NEW CARBONACEOUS MATERIALS AND METHODS FOR MAKING HYDROGEN AND LIGHT HYDROCARBONS FROM SUCH MATERIALS

Abstract: Carbonaceous materials comprising major amounts of carbon, and minor amounts of hydrogen and ferrous group metal components, particularly nickel and cobalt, react with steam at low temperatures, and produce commercially attractive quantities of such gases as hydrogen, methane, carbon oxides and other light hydrocarbons.

Description: NEW CARBONACEOUS MATERIALS AND METHODS FOR MAKING HYDROGEN AND LIGHT HYDROCARBONS FROM SUCH MATERIALS This invention relates to new processes for making hydrogen, oxides of carbon, methane, other light hydrocarbons, and mixtures of two or more of these products by reacting carbonaceous materials comprising carbon, ferrous group metal components, and hydrogen with steam. These processes produce commercially attractive product yields in commercially attractive temperature ranges. The invention also relates to new carbonaceous materials comprising carbon, hydrogen, and ferrous group metal components, particularly nickel and cobalt. To make these new carbonaceous materials, we react a gaseous mixture that includes carbon monoxide and hydrogen with one or more ferrous group metal components. Copending United States patent application Serial Number 99,789, filed December 3, 1979 in the United States Patent and Trademark Office, discloses a broad class of carbonaceous materials that include the new carbonaceous materials of this invention. That application also discloses methods for making our new carbonaceous materials. By this reference, we incorporate in this application the entire disclosure of that application, and of the applications referred to therein, namely United States patent application Serial Number 917,2 0 and United States patent application 817,647 filed in the United States Patent and Trademark Office on June 20, 1978 and Juiy 21, 1977, respectively. The new carbonaceous materials include a major amount of carbon, 'and minor amounts of hydrogen, and one or more ferrous group metal components. The new carbonaceous materials include from about 55 percent by weight to aoout 98 percent by weight of carbon, and preferably from about 75 percent by weight to about 95 percent by weight. The ferrous group metal components constitute an amount in the range of about one percent to about 44 percent, ' " REA preferably in the range of about 25 percent to about 5 percent by weight, of the carbonaceous material. At these high carbon-to-metal ratios, the carbonaceous materials react readily with steam to produce large, commercially attractive quantities of hydrogen, methane, and/or other light hydrocarbons in commercially attractive temperature ranges. Moreover, our carbonaceous materials exhibit excellent fluidity in fluid bed reactors, where these carbonaceous materials are reacted with steam. These carbonaceous materials also include hydrogen in amounts ranging from about 0.1 to about 1.0 percent by weight. Measured by low temperature gas adsorption methods, the carbonaceous materials have to^ai surface areas in the range of about 100 to about 300 square meters per gram of carbonaceous material, and pore volumes in the range of about 0.3 to about 0.6 milϋliters (ml) per gram of carbonaceous material. The ferrous group metal components in our new carbonaceous materials are selected from the group consisting of nickel, cobalt, nickel alloys, and cobalt alloys, and mixtures of these metals and alloys. Broadly, iron constitutes no more than about 30 percent by weight, and preferably no more than about 10 percent by weight, of the ferrous group metal component content of our new carbonaceous materials. Nickel and cobalt constitute at least 70 percent by weight of the ferrous group metal component content in our carbonaceous materials. Our new carbonaceous materials, prepared by the deposition processes referred to hereafter, typically include several phases. The major phase includes about 95% to about 99.996 carbon by weight, and hydrogen in an amount of about 0.1 percent to about 1 percent. The balance, if any, is one or more of the ferrous group metal components set forth above. Dispersed throughout this major phase are ferrous group metal component-rich minor phases comprising at least about 50 percent by weight of such metals as explained and as limited above. The remainder of the minor phases is principally carbon, but may include some hydrogen. Made by our preferred deposition methods, our new carbonaceous materials appear fibrous under the high magnification of a transmission or scanning electron microscope. Figure 5 is a scanning electron micrograph of a cobalt-containing carbonaceous fiber. This fibrous carbonaceous material contains more than about 90 percent by weight carbon, and includes at least about 5 percent by weight of cobalt-rich minor phases of the kind describeα above, as indicated at the arrow in FIG. 5. Broadly, the methods for making our new carbonaceous materials comprise depositing carbon from carbon monoxide-containing gas mixtures over one or more ferrous group metal initiators. In the process of carbon deposition, ferrous metal is transferred from the inititor to our carbonaceous material and becomes an integral part of these materials as described above. The ferrous group metal starting materials, called initiators in the deposition reaction to distinguish them from ferro.us group metal components in our new carbonaceous materials, can be supported or unsupported ferrous group metals, ores, alloys or mixtures of such species. The deposition processes take place at pressures in the range of about 1 to about 100 atmospheres or more, and at temperatures in the range* of about 300OC to about 700oc. Where the ferrous group metal component includes more than about 70 percent by weight nickel, and the carbon deposition temperature is in the range of about 30QOC to about 500 C, the carbonaceous material is especially suitable for making methane fay reaction with steam. At deposition temperatures above about 550°C, and especially where the ferrous group etai component is more than about 70 percent b weight cobalt, the carbonaceous material is especially suitable for making hydrogen by reaction with steam. Our new carbonaceous materials are highly reactive with steam at pressures in the range from about 1 to about 100 atmospheres or more and at temperatures in the range of about 50QOC to about 75QOC. From these steaming reactions, we obtain product gas mixtures that include hydrogen, carbon monoxide, carbon dioxide, methane and other light hydrocarbons. The quantities of each gas produced in the steaming reactions depend on the nature of the carbonaceous material and the temperature and pressure at which the steam gasification takes place. In particular, carbonaceous materials formed at temperatures in the range of about 300OC to about 50&OC, especially those formed in this temperature range from nickel alone or from ferrous group metal components containing at least about 70 percent by weight nickel, tend to produce substantial quantities of methane in the steam gasification reactions of this invention. By contrast, carbonaceous materials formed at temperatures above about 55QOC, especially those carbonaceous materials formed above this temperature from cobalt alone or from ferrous group metai components containing at least about 70 percent by weight cobalt, tend to produce substantial quantities of hydrogen in the steam gasification reactions of this invention. Where the molar ratio of steam fed to carbon gasified is at least aoout 3, (and therefore exceeds the amount required for thermodynamic equilibrium), and the steam gasification pressure is in the range of about I to about 10 atmospheres, the gasification reaction tends to produce hydrogen in large quantities, especially where the carbonaceous material is cobalt-based. Where the molar ratio of steam fed to carbon gasified is less than a out 3, and the steam gasification pressure is in the range of about 10 to about 100 atmospheres, (and therefore nearly equals the amount required for thermodynamic equilibrium), the gasification reaction tends to produce methane in large quantities, especially where the carbonaceous material is nickel-based. The gaseous products initially formed in the steaming reactions of this invention can be converted to gas mixtures richer in hydrocarbons, hydrogen, or both, by lowering the temperature of the gaseous products and contacting these products with either fresh or partially reacted carbonaceous material in the range of about 300°C to about 5QQOC, and by adjusting the pressure and steam feed rate to produce the desired gases, as explained below. Our new carbonaceous materials serve distinctly different purposes in the initial steam gasification process of this invention and in the subsequent, lower temperature conversion reaction of the gasification products from the steaming reactions. In the steaming reactions, our new carbonaceous materials participate as reactants. In the subsequent conversion of the steam gasification products to either hydrogen-rich or hydrocarbon-rich product gas mixtures at temperatures below the steam gasification temperatures our carbonaceous materials serve as a catalyst. The carbon monoxide-containing gas mixtures used in the deposition processes for making our new carbonaceous materials can be low pressure or high pressure producer or synthesis gases. Such gas mixtures may include substantial quantities of nitrogen and carbon dioxide, but must contain little or no sulfur compounds such as hydrogen sulfide, carbon disulfide or sulfur dioxide. If necessary, carbon monoxide-containing gas mixtures are pretreateo by known methods for removing sulfur-containing gases be ore carbon deposition begins. Carbon deposition removes some of the carbon from the carbon monoxide-containing gas mixtures at nearly 100 percent thermal efficiency since the heat of reaction may remain as sensible heat in the carbon monoxide- depleted fuel gas stream. The reaction heated, carbon monoxide-depleted gas mixture from the carbon deposition reaction is a good fuel source for generating combined cycle electric power. A surprising and unexpected aspect of our methods for steam gasification of the new carbonaceous materials is that where such carbonaceous materials contain iron as the chief ferrous metal component, such carbonaceous materials have quite low rates of reactivity with steam at temperatures in the range of about 500oc to about 600OC. Steam gasification, of such carbonaceous materials at temperatures above about 700OC is adversely affected by the side reaction of the iron component with steam, ano gasification ceases long before all of the carbon is gasified. By contrast, our new carbonaceous materials, which contain substantial amounts of nickel, cobalt, nickel alloys, cobalt alloys and mixtures thereof, have high reaction rates with steam, and do not suffer from deactivating side reactions. Figure 1 illustrates the range of steam reactivities with several different carbonaceous materials, including those of our invention. To obtain the data illustrated in the graph in FIG. i, we passed gas mixtures comprising Z5 percent carbon monoxide and 15 percent hydrogen over small samples of iron, nickel and cobalt initiators until the carbon-to-metal ratio of each sample reached four or more. We then steam gasified 0.5-gram samples of each carbonaceous material at progressively increasing temperatures, and " measured the rate of production of the dry gasification products formed. As FIG. 1 shows, the reactivities of these carbonaceous materials with steam varied greatly. The cobalt-containing carbonaceous material gasified rapidly at 50Qoc. By contrast, the iron-based carbonaceous material was inactive until the temperature reached 80Qoc, Accordingly, the nickel and cobalt-based carbonaceous materials are far more attractive for commercial manufacture of hydrogen and methane, particularly because the steam/carbonaceous material reactions are endothermic, and must be driven by indirect heat transfer. At temperatures in the range of aoout 5000c to about 600oc, where our nickel- based and cobalt-based carbonaceous materials readily steam gasify, indirect heat transfer is easily effected by state of the art techniques. At 800<->c and higher, indirect heat transfer is difficult to achieve and costly as well. Figure 2 illustrates the effect that the temperature of carbon deposition exerts on the composition of product gases made by steam gasification of the new carbonaceous materials of our invention. To show this effect, we prepared two different cobalt-based carbonaceous materials by depositing carbon from a mixture comprising 85 percent carbon monoxide and 15 percent hydrogen at atmospheric pressure. We prepared both carbonaceous materials by reaction with cobalt powder, forming one sample at 450°C and the other at 650°C. We continued the deposition reaction until we obtained a carbon-to-cobalt weight ratio of ten. We then reacted each sample with steam at 550oC and 10 atmospheric pressure. As FIG. 2 shows, the carbonaceous material deposited at 650OC produced far more hydrogen in the steam gasification reaction then oid the cobalt-based carbonaceous material produced at 50OC Indeed, after removing the carbon dioxide formed during steam gasification, the carbonaceous material formed at 650OC produces nearly pure hydrogen upon steaming at 15 55C C. The data in Tables 1 and 2 show differences in final product gas composition where the products of steam-carbon gasification of carbonaceous reactants containing different ferrous group metals further react at temperatures below the carbon gasification point of about 5Q0oC. In Table 1, a 20 carbonaceous material comprising about 90 percent carbon and about 9 percent nickel, prepared by carbon deposition on nickel powder, at about 450OC, catalyzed the f rther conversion of a typical steam-carbon gasification mixture of carbon monoxide, hydrogen and steam at 4QGOC and about 1 atmosphere pressure in a steady flow reactor. As Table 1 shows, nearly ail of the carbon 25 monoxide was converted to methane and carbon dioxide, with very little additional gasification of solid carbon (0.04 gram out of 0.83 gram in 203 minutes). Table 2 relates to an identical run, with one exception: The carbonaceous material contained cobalt instead of nickel (about 90 percent 0 carbon, and about 9 percent cobalt). These data show that coDalt-based carbonaceous material is less effective in converting the gas mixture to methane than the nickel-based material (27.2 percent methane for nickel-based; 9.5 percent, for cobalt-based), but more effective in shifting to hydrogen (49.8 percent hydrogen from cobalt-based material; 27.0 percent for nickel-based 35 material). TABLE 1. FURTHER CONVERSION OF STEAM-CARBON GASIFICATION PRODUCTS OVER A NICKEL-CARBON (90% CARBON) CARBONACEOUS MATERIAL AT 400°C -I PUT- -OUTPUT- SAMPLE TIME Η?/C0 H 2 CO "20 VOLUME CO. CO CH 4 H 2 NO. (MIN) MOLE % CC LIQUID ( it) H 2 MOLE % 1 7.7 .33 48.0 51.5 .16 .25 29.0 34.5 0.9 24.6 1 .1 2 26.6 1.1 48.0 51.5 .56 .91 29.0 34.5 1 .0 24.7 0.8 3 43.9 1.9 48.0 51.5 .92 1 .5 27.5 33.6 1 .3 26.3 0.7 4 63.4 2.7 48.0 51.5 1.3 2.2 31.1 34.5 0.0 23.2 0.9 5 81.0 3.4 48.0 51.5 1.7 2.8 25.3 34.2 0.9 29.4 0.9 6 123 5.2 48.0 51.5 2.6 4.2 24.3 35.1 0.9 29.4 0.9 7 193 8.2 48.0 51.5 4.1 6.7 25.2 35.4 0.9 28.0 0.9 8 203 8.6 48.0 51.5 4.3 7.0 24.3 35.4 1 .0 29.3 0.6 AVERAGE 27.0 34.7 1 .0 27.2 .85 H 2 /C0 FLOW 42.5 CC/MIN 025°C H 2 0 FLOW 0.021 CC (LIQUID)/MIN P 25°C SAMPLE WEIGHT .92g NET CARBON LOSS .04g 9 TABLE 2. FURTHER CONVERSION OF STEAM-CARBON GASIFICATION PRODUCTS OVER Λ COBALT-CARBON (90% CARBON) CARBONACEOUS MATERIAL AT 400°C -INPUT- - υu i ru r — SAMPLE TIME "2/CO H, CO 'H 2 0 v τ H 2 co 2 CO CH 4 N 2 NO. (MIN) ω MOLE % CC LIQUID M0LE% 1 10.5 .44 48.5 50.5 .22 .45 50.6 29.8 3.3 12.0 1 .2 2 25.'7 1.1 48.5 50.5 .53 1 .2 49.5 28.5 4.2 10.4 1 .4 3 40.8 1.7 48.5 50.5 .85 1 .7 49.3 27.9 4.7 9.3 2.4 4 55.2 2.3 48.5 50.5 1.2 2.5 45.7 28.0 5.0 8.8 2.3 5 72.1 3.1 48.5 50.5 1.5 3.3 52.9 28.0 5.1 8.6 1 .0 CO 6 89.4 3.8 48.5 50.5 1.9 4.1 54.8 28.0 5.0 8.9 0.9 7 100.6 4.3 48.5 50.5 2.1 4.6 46.4 28.0 5.1 8.9 1 .4 8 110.4 4.7 48.5 50.5 2.3 5.1 52.3 28.0 5.1 9.0 1 .2 AVERAGE 49.8 28.1 4.6 9.5 1.5 i C0 FLOW 42.5 CC/MIN 025°C H 2 0 FEED 0.021 CC LIQUID/MIN 025°C SAMPLE WEIGHT 1.08g NET CARBON GAIN 0.02g *\ Pressure has no significant effect on the rate at which steam gasification of our carbonaceous materials proceeds, but does affect the composition of the product gases obtained. Figure 3 and Table 3 set forth data obtained from steaming a nickel-based carbonaceous material at 650oC at three different ■ pressures, namely one atmosphere, 4.4 atmospheres, and 7.8, atmospheres. We conducted all these runs in small, fluidized bed, steady flow reactors at a constant steam feed rate of 23 standard cubic centimeters per minute per gram of carϋon initially in the reactor. Figure 3 shows that the carbon gasification rate was nearly linear until substantially ail the carbon was gasified. Moreover, this rate did not vary appreciably with pressure. By contrast, the product composition set forth in Table 3 did change substantially depending on the pressure. As the pressure rose from one atmosphere to 7.H atmospheres, the methane concentration tripled, the carbon monoxide concentration decreased by a factor of two, the hydrogen concentration decreased from about 53 percent to about 43 percent, and the carbon dioxide concentration rose from about 21 percent to about 31 percent. Figure 4 shows that our new carbonaceous materials can cycle many times between the carbon-rich states entering the steam gasification process of our invention, and the carbon-lean states resulting from the steam gasification processes of our invention. To illustrate this point, we prepared a one gram sample of a carbonaceous material comprising about 90 percent carbon and about 9 percent cobalt by depositing carbon from a gas mixture comprising about 85 percent carbon monoxide and about 15 percent hydrogen at 45C/OC and one atmosphere pressure. We steam gasified this carbonaceous material at 550OC and one atmosphere pressure until we had gasified about 45 percent of its carbon content. We then returned the residue to the deposition reaction, and resumed deposition until the carbon content had attained the pre-gasif ication levels. We repeated this cycle of carbon deposition and steam gasification nine times, and obtained the data set forth in FIG. 4. Figure 4 shows that the rate of steam gasification did not vary significantly from one cycle to the other. The following examples show that the cobalt-based carbonaceous materials of our invention react readily with steam, at low temperatures to produce commercially attractive quantities of gas mixtures comprising hydrogen, carbon oxides, and methane, at a rate of at least about 0.2 moles of carbon TABLE 3. PRODUCT COMPOSITION DEPENDENCE ON PRESSURE DRY PRODUCT GAS COMPOSITION, MOLE PERCENT PERCENT CARBON 1 ATM 4.4 ATM (50 PSIG) 7.8 ATM (100 PSIG) COMPONENT GASIFIED 10 52.2 44.5 41.8 HYDROGEN SO 52.9 48.7 43.5 90 53.6 51 .1 45.9 10 3.0 12.6 15.9 METHANE 50 4.9 10.2 14.5 90 3.0 8.3 12.5 10 23.9 14.1 11.2 CARDON MONOXIDE 50 21 . 1 11 .4 9.6 90 20.8 9.7 10.3 10 20.1 28.8 31.1 CARBON DIOXIDE 50 21.1 29.7 32.4 90 21 . β 30.9 31.3 NICKEL BASED CARBONACEOUS REΛCTΛNT - 90% C - 9% Ni STEΛMED ΛT 650°C FOR ΛLL RUNS STEAM FEED RATE - 23 STD CC/MIN/INITIΛL GRΛM CARBON IN REACTOR u gasified per mole of carbon present per hour when steam is f?d to the reaction at the rate of about 1.0 mole per hour per mole of carbon present at a temperature of about 550OC and at a pressure of about 1 atmosphere. Into a horizontal tube reactor we placed 0.5 gram of reduced coDalt oxide powder, and fed to the reactor a stream of 200 standard cubic centimeters per minute of a gas mixture comprising Z5 percent carbon monoxide and 15 percent hydrogen at 450°C and 1 atmosphere pressure. We continued this procedure until 3.3 grams of carbonaceous material formed. We removed the carbonaceous material formed, and determined that the carbonaceous material comprised about 87 percent carbon, about 12 percent cobalt, and about 1 percent hydrogen. We divided these materials into three one gram samples, and placed each sample in turn in a smail, vertical, fixed bed reactor with the sample suspended between quartz wool plugs. We placed the reactor in a tube furnace which controlled the reactor temperature throughout the steam gasification process. We fed steam to the reactor at atmospheric pressure and at a rate of 20.8 standard cubic centimeters per minute, holding the temperature at 5250C during the first run. We measured the volume of dry product gasses formed with a wet test meter, and determined the composition of the mixture by gas chromatography. We condensed and periodically weighed the unreacted steam. We continued each run until no further gas formed. We repeated these runs two additional t' es, once at 550°C, and once at 600 *>C. Tables 4, 5, and 6 present the outlet gas composition, the volume of product gas, the cumulative percent carbon gasified as a function of time and the average carbon balances obtained in these runs. Figure 6 plots the percent carbon gasified as a function of time at each temperature. The carbon gasification rates, shown by the slopes of the lines in FIG. 6, were nearly constant until nearly all the carbon in the samples gasified. The gasification rates increased slightly with temperature, primarily because of equilibrium considerations. As reaction temperature increased, the amount of carbon gasified per mole of steam fed to the reactor rose at equilibrium. As Table 7 and FIG. 7 show, these runs operated at near- equilibrium conditions. The run represented by Table 7 occurred at 55QoC and the run represented by FIG. 7 occurred at 60ϋoc. From the slopes of the lines shown in FIG. 6, we derived the overall carbon gasification rates at the conditions of temperature, pressure and steam feed rate used. For example, at 55Goc, 28 percent of the original carbon gasified in one hour, meaning that the carbon gasification rate was 0.28 mo TABLE 4. TYPICAL DATA SET AND CARBON MASS BALANCE FOR PACKED-BED CARBON-STEAM REACTION (87% C - 13% Co, 525°C) 1 SRAMS CARBON PRODUCT COMPOS IT ION PERCENT REACTION 1 ORY PRODUCT GAS , MOL t GASI FIED CARBON TIME , MIN. VOLUME , CC (STP) ___2 ££ ^ co 2 CUMULAT I VE GASIF EO 10 142 32.4 3,8 2.3 16.7 44.4 0.029 3.2 20 312 37.8 3.8 2.6 19.2 36.0 0.062 7.0 40 595 32.7 3.3 2.3 16.4 44.8 0.117 13.4 60 907 38.2 3.8 2.6 19.2 36.0 0.179 20.3 90 1332 33.3 3.3 3.1 16.7 44.6 0.262 29.8 120 1705 38.7 3.8 2.2 19.2 36.1 0.360 39.7 150 2210 33.8 3.0 1.6 16.8 44.7 0.431 48.9 l-υ 1B0 2606 28.4 2.2 1.2 14.0 54.0 0.500 56.8 210* 3003 34.7 2.4 1.1 16.9 44.8 0.572 65.3 AVERAGE MASS BALANCE OVER REACT ION rAimn-j n_ιι AUΓC UNGΛS I F IED CARBON ♦ CARBON PRODUCT VISES „ O.OB52 ♦ .796 y CARBON BALANCE - CARBOrCHARGTn π .όoo7) 7eή) * 100 » 10 OXYGEN OUT ■ 0.0575 MOLES HYDROGEN OUT « 0. 1 17 MOLES REACTION CONTINUEO TO EXTINCTION (330 MIN TOTAL REACTION TIME) TABLE 5. TYPICAL DATA SET AND CARBON MASS BALANCE FOR PACKED-BED CARBON-STEAM REACTION (87% C - 13% Co, 550°C) PERCENT REACTION DRY PRODUCT GAS PRODUCT COMPOSITION, MOL 1 GRAMS CARBON GASIFIED CARBON TIME, MIN. VOLUME, CC (STP) ..„ CO CH. CO, H 2 CUMULATIVE GASJF ED 10 113 17.4 4.3 1.7 10.5 55.8 0.020 2.3 30 510 37.6 8.1 6.6 20.2 27.5 0.114 12.9 50 907 37.8 7.9 6.5 19.7 28.1 0.206 23.3 70 1332 37.8 7.7 6.4 19.6 28.3 0.305 34.4 90 1728 38.6 7.7 5.8 19.8 28.0 0.395 44.6 110 2125 39.2 7.6 5.2 20.2 27.8 0.485 54.7 130 2465 40.0 7.2 5.0 20.2 28.0 0.560 63.2 i-n 150 2833 36.4 6.0 3.5 18.0 36.1 0.639 72.1 170* 3173 38.7 4.4 1.9 18.4 36.5 0.706 79.7 AVERAGE MASS BALANCE OVER REACTION CARBON BALANCE UNGΛSIFIEO CARBON ♦ CARBON IN PRODUCED GAS _ 0.0719 * 0.805 X 100 CARBON CHARGED .8056 OXYGEN OUT 0.050 MOLES 0 ? HYDROGEN 0U1 [ 0.104 MOLES H 2 M 2 /0 2 * ?.on REACTION CONTINUED TO EXTINCTION (230 MIN TOTAL REACTION TIME) TABLE 6. TYPICAL DATA SET AND CARBON MASS BALANCE FOR PACKED-BED CARBON-STEAM REACTION (87% C - 13% Co, 600°C) P RODUCT COMPOSIT ION. MOL Al GRAMS CARBON PERCENT REACTION DRY PRODUCT GAS GASIFIED CARBON TIME, MIN. VOLUME. CC (STP) C —-U-Λ| cg 2 li 2 o CUMULATIVE GASIFIED 10 286 43.1 24.4 5.0 13.7 13.8 0.066 7.1 30 575 45.2 24.9 5.1 14.2 10.6 0.203 22.0 50 863 45.3 24.4 5.0 14.3 11.0 0.338 36.6 70 1,148 44.5 23.6 4.9 14.3 12.7 0.469 50.8 90 1,428 44.3 21.6 4.7 15.0 14.4 0.593 64.2 110 1,705 44.1 20.4 4.7 15.5 15.3 0.713 77.2 • * • » 130 1,977 44.9 15.9 3.6 17.4 18.2 0.821 88.9 150* 2,199 25.2 3.5 0.3 10.7 60.3 0.855 92.5 AVERAGE MASS BALANCE OVER REACTION CARDOri BALANCE a (UNGΛSIFIED CARBON ♦ CARBON IN PRODUCT GASES) w 1ftn CARBON CHARGED * ,uu REACTION VOLUNTARILY TERMINATED. TABLE 7. COMPARISON OF MEASURED STEAM-CARBON REACTION PRODUCTS WITH EQUILIBRIUM CALCULATIONS AT 550 β C (87% C - 13% Co) EQUILIBRIUM COMPOSITION MEASURED AT 550°C* AT 550°C (DRY BASIS) (DRY BASIS) 42.9% 52.2* CO. t 30.85 27.51 CH, 14.9ϊ 9.2Ϊ- CO π .3* 11.lt 1 ATM PRESSURE carbon gasifϊeα per hour per mole of carb ' on initially in the reactor. The steam feed rate in this run was 0.752 moles of steam per hour per mole of carbon initially placed in the reactor. Because our processes operate close to equilibrium conditions, the overall carbon gasification rate is primarily a function of the steam feed rate, as FIG. S shows. There, the steam utilization at 600OC is near equilibrium throughout the run. Figure 9 is a block diagram showing some of the advantages of a preferred embodiment of our new processes for producing methane, or other synthetic natural gas, and electric power, from coal. In FIG. 9, coal from source 1 passes on path 2 to coal gasification and clean-up zone 3. There, the coal is converted to a gaseous mixture of nitrogen, carbon monoxide, carbon αioxiαe and hydrogen, and the ash, sulfur and water content of the mixture is reduced to acceptable levels by known methods. One advantage of our processes is that we can make synthetic natural gas by reacting coal with air instead of oxygen. Unlike other synthetic gas manufacturing processes, our processes are compatible with feed stocks containing substantial amounts of nitrogen ana carbon dioxide. The cold, clean product gas then passes along path <■* to carbon deposition zone 5 where formation of our carbonaceous materials Dy deposition over one or more ferrous group metal initiators takes place. Some of the fuel gas may pass along path 6 directly to power generation zone 7, if desired, for combustion with air to generate base load and/or peaking power. Depleted fuel gas passes on path S to zone 7 for conversion to power in the same way. Catalytically-active carbon rich carbonaceous material passes on path 9 to steam gasification zone 10 for reaction with steam to produce carbon monoxide, carbon dioxide, hydrogen, methane or possibly other light hydrocarbons, as desired. Carbon lean carbonaceous material is returned on patn li to carbon deposition zone 5. Nearly all of the heating value of the carbonaceous material can be converted to methane or hydrogen in our steam gasification processes. Following the process steps outlined in FIG 9, we can withdraw, say, from about 25 percent to about 50 percent of the initial heating value from a carbon monoxide/hydrogen-containing fuel gas in the form of carbon, then use the depleted fuel gas as an energy source to generate electric power or to produce power quality steam. The withdrawn carbon, which is embodied in our new carbonaceous materials, can be steam gasified to convert from about O percent to about Z0 percent of the carbon to hydrogen, carbon oxides, methane, and other light hydrocarbons. The carbon-depleted carbonaceous materials can be enriched in carbon by further carbon deposition from carDon monoxide/hydrogen gas mixtures such as the fuel gas referred to above, using the carbon-lean carbonaceous material from the steam gasification. Figure .10 shows one embodiment of a reactor for gasifying our carbonaceous materials under fluid bed conditions with steam. Our carbonaceous ' materials enter reactor 101, which has a high length-to-diameter ratio, on path 102, and pass downwardly under fluiαizing conditions on path 102 toward the ^° bottom of reactor 101. Superheated steam enters reactor 101 alon path 103 and passes upwardly into contact with the descending carbonaceous materials. Hot combustion gasses enter reactor 101 in pipes, separate from the carbonaceous material, and pass through path 103 to provide the heat required for reaction of steam with the carbonaceous materials. Carbon monoxide, hydrogen, methane 5 and other gasses formed in hot reactor zone A pass upwardly through cooler zone B, where shift methanation reactions take place, but no further carbon gasifies. Product gasses exit reactor 101 on path 105, are cooled in cooling means 106, and then passed through bag house 107, where unreacted carbon is captured for return to reactor 101. Methane-rich gas passes from bag house 107 on path 108 • *" for removal of carbon dioxide and other conventional polishing steps. Ferrous group metal component-rich material exits reactor 101 at the bottom, on path 108, and may be returned, if desired, to a carbon deposition reactor. Figure 11 shows, in block diagram, a material and heat balanced system for the conversion of our carbonaceous materials to methane, assuming steam- carbon equilibrium at 550OC and 200 psig. Carbonaceous material passes from storage zone 201 on path 202 to reactor 203. Steam enters reactor 203 on path 204 and contacts the carbonaceous materials for production of methane, carbon monoxide, hydrogen and other gases. This gas mixture exits the reactor zone on path 205, passes through superheater 206, and then, on path 207, to zone 208 0 where carbon dioxide and water are removed. From zone 208, product gas passes on path 209 to polishing methanator 210, from which the product methane gas emerges on path 211. Some of the product gas on path 205 is drawn off on path 212, passed to radiant boiler 213 in combination with air added on path 21 , and then fed 5 indirectly in pipes into reactor 203 on path 214 to provide added heat there. 3S-EA These gases leave reactor 203 on path 222, pass through superheater 218, ano boiler 219.

Claims: WHAT 15 CLAIMED 15: 1. A carbonaceous material comprising carbon in an amount from about 55% by weight to about 98% by weight; hydrogen in an amount from about 0.1 ^ to about 1% by weight; and at least one ferrous group metal component selected from the group consisting of nickel, cobalt, nickel alloys, and cobalt alloys, said ferrous group metal component containing not more than about 30 1 *. by weight of iron. 1 2. A carbonaceous material comprising a major phase that includes from 2 about 95% to about 99.9% by weight carbon, from about 0.1% to about 1% by 3 weight hydrogen, and the balance, if any, a ferrous group metal component 4 selected from the group consisting of nickel, cobalt, nickel alloys, and cobalt 5 alloys, and minor phases dispersed in said major phase consisting of nodules β comprising carbon and at least 50% by weight of at least one ferrous group metal 7 component selected from the group consisting of nickel, cobalt, nickel alloys and 8 cobalt alloys wherein iron constitutes less than about 30%' by weight of the 9 ferrous metal component. 3. A carbonaceous material comprising carbon, hydrogen, and at least one ferrous group metal component selected from the group consisting of nickel, cobalt, nickel alloys, and cobalt alloys, said ferrous group metal component containing not more than about 30% by weight of iron, said ferrous group metal component being dispersed throughout the carbon and intimately associated with and at least partly bonded to the carbon, said carbon having a steam gasification rate at about 5Q Q C and about 1 atmosphere pressure of at least about 0.2 mole per hour per mole of carbon present in said carbonaceous material where steamis fed to said gasification at a rate of about 1.0 mole per hour per mole of carbon present in said carbonaceous material. - U -yEJC 4. The carbonaceous material of claim 1 or claim 2 or claim 3 in which the ferrous group metal component is nickel. 5. The carbonaceous material of claim 1 or claim 2 or claim 3 in which the ferrous group metal component is cobalt. 6. The carbonaceous material of claim 1 or claim 2 or claim 3 wherein the ferrous group metal component in said carbonaceous material contains less than about 10% by weight of iron. -7. The carbonaceous material of claim 1 or claim 2 or claim 3 wherein the ferrous group metal component constitutes an amount from about 5% to about 25% by weight of said carbonaceous material. 8. The carbonaceous material of claim 1 or claim 2 or claim 3 formed by depositing carbon from a gas mixture comprising carbon monoxide and hydrogen in the presence of a ferrous group metal initiator. 9. The carbonaceous material of claim 8 wherein said carbon deposition is carried out at a temperature in the range of about 30QOC to about 700oC, and at a pressure of at least about 1 atmosphere. 10. The carbonaceous material of claim 8 wherein said carbon deposition takes place at a temperature of at least about 550OC, in the presence of cobalt and at a pressure of at least about one atmosphere. 11. The carbonaceous material of claim 8 wherein said deposition takes place at a temperature of less than about 500 C, in the presence of nickel and at a pressure of at least about 1 atmosphere. 12. The carbonaceous material of claim 8 wherein said ferrous group metal initiator is supported. 13. The carbonaceous material of claim 1 or claim 2 or claim 3 wherein said material is fibrous and has a total surface area, measured by gas absorption, in the range of about 100 to about 300 square meters per gram of carbonaceous material. 14. The carbonaceous material of claim 1 further comprising a support or said material. 15. The carbonaceous material of claim 2 further comprising a support or said material. 16. The carbonaceous material of claim 3 further comprising a support for said material. 17. A process comprising reacting the carbonaceous material of claim 1 or claim 2 or claim 3 or claim. 14 or claim 15 or claim 16 with steam in an amount sufficient to gasify at least some of the carbon in said carbonaceous material at a pressure of at least about 1 atmosphere and at a temperature in the range of about 550OC to about 7000O 18. The process of claim 17 further comprising contacting the products of gasification with said carbonaceous material at a temperature in the range of about 400OC to about 550OC and at a pressure of at least about 1 atmosphere. 19. The process of claim 17 wherein the ferrous group metal component s nickel. 20. The process of claim 17 wherein the ferrous group metal component s cobalt. 21. The process of claim 18 wherein the ferrous group metal component is nickel. 22. The process of claim 18 wherein the ferrous group metal component is cobalt. 23. The process of claim 17 wherein said ferrous group metal component contains less than about 10% by weight of iron. . 24. The .process of claim 18 wherein said ferrous group metal component contains less than about 10 percent by weight of iron. 25. The process of claim 17 or claim IS wherein the molar ratio of steam fed to the carbon gasified is less than about 3. 26. The process of claim 17 or claim 18 wherein the molar ratio of steam fed to the carbon gasified is at least about 3. 27. A process comprising contacting a carbonaceous material comprising a major phase that includes from about 95% to about 99.9% carbon, from about 0.1% to about 1% hydrogen, and the balance, if any, of ferrous group metal components selected from the group consisting of nickel, cobalt, nickel alloys and cobalt alloys, and minor phases dispersed in major phase consisting ofnodules comprising carbon and at least 50 percent by weight of at least one ferrous group metal component selected from the group consisting of nickel, cobalt, nickel alloys, and cobalt alloys wherein iron consitutes less than about 30 percent by weight of the errous metal component, with steam wherein the ratio of steam fed to carbon gasified exceeds the amount required for thermodynamic equilibrium at a pressure in the range of about i to about 10 atmospheres and at a temperature in the range of about 550OC to about 70QOC. 28. The process of claim 27 further comprising contacting the steam gasification product with said carbonaceous material at a temperature in the range of about 30QOC to about 550oC and at a pressure in the range of about 1 to about 10 atmospheres. 29. The process of claim 27 or claim 28 in which the ferrous group metal component is cobalt. 30. The process of claim 27 or 28 in which the ferrous group metal component of said carbonaceous material includes less than about 10 percent iron oy weight. 31. The process of claim 27 or 28 in which the molar ratio of steam to carbon gasified is greater than about 3. 32. The process of claim 27 or 28 in which said carbonaceous material is prepared by depositing carbon from a gas stream comprising carbon monoxide and hydrogen in the presence of an initiator that includes said ferrous group metal component, said carbon deposition taking place at a temperature in the range of about 50OC to about 700OC and at a pressure of at least about 1 atmosphere. 33. A process comprising contacting carbonaceous material with steam wherein the ratio of steam fed to carbon gasified is substantially the amount required for thermodynamic equilibrium, at a pressure in the range of about 10 atmospheres to about 100 atmospheres and at a temperature in the range of about 550oc to about 700oc, said carbonaceous material including a major phase comprising about 95% to about 99.9% carbon, about 0.1 percent to about 1 percent hydrogen and the balance, if any, ferrous group metal components selected from the group consisting of nickel, cobalt, nickel alloys and cobalt alloys, and minor phases dispersed in said major phase consisting of nodules comprising carbon and at least 50% by weight of at least one ferrous group metal component selected from the group consisting of nickel, cobalt, nickel alloys, and cobalt alloys wherein iron constitutes less than about 30% by weight of the ferrous metal component. OMPI 34. The process of claim 33 further comprising contacting the steam gasification products with said carbonaceous material at a temperature in the range of about 300°C to about 550OC and at a pressure in the range of about 10 to about 100 atmospheres. 35. The process of claim 33 or claim 34 in which the ferrous group metal component is nickei. 36. The process of claim 33 or claim 34 in which the ferrous group metal component in said carbonaceous material contains less than aoout 10 percent iron by weight. 37. The process of claim 33 or claim 34 in which the molar ratio of steam fed to carbon gasified is less than about 3. 38. The process of claim 33 or claim 34 in which said carbonaceous material is prepared by depositing carbon from a gas stream comprising carbon monoxide and hydrogen in the presence of an initiator that includes said ferrous group metal component, said carbon deposition taking place at a temperature in the range of about 400OC to about 525oC and at a pressure in the range of about 1 to about 100 atmospheres. 39. A process comprising contacting at least one ferrous group metal initiator selected from the group consisting of nickel, cobalt, nickel alloys, and cobalt alloys, with a fuel gas comprising carbon monoxide and hydrogen to form a carbonaceous material that includes from about 25% to about 50% of the initial heating value of said fuel gas in the form of carbon; said carbonaceous material comprising carbon in an amount from about 55% by weight to about 98% by weight; hydrogen in an amount from about 0.1% to about 1% by weight; and at least one ferrous group metal component selected from the group consisting of nickel, cobalt, nickel alloys, cobalt alloys and said ferrous group metal component containing not more than about 30% by weight of iron; separating said carbonaceous material from said fuel gas, leaving from about 50% to about 75% of the initial heating value in said fuel gas; contacting said carbonaceous material with steam in an amount sufficient to gasify aoout 40% to about 80% of the carbon in said carbonaceous material at a temperature in the range of from about 55QOC to about 700OC, and at a pressure of at least about 1 atmosphere and utilizing the depleted fuel gas as an energy source to generate electric power or to produce steam. 40. The process of clairh 39 wherein the products resulting from the steam gasification are contacted with additional carσonaceous material at a temperature in the range of about 300OC to about 500OC, and at a pressure of at least about 1 atmosphere. 41. The process of claim 39 or claim 40 wherein at least a portion of the carbon-lean carbonaceous material produced in the reaction of steam with said carbonaceous material is- reacted with a gaseous mixture comprising carbon monoxide and hydrogen to deposit additional carbon on said carbon-lean carbonaceous material. 1 42. A process comprising contacting at least one ferrous group metai 2 initiator selected from the group consisting of nickel, cobalt, nickel alloys 3 andcobalt alloys with a fuel gas comprising carbon monoxide and hydrogen to 4 form a carbonaceous material that includes from about 25% to about 50% of the 5 initial heating value of said fuel gas in the form of carbon; said carbonaceous 6 material comprising carbon in an amount from about 55% by weight to about 7 98% by weight; hydrogen in an amount from about 0.1% to about 1% by weight; 8 and at least one ferrous group metal component selected from the group 9 consisting of nickel, cobalt, nickel alloys and cobalt alloys and said ferrous group 10 metal component containing not more than about 30% by weight of iron; 11 separating said carbonaceous material from said fuel gas, leaving from about 12 50% to about 75% of the initial heating value in said fuel gas; contacting said 13 carbonaceous material with steam - in an amount exceeding the amount required 14 to gasify from about 40% to about 80% of the carbon in said carbonaceous 15 material at a temperature in the range of about 55G°C to about 70COC, and at a 16 pressure of at least about 1 atmosphere; and utilizing the depleted fuel gas as an 17 energy source to generate electric power or to produce steam. 43. The process of claim 42 wherein the products resulting from the steam gasification are contacted with additional carbonaceous material at a temperature in the range of about 300oc to about 5509C, and at a pressure of at least about 1 atmosphere. 44. The process of claim 42 or claim 43 wherein at least a portion of the carbon-lean carbonaceous material produced in the reaction of steam with said carbonaceous material is reacted with a gaseous mixture comprising carbon monoxide and hydrogen to deposit additional carbon on said carbon-lean carbonaceous material. 45. A process comprising contacting the carbonaceous material of claim 1 or claim 2 or claim 3 or claim 15 or claim 15 or claim 16 with steam in an amount sufficient to gasify about 40 percent to about 80 percent of the carbon in said carbonaceous material at a temperature in the range of about 550oc to about 700°C, and to produce a carbon-lean carbonaceous material, and reacting said carbon-lean carbonaceous material with a gaseous mixture comprising carbon monoxide and hydrogen to deposit additional carbon on said carbon- leancarbonaceous material, thus forming a carbon-enriched carbonaceous material. 46. The process of claim 45 further comprising reacting said carbon- enriched carbonaceous material with steam at a temperature in the range of about 550oc to about 700 Q C to gasify about 40 percent to about 80 percent of the carbon in said carbon-enriched carbonaceous material.

Inventors: BLUMENTHAL JACK L, BURK MAKSYMILIAN
Applicants: TRW INC
Application year: 1982
Main classification: C01G31
IPC codes: C01B3, C10J3