vary depending on the particular feed gases, the catalyst composition, the pressure and the space velocity employed. Under typical operating conditions, the feed gas will be introduced at a standard gas hourly space velocity (GHSV) between 1,000 hr ^*1 and 2,00,000 hr ^"1 , and preferably at a GHSV greater than 100,000 hr ^"1 . The linear space velocity ranges from 0.1 meter per second to 300 meters per second. The pressure for the process is held from 1 atmosphere (arm) to 300 atms.

The hydrocarbon feed gas and the oxygen source feed is preheated to a temperature from 100 ⁰ C to a temperature of 800 ⁰ C before being fed into the reactor.

The feed temperature should be high enough to allow the reaction to light-off. The catalyst, packed in a fixed bed, is preheated to a temperature from 100 ⁰ C to a temperature of 800 ⁰ C. As the feed passes through the catalyst bed, the temperature of the bed will vary depending on the space velocity, the feed composition, and the feed preheating temperature. However, the temperature should be regulated as necessary to maintain the catalyst bed temperature at greater than 500 ⁰ C during the CPOx process.

To evaluate the catalysts for use in the CPOx process, a catalyst bed is prepared by loading 30x40 mesh catalyst particles into a 10mm inside diameter tubular reactor with a two-fold dilution using similarly-size quartz particles. The catalyst bed is subjected to a nitrogen (N ₂ ) purge for a predetermined time period. After the N ₂ purge, pure Kb gas is fed into the reactor at a temperature of 18 ⁰ C to 32 ⁰ C at a flow rate of 100 cm ³ /min. The catalyst is reduced in the pure hydrogen gas stream by heating the system at a rate of 20°C/min until the temperature of the reactor reaches 85O ⁰ C. The

system is then held at 850 ⁰ C for 1 hour. After reduction, the reactor is cooled down to

a temperature of less than 100 ⁰ C with a H ₂ gas flow. When the temperature is below

100 ⁰ C, the H ₂ gas feed stream is replaced with a methane feedstream introduced at a

flow rate of 100 cm ³ /min, and the methane is allowed to flow through the reactor until the H ₂ gas is completely replaced. Oxygen (O ₂ ) gas and/or steam are then introduced gradually, for example at a flow rate of about 20 cm ³ /min, to avoid reaching explosion limits and re-oxidizing the catalyst. The flow rates of CH ₄ and O ₂ are controlled by mass flow controllers. When target flow rates are achieved, the power on the furnace is turned on and the reactor system starts to heat up. During the heating process, the catalyst temperature, which is measured by a thermal -couple in a quartz thermal well

that sets in the middle of the catalyst bed, will increase rapidly as the catalyst lights off. After light-off, the furnace is turned off to let the temperature stabilize. When the catalyst bed temperature stabilizes, the reactor and bed are heated to the desired temperature by adjusting the temperature setting of the furnace. After the feed gases pass through the catalyst bed, the resulting effluent first passes through an ice-bath,

which is kept at -15°C to remove any water in the effluent and the remaining gas is analyzed by a gas chromatograph equipped with two columns, a 5A molecular sieve column for H ₂ , O ₂ , N ₂ , CH ₄ and CO, and a TDX-Ol column for CO ₂ .

The catalyst composition and process of the present invention is exemplified in the examples set forth herein. These examples are not to be taken as limiting the present invention in any regard. For the examples, the hydrocarbon source is methane gas and the oxygen source is air. The gas hour space velocity (GHSV) is 500,000/hr.

The catalyst bed temperature is varied from 700 ⁰ C to 1000 ⁰ C, the CHVO ₂ ratio is

varied from 1.6 to 2.0, and H ₂ O/CH ₄ ratio is varied from 0.0 to 2.5. The stability of each catalyst is defined as the time in hours for methane conversion or hydrogen selectivity to decrease by 1%.

Example 1: A catalyst is prepared according to the invention using an alumina support having a surface area of about 4.7 m /g and a pore volume of about 0.45 cc/g (referred to hereafter in the Examples as the "high surface area" alumina support), platinum is introduced in the form of tetra-ammine platinum nitrate solution and rhenium is introduced in the form of a perrhenic acid solution. Sufficient platinum is impregnated onto the support to achieve a target platinum loading of about 0.5 wt%, the

platinum-impregnated support is then dried at about 150 ⁰ C for about 18 hours, and the

dried platinum-impregnated support is then calcined at about 410 ⁰ C for about 2 hours. Rhenium is then impregnated on the platinum-impregnated support to achieve a target

rhenium loading of about 2.0 wt%, the rhenium-impregnated support is then dried at

about 150 ⁰ C for about 18 hours, and the rhenium-impregnated support is then calcined

at about 410 ⁰ C for about 2 hours. The resulting catalyst comprises about 0.45 wt% Pt and about 1.93 wt% Re. Example 2: A catalyst is made as in Example 1 except the target platinum loading is about 0.25 wt% and the target rhenium loading is about 2.25 wt%. The resulting catalyst comprises about 0.30 wt% Pt and about 2.36 wt% Re.

Example 3: A catalyst is made as in Example 1 except the target platinum loading is about 0.75 wt% and the target rhenium loading is about 1.75 wt%. The resulting catalyst comprises about 0.55 wt% Pt and about 1.69 wt% Re.

Example 4: A catalyst is made as in Example 1 except the target platinum loading is about 1.0 wt% and the target rhenium loading is about 1.5 wt%. The resulting catalyst comprises about 0.76 wt% Pt and about 1.59 wt% Re.

Example 5: A catalyst is made as in Example 4. The resulting catalyst comprises about 0.71 wt% Pt and about 1.00 wt% Re.

Example 6: A catalyst is made as in Example 1 except the target platinum loading is about 1.5 wt% and the target rhenium loading is about 1.0 wt%. The resulting catalyst comprises about 0.99 wt% Pt and about 1.13 wt% Re.

Example 7: A catalyst is made as in Example 6. The resulting catalyst comprises about 1.42 wt% Pt and about 0.68 wt% Re.

Example 8: A catalyst is made as in Example 1 except the target platinum loading is about 2.0 wt% and the target rhenium loading is about 0.5 wt%. The resulting catalyst comprises about 1.13 wt% Pt and about 0.62 wt% Re.

Example 9: A catalyst is made as in Example 1 except the target platinum loading is about 0.25 wt% and the target rhenium loading is about 1.0 wt%. The resulting catalyst comprises about 0.23 wt% Pt and about 0.90 wt% Re.

Example 10: A catalyst is made as in Example 1 except the target platinum loading is about 0.1 wt% and the target rhenium loading is about 0.4 wt%. The resulting catalyst comprises about 0.08 wt% Pt and about 0.52 wt% Re.

Example 11: A catalyst is made as in Example 1 except the target rhenium loading is about 2.5 wt% and no platinum is added (i.e. the target platinum loading is 0.0 wt%). The resulting catalyst comprises about 2.1 wt% Re. Example 12: A catalyst is made as in Example 1 except the target platinum loading is about 2.5 wt% and no rhenium is added (i.e. the target rhenium loading is 0.0 wt%). The resulting catalyst comprises about 2.25 wt% Pt.

Example 13: A catalyst is made as in Example 12. The resulting catalyst comprises about 1.67 wt% Pt. Example 14: An alumina support having a surface area of 4.7 m ² /g and a pore volume of 0.45 cc/g without other metals added is used as a catalyst.

Example 15: A catalyst is prepared as in Example 1 except that the rhenium-

impregnated support is not calcined at 410 ⁰ C after being dried at 150 ⁰ C. The resulting catalyst comprises about 0.38 wt% Pt and about 1.75 wt% Re. Example 16: A catalyst is prepared as in Example 15 except that an alumina support having a surface area of about 237 m ² /g and a pore volume of about 0.56 cc/g is used to prepare the catalyst and the rhenium- impregnated support is not calcined at

410 ⁰ C after being dried at 150 ⁰ C. The resulting catalyst comprises about 0.45 wt% Pt

and about 1.95 wt% Re.

Example 17: A catalyst is prepared as in Example 1 except that an alumina support having a surface area of about 237 m ² /g and a pore volume of about 0.56 cc/g is used to prepare the catalyst. The resulting catalyst comprises about 0.49 wt% Pt and about 2.1 wt% Re, and has a surface area of about 216m ² /g. Example 18: A catalyst is prepared as in Example 17 except the AI ₂ O ₃ support

is calcined at about 1400 ⁰ C before loading impregnation with either Pt or Re. The resulting catalyst comprises about 0.42 wt% Pt and about 0.0 wt% Re, and has a surface area of about 2.3m ² /g.

Example 19: A catalyst is prepared as in Example 18 except that the rhenium- impregnated support is not calcined at 41O ⁰ C after being dried at 150 ⁰ C. The resulting catalyst comprises about 0.36 wt% Pt and about 0.97 wt% Re.

Example 20: A catalyst is prepared as in Example 18 except that the rhenium precursor is ammonium perrhenate. The resulting catalyst comprises about 0.47 wt% Pt and about 1.70 wt% Re. Example 21: A catalyst is prepared as in Example 1 except the platinum is replaced by palladium added in the form of tetra-ammine palladium hydroxide for a target Pd loading of 0.5 wt%. The resulting catalyst comprises about 0.50 wt% Pd and about 0.94 wt% Re.

Example 22: A catalyst is prepared as in Example 1 except the platinum is replaced by rhodium added in the form of rhodium nitrate for a target Rh loading of 0.5 wt%. The resulting catalyst comprises about 0.56 wt% Rh and about 1.33 wt% Re.

Example 23: A catalyst is prepared as in Example 1 except the platinum is replaced by ruthenium added in the form of ruthenium nitrosyl nitrate for a target Ru loading of about 0.5 wt%. The resulting catalyst comprises about 0.46 wt% Ru and about 1.05 wt% Re.

Example 24: A catalyst is prepared as in Example 1 except the platinum is replaced by iridium added in the form of iridium acetate for target Ir loading of 0.5 wt%. The resulting catalyst comprises about 0.41wt% Ir and 1.01 wt% Re.

Example 25: (comparative) An alumina support having a surface area of 4.7 m ² /g and a pore volume of 0.45 cc/g is impregnated with Rh(NO ₃ ) ₃ solution using incipient wetness method for a target Rh loading of 4.0 wt%. The catalyst is dried at about 150 ⁰ C after impregnation for about 18 hours and is then calcined at about 410 ⁰ C for about 2 hours.

Example 26: (comparative) The catalyst is made exactly as described in Example 25 except that the final Rh loading on the catalyst is about 2 wt%.

The catalysts of Examples 1, 5, 1, 9 - 10, 12, 17 - 18, and 21 - 26 are subjected

to performance testing in a fixed bed reactor heated to 900 ⁰ C. A feedstream comprising methane and steam and an oxygen feedstream are fed into the reactor at a GHSV - 500,000/h such that the CU ₄ ZO ₂ = 2 and the H ₂ O/CH ₄ = 0.

Table 1: Catalyst performance at CH ₄ IOi= 2, H ₂ O/CH ₄ = O,

GHSV = 500,000 and 900 ⁰ C

The catalysts of Examples 2 - 4, 6, 8, 11, 13 and 14 are subjected to

performance testing in a fixed bed reactor with the temperature adjusted between 700 ⁰ C

and 1000 ⁰ C and then back to 700 ⁰ C using a 100 ⁰ C step function wherein sufficient time

is provided between temperatures changes to allow the reactor temperature to stabilize

(as determined by collection of at least three data points). The initial catalyst activity expressed as percent methane conversion is measured at each 100 ⁰ C interval.

Table 2: Initial catalyst activity at 700 ⁰ C to 1000 ⁰ C

It has been observed that when using a rhenium-comprising catalyst for the catalytic partial oxidization process, and particularly when the rhenium is used in combination with platinum, the catalyst is better able to maintain the conversion of methane to hydrogen and carbon monoxide at relatively high conversion rates for a substantially longer time on stream than is observed with conventional rhodium catalysts.

Figure IA is a TEM image of the Re-Pt catalyst of Example 1 as prepared and reduced. Figure IB is a TEM image of the same catalyst at a higher magnification. Figure 1C is a TEM image of the same catalyst after being subjected to CPOx conditions in the presence of a methane and steam feedstream and an oxygen feedstream wherein the CH ₄ VO ₂ = 2 and the H ₂ O/CH ₄ = 0 for about 235 hours at

900 ⁰ C. As shown in Figures IA - 1C, the catalyst maintains its integrity even after

about 235 hours on-stream at 900 ⁰ C.

Figures 2A - 2D demonstrate graphically the relative performance of the Re-Pt catalyst of Example 1 with the traditional rhodium catalysts of Examples 25 and 26. As

shown in Figure 2A, the inventive Re-Pt catalyst demonstrates a higher level of methane conversion for a longer period of time. The Re-Pt catalyst is also more selective with respect to hydrogen and carbon monoxide than are the rhodium catalysts, as shown in Figures 2B and 2C. The Re-Pt catalyst is also better able to maintain the desired H ₂ /CO ratio of about 2.0 for a longer period on stream than can the traditional rhodium catalysts, as demonstrated in Figure 2D.

It is understood that variations may be made to the process described herein which would fall within the scope of this development, for example, using the catalyst in a syngas generation process with the addition of CO ₂ in the feed stream or the recycle of effluents from the down stream processes.