JPS58500445A - Novel carbonaceous material and method for producing hydrogen and light hydrocarbons from this material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Novel carbonaceous material and method for producing hydrogen and light hydrocarbons from this material The present invention involves reacting a carbonaceous material consisting of carbon, an iron group metal component, and hydrogen with water vapor. Possibly hydrogen, carbon oxides, methane, and other light hydrocarbons, and their production. One of the articles relates to a novel method for the preparation of further mixtures.

These methods provide commercially attractive product yields at commercially attractive temperature ranges. give.

The present invention consists of chopped carbon, hydrogen, iron group metal components, especially nickel and cobalt. Concerning new carbonaceous materials.

In order to produce this new carbonaceous material - a gaseous mixture comprising carbon oxide and hydrogen; Reacting an object with one or more iron group metal components.

Co-pending U.S. patent application filed 7243/7979 with the U.S. Patent Office 9q, No. 71 discloses a broad set of carbonaceous materials, including the novel carbonaceous materials of the present invention. I'm doing it. The patent application also discloses a method for producing the novel carbonaceous material of the present invention. I'm doing it. In this application, the above-mentioned applications and and U.S. Patent Application No. 9/7,2 filed with the U.S. Patent Office on July 27, 7977. 'lO, Fang g/7. A'@No. 7 is referred to here.

This new carbonaceous material contains a large amount of carbon, a small amount of hydrogen, and one or more Contains iron group metal components.

The novel carbonaceous material has a weight percent of about SS to about 9 g, preferably about 7! ;~about 95% by weight contains carbon. The iron group metal component preferably comprises about 7% to about 1% by weight of the carbonaceous material. Preferably, the amount is in the range of about -3 to about S weight. This high carbon-to-metal ratio Carbonaceous materials react readily with water vapor and are commercially available in large quantities at commercially attractive temperature ranges. produces attractive amounts of hydrogen, methane, and (also cough) other light hydrocarbons. . Furthermore, when these carbonaceous substances are reacted with water vapor, these carbonaceous substances shows excellent fluidized dust in a fluidized bed reactor. The carbonaceous material also has about 0.7 to about 8 % by weight of hydrogen. Measured by low temperature gas adsorption method, carbonaceous The material has a total surface in the range of about 700 to about 300'L2 per i.g. The pore volume ranges from about 0.3 to about 0.4 ml per 7 g of solid material.

The iron group metal components in this new carbonaceous material include nickel, cobalt, nickel alloy, selected from the group consisting of cobalt alloys and mixtures of these metals and alloys.

Generally, iron preferably makes up about 30- or less by weight of the iron group metal content of the novel carbonaceous material. or about 70% by weight or less. Nickel and cobalt are carbonaceous substances It constitutes at least 70% by weight of the iron group metal component content in the material.

This new carbonaceous material, produced by the precipitation method described below, typically It contains that aspect. The major phase is about 9S to about 99.9 weight % carbon and about 0.1% to about 1% hydrogen by weight. The remaining 7 types are listed above. or higher iron group metal components. This main phase is well distributed and explained above. A metal bundle rich in iron group metals comprising at least about 50% by weight, such as There is a minor phase. The remainder of the minor phase is mainly carbon, but young Can contain dry hydrogen.

When prepared by the preferred precipitation method of the present invention, the new carbonaceous materials can be appears fibrous under the high magnification of a scanning electron microscope. Spear S Figure 14. cobalt-containing carbon This is a scanning electron micrograph of quality fibers. This fibrous carbonaceous material is about 90% carbon by weight. As shown by the arrow in the Fang S diagram, it contains a minor phase rich in the above types of cobalt. containing at least about S weight percent.

Broadly speaking, the method for producing the new carbonaceous material involves extracting seven types of carbon from a carbon monoxide-containing gas mixture. or more consisting of precipitation on an iron group metal initiator. In the carbon precipitation process, The iron group metals move from the initiator to the carbonaceous material, and as described above, they are integrated into these materials. become a part. In order to distinguish it from the iron group metal component in this new carbonaceous material, precipitation reaction Iron group metal raw materials called initiators are supported or unsupported iron group metals, ores, It can be an alloy, or a mixture thereof.

The precipitation process ranges from about 300 to about 700 cc at about 7 to about 100 atmospheres or more. It is carried out in a circle. The iron group metal component contains approximately 70% by weight or more of nickel, and carbon precipitation When the temperature is in the range of about 30θ to about s o occ, this carbonaceous material It is particularly suitable for the production of methane by reaction with air. At precipitation temperatures above about SSθ , especially when the iron group metal component is about 70% by weight or more of cobalt. The quality is particularly suitable for the production of hydrogen by reaction with water vapor.

The novel carbonaceous material can be produced at pressures of from about 7 to about 100 atmospheres or more, from about 300 to about Highly reactive with water vapor at temperatures in the range of 750°C. This steaming reaction Product gas mixture containing hydrogen, carbon oxides, carbon dioxide, methane, and other light hydrocarbons. A compound is obtained. The amount of each gas produced in the steaming reaction depends on the nature of the carbonaceous material. and the temperature and pressure at which the steam gasification is carried out. In particular, about 300 to about 5oo C′C, especially from nickel alone or at least about 70% by weight nickel. The carbonaceous material produced in this temperature range from iron group metal components including Gasification reactions tend to produce substantial amounts of methane.

In contrast, at temperatures above about 550°C, especially cobalt alone or at least about Carbonaceous material produced above this temperature from an iron group metal component containing 70% by weight of cobalt properties tend to produce substantial amounts of hydrogen in the steam gasification reactions of the present invention.

The molar ratio of feed steam to gasified carbon is at least about 3 (where thermodynamic equilibrium requires (exceeding the amount of carbon If the material is cobalt-based, the gasification reaction tends to produce large amounts of hydrogen. Ru. The molar ratio of feed steam to gasified carbon is about 3 or less, and the steam gasification pressure is about 10 to In the range of about 100 atm (approximately equal to the amount required for thermodynamic equilibrium there), the When the carbonaceous material is nickel-based, the gasification reaction tends to produce large amounts of methane. There is a direction.

The temperature of the gaseous products initially produced in the steaming reaction of the present invention is lowered. contact with fresh or partially reacted carbonaceous material in the range of about 300 to about 5 oocc. by contacting and applying pressure to obtain the desired gas as described below. Hydrocarbon-, hydrogen-, or both-rich gases can be can be converted into a gas mixture.

This novel carbonaceous material can be In the subsequent low-temperature conversion reaction of the gasification products from the steaming reaction, significantly Worked for different purposes. In the steaming reaction, this new carbonaceous material Contributes as a reactant. Hydrogen-rich or charcoal at temperatures below the sulfurization temperature of water vapor In the subsequent conversion of the steam gasification product to a product gas mixture rich in hydrogen hydride, , this carbonaceous material acts as a catalyst.

Carbon monoxide-containing gas mixture used in the precipitation process to produce this new carbonaceous material The gas can be low pressure or high pressure generator gas or synthesis gas. like this The gas mixture can contain significant amounts of nitrogen and carbon dioxide, but sulfur Eliminates most or all of sulfur compounds such as hydrogen hydride, carbon disulfide, or sulfur dioxide. shall not contain too much. If necessary, remove sulfur-containing gases before starting carbon deposition. For this purpose, the carbon monoxide-containing gas mixture is pretreated by known methods.

Carbon deposition removes carbon young from carbon monoxide-containing gas mixtures with almost 700% thermal efficiency. Remove dryness. The heat of reaction occurs as significant heat in a fuel gas stream depleted of carbon monoxide. This is because it can remain. Carbon monoxide heated by reaction from carbon precipitation reaction This gas mixture is a good fuel source for combined cycle power generation.

This water vapor of the new carbonaceous material is a surprising advantage of the oxidation process. When the carbonaceous material contains iron as the main iron group metal component, the carbonaceous material has about 300% It has a very low reaction rate with water vapor at temperatures in the range of ~0~0''C. Steam gasification of such carbonaceous materials at temperatures above 70θ℃ involves the interaction of iron components and water vapor. Gasification stops long before all the carbon is gasified due to side reactions.

In contrast, substantial amounts of nickel, cobalt, nickel alloys, co-Gult alloys, This novel carbonaceous material containing and mixtures thereof has a high reaction rate with water vapor. , does not undergo inactivation side reactions. Figure 17 shows several different materials including the carbonaceous material of the present invention. This shows the range of water vapor reactivity with carbonaceous materials.

To obtain the data shown graphically in Figure 1, - carbon oxide is 3% and hydrogen is%? until the carbon-to-metal ratio of each sample reached 47°C or higher. A small sample of iron, nickel, and co-Gult initiator was sent over. Then gradually raise the temperature , o, s g samples of each carbonaceous material are steam-gasified, and the resulting dry gasification products are The production rate was measured. As shown in Figure 17, the relationship between these carbonaceous substances and water vapor is Reactivity changed significantly. Cobalt-containing carbonaceous material j quickly turns into gas at 5ooCc It became. In contrast, iron-based carbonaceous materials are It was inactive. Therefore, the reaction between Gτ water vapor and carbonaceous material is endothermic and indirect. It is not suitable for commercial production of hydrogen and methane as it needs to be driven by heat transfer. Nickel- and co-Glut-based carbonaceous materials are much more attractive and . This nickel- and cobalt-based carbonaceous material is easily steam gasified At temperatures in the range of about SOO to about too"C, indirect heat transfer is within the state of the art. more easily done. goθ'')C and 1 at higher temperatures, the indirect heat transfer is It is difficult to achieve and costly. Figure 2 shows water evaporation of the novel carbonaceous material of the present invention. 2 shows the effect of carbon deposition temperature on the composition of product gas produced by gas gasification.

This is a number to show the effect of this carbon precipitation temperature. Two different cobalt-based Created a carbonaceous material. /sample lIs oC'C and other samples bs.

By forming at ℃, an inner carbonaceous sample is created by reaction with cobalt powder. It was. The precipitation reaction was continued until a carbon to co-gurt weight ratio of 10 was obtained. Tooth diagram As shown in Figure 2, the carbonaceous material precipitated at 630°C is Produces much more hydrogen in steam gasification reactions than baltic-based carbonaceous materials Ta. In fact, after removal of the carbon dioxide produced during steam gasification, A! iMade at 0℃ Carbonaceous 'vr　'J: Well, when steamed at 0℃, it becomes almost pure hydrogen. generate.

The data in the Tables 1 and 2 are for water vapor of carbonaceous reactants containing different iron group metals. If the carbon gasification products are further reacted at a temperature below the carbon gasification point of about 500°C shows the difference in final product gas composition. On the Fang 7 table, approximately 5OCc is applied on nickel powder. Carbon precipitation (carbon consisting of about 90% carbon and about 9% nickel) The quality material is reacted with carbon monoxide, hydrogen, and water vapor in a stationary reactor at q00°C and approximately /atm. Further conversion of the conventional steam-carbon gasification mixture is catalyzed. As Table 17 shows, Almost all of the carbon oxides are converted to methane and carbon dioxide, and almost all of the solid carbon is converted to methane and carbon dioxide. It does not gasify at all (from 0.g39 to 0.09g in 203 minutes).

The jp2 table is related to the same experiment with one exception: Carbonaceous materials are a substitute for nickel. (approximately qO of carbon and approximately 9% cobalt). these days From the above, cobalt-based carbonaceous materials are used to convert the gas mixture into methane. Although much less effective than nickel-based catalysts, nickel-based methane27 ．． 24r, q, s% on a co-root basis), even more important for conversion to hydrogen. (Hydrogen llq, g% from co-gurt-based materials, nickel-based materials? It can be seen that these are the core and the θ section).

10 111 Stacked stones 8-5 [! 0445 (6) Pressure increases as water vapor gasification of carbonaceous material progresses does not have a significant effect on the rate of production, but does affect the composition of the resulting product gas. . , 1-. Figure 7 and Table 3 show three different pressures: 1 atm, +, y atm. Steaming of Niracle-based carbonaceous material with A & Ooc at 1g atm. The data obtained are shown below. 3 standard cr/min per g of initial carbon in the reactor Perform all these experiments in a small fluidized bed steady flow reactor, with a constant steam feed rate. became. Figure 3 shows that the carbon gasification rate is almost constant until virtually all the carbon is gasified. Indicates that it is linear.

Furthermore, the carbon gasification rate did not change appreciably with pressure. to this In contrast, the product composition shown in Table 3 varied substantially depending on pressure. pressure is l From atmospheric pressure? When the pressure rises to 4 atmospheres, the methane concentration triples and the carbon oxide concentration is halved. The hydrogen concentration decreased from about 33% to about 3%, and the carbon dioxide concentration decreased from about -/%. It increased from 37 cm to 37 cm.

Figure 1 shows the carbon-rich state entering the steam gasification process of the present invention and the steam gas of the present invention. This new carbonaceous material can be recycled many times between carbon-poor conditions resulting from the oxidation process. Show that you can do it.

From a gas mixture consisting of about gs% carbon monoxide and about i3% hydrogen, ttsoC′C,i By precipitating carbon under atmospheric pressure, charcoal consisting of approximately 90% carbon and approximately q% cobalt is produced. Samples/g of prime material were prepared. until about xis% of its carbon content is gasified. This carbonaceous material was steam-gasified at 550° C. and 7 atm. Then the residue is precipitated out and precipitation was started again until the carbon content reached the pre-gasification level. Carbon precipitation This cycle of water and steam gasification was repeated nine times, and the data shown in Figure 19 was obtained. . The graph shows that the steam gasification rate does not change significantly from one cycle to another. It shows that there was no.

water vapor per mole of carbon present at a rate of about When fed to the reaction, at least about 0.2 moles per mole of carbon present per 7 hours. At the rate of gasification of carbon, the cobalt-based carbonaceous material of the present invention’ can be combined with water vapor at low temperatures. Easily reacts and makes gas mixtures consisting of hydrogen, carbon oxides, and methane commercially attractive The following examples show that it is produced in amounts.

14 0.5 g of reduced cobalt oxide powder was placed in a horizontal tube reactor, and -3% of carbon oxide g was added. A gas mixture consisting of 1S% hydrogen - 〇〇 standard cubic meters/minute flow is reacted at ttho °C/atm. Sent to Oki. This operation was continued until 3.3 g of carbonaceous material was produced.

The produced carbonaceous material is removed, and this carbonaceous material has a carbon content of 7%, approximately , was determined to consist of 7% hydrogen. Divide this material into three 7g samples and The sample was placed in a small vertical fixed bed reactor, and the sample was suspended between quartz wool Zorags. . During the steam gasification process, the reactor was placed in a tube furnace with controlled reactor temperature. water vapor Send air to the reactor at a rate of 20-g drift mark/min at atmospheric pressure, fang/s during the experiment, 2s. It was kept at oC. Measure the volume of dry product gas produced with a wet gas meter and The composition of the mixture was determined by chromatography. Condenses unreacted water vapor, Weighed regularly. Each experiment was continued until no more gas was produced. these The experiment was repeated Ku times, once at 550°C and 7 times at 00°C. Fang q, Tables s and b show the gas composition, product gas volume, and gas as a function of time obtained in this experiment. It shows the cumulative amount of carbon sulfide and the average carbon budget.

Figure 6 shows the plot of gasified carbon as a function of time at each temperature.

The carbon gasification rate, indicated by the slope of the line in the λ・6 diagram, is almost all in the sample. remained almost constant until the carbon gasified. Primarily for equilibrium reasons, Ga The oxidation rate increased slightly with temperature. As the reaction temperature increases, the amount of water fed to the reactor increases. The amount of carbon gasified per mole of water vapor increased to equilibrium. , t-7 table and fang 7 diagram are This shows that these experiments were conducted under near-equilibrium conditions. Experiments shown in Table 7 was at SSO, and the experiment shown in Figure 7 was conducted at θθ°C.

From the slope of the line shown in the diagram, the total The carbon gasification rate was obtained. for example,! ; At 5θ℃, 23% of the original carbon is 7 o'clock The carbon gasification rate is 7 hours per mole of initial carbon in the reactor. Gasified carbon 0. ．． It means that it was 2g mole.

8 20 Comparison of measured steam-carbon reaction raw materials and equilibrium calculated values at SSO°C (gq%C-73%Co) At 330℃ at 5θ℃ Equilibrium composition/measurement (Dry standard) (Dry standard) H242.9% 52.2% Co 3 (1st and 8th section 27.5% CH4] 4.9% 9.2% Co 11.3% 11.1% The water vapor feed rate in this experiment was determined by the amount of water per mole of carbon initially introduced into the reactor. Steam 0. '/32 mol/hour.

Since the method of the present invention operates near equilibrium conditions, the total carbon gas The conversion rate is primarily a function of the steam supply rate. In this case, water vapor in AOOcc Air utilization is close to equilibrium throughout the experiment.

Fang9 plans to produce methane, raw or other synthetic natural gas, and electricity from coal. 1 is a block diagram illustrating some of the advantages of a preferred implementation of the novel method; FIG.

In the diagram, coal from source 1 passes through passage 2 and coal goes to sulfurization and refining zone 3. move on. Here, coal is converted into a gaseous mixture of nitrogen, carbon oxides and carbon dioxide. The ash, sulfur and water contents of the mixture are reduced to acceptable levels by known methods. Ru. An advantage of the method of the invention is that by reacting the coal with air instead of oxygen, 1. Unlike other synthetic gas production methods, the present invention The process is compatible with feedstocks containing significant amounts of nitrogen and carbon dioxide. Then cool The purified product gas passes through passage 4 to carbon deposition zone 5 where it is separated or A carbonaceous material is produced by precipitation on the above iron group metal initiator. wish At this time, some of the fuel gas can go directly to the power generation zone 7 through the passage 6, and the It burns with air to generate base load and peak power. dried up fire The feed gas passes through passage 8 to zone 7 for conversion into electrical power as well.

The catalytically active carbon-rich carbonaceous material passes through passage 9 into water for reaction with water vapor. Go to steam gasification zone 10 and produce carbon monoxide, carbon dioxide, hydrogen, methane as desired. , produce slag or other light hydrocarbons. In this steam gasification method, most of the carbonaceous materials are Almost all of the heat of combustion can be converted into methane or hydrogen.

According to the process steps outlined in Figure 9, -carbon oxide/hydrogen-containing fuel is Approximately 23% to approximately Sθ% of the initial combustion heat can be extracted from the gas in the form of carbon. The fuel gas that is depleted in the process is used as an energy source to generate electricity or power Can produce high quality steam. The extracted carbonaceous material embodied in the novel carbonaceous material of the present invention Carbon is steam-gasified to convert approximately ’IQ to approximately goes of carbon into hydrogen, carbon oxides, and metals. Tan, which can be converted to other light hydrocarbons. Carbon poor carbon products from steam gasification further carbon from a carbon monoxide/hydrogen gas mixture such as the fuel gas above. The precipitation can deplete carbon and enrich the carbonaceous material with carbon.

Figure 70 shows a reactor for gasification of carbonaceous materials with steam under fluidized bed conditions. Indicates embodiment.

In the diagram, the carbonaceous material passes through passage 102 into a reactor having a high length-to-diameter ratio. 101 and proceed downwardly through passage 102 to the bottom of reactor 101 under fluidized conditions.

Superheated steam enters the reactor 101 through the passage 103 and proceeds upwards, causing carbon to fall. contact with a substance. The hot combustion gas enters the reactor 101 in a separate tube from the carbonaceous material, It passes through passage 103 and provides the heat necessary for the reaction of the water vapor with the carbonaceous material.

Carbon monoxide, hydrogen, methane and other gases produced in the thermal reactor zone (A) are transferred to the cooler zone. Proceeding upward through zone (B), where a transitional methanation reaction occurs, further carbon is Does not gasify. Product gas exits reactor 101 in passage 105 and is cooled in cooling device 106. The unreacted carbon is then cooled and passed through the Gusoge House 107, where the unreacted carbon is transferred to the reactor 1. Captured to return to 01. Methane-rich gas comes from Bag Us 107 Passage 108 leads to carbon dioxide removal and other conventional polishing steps. .

Materials rich in iron group metal components pass through passage 108 and exit reactor 101 at the bottom, but not as desired. When needed, it can be returned to the carbon precipitation reactor.

Off figure 7! ;! ; Assuming water vapor-carbon equilibrium at OcC', 200 psig and the block line of a system with a balance of matter and heat to convert this carbonaceous material into methane. Show the diagram.

In the figure, carbonaceous material passes from storage zone 201 through passage 202 to reactor 203. move on. Water vapor enters reactor 203 in passage 204, containing methane, carbon oxide, hydrogen, Contact with carbonaceous materials for the production of other gases. This gas mixture passes through passage 205 Exiting the reactor zone, passing through superheater 206 and then through passage 207 to zone 208 carbon dioxide and water are removed here. From zone 208, the product gas passes through 209 to a polishing methanator 210 from where the product methane gas exits through passage 211.

Product gas in passage 205 is removed through passage 212 and added in passage 214. It is sent to the radiant mailer 213 along with the added air, and then passes through the passage 214 and is separated by a pipe. Directly to reactor 203 to provide additional heat. This gas passes through passage 222. It leaves the reactor 203 and passes through a superheater 218 and a mailer 219.

Engraving (no changes to the content) Fig, 1 Gasified next element Z 2 minutes reaction time Fig, 3 time, 8 Cobalt-rich f′ phase Fig, 3 Rebellion time 2 minutes It turned into a s; the original σ returned to the back Fig, 7 Between songs, 8 Fig, 8 Fig, 9 1.10 1] Commissioner of the Patent Office 3 Person making the amendment Relationship to the case: Applicant Name T.R.W. Incoholated 4 Agent Pa ・　Amendment order dated December 2, 1982/Usu A international search report In+amauya+aeolbau. -H-82100310! ! 11FI eATlo110F 5LIaJ ward eT MATTER+ll m enl c lamllcsllu+ +ymWh metalt, ma-can allll '1111111111 Inum Hatake-eal P-1Ckmtmkn O P mouth w b ham Hamonal Oaa-mtlaa and Il’C NT, CL, 3COIG 31100; Cl0J 3100; Cl0K 1100□, S, CL, 252/191.4B/197R=-denSll reffilC1allllllRυ*ak+nwl+252/191.373 585/733U, 6. 48/197R, 203 423/439,459 0ecuIII4nulla11shigutchwiaun+廿laa&l1mmu mOmu+matu+m+olhaEde++ILIVI@-RoIlCIImn uarmlaclvdedr+mFbldiSaanhad+koeuMiNTI IGONsION Kasumi KOToII! IIUJV^NT■Y”1C11a++6f lalQ6cwmeL11wHhlRdlcamm1wj@SIN@N1m1# , 611h@Ml+Tan1Mmm191MIIIlblt+mMIlIC1m 1mN6.1lUS, A, 2,686,819 Published 17 August 1954. 17-46 Johnson US, A, 4,134,907 Published 16 January y 1979 1-16Stephens US, A, 4,211,669 Published 8 July 198 0. 1-16akman US, A, 4,242JO3Published 30 Decerrhe r　1　1-46Rab.

uS, A, 4,242,104 Published 30 Deceyb er　　　1-46lost

Claims (1)

[Claims] (1) about SS to about 9 g% by weight of carbon and about θ, a to about /% by weight hydrogen; , nickel, cobalt, nickel alloys, and cobalt alloys. Consisting of at least seven iron group metal components, However, the iron group metal component contains approximately 30% by weight or less of iron; A carbonaceous substance consisting of. (2) Carbon about 9s to about 99.9% by weight and hydrogen about θ, / to about 7% by weight and the rest Ni Iron group metals selected from the group consisting of cobalt, nickel alloys, and cobalt alloys. A main phase containing components, Selected from the group consisting of nickel, cobalt, nickel alloy, cobalt alloy, and iron at least one iron group metal comprising about 30% or less by weight of the iron group metal component; The main phase consists of nodules consisting of at least 50% by weight of the genus component and carbon. Minor phases dispersed in A carbonaceous substance consisting of. (3) Carbon, hydrogen, and nickel, conochrite, nickel alloy, cobalt alloy consisting of at least seven iron group metal components selected from the group consisting of The composition contains approximately 30% by weight or less of iron, and the iron group metal component is easily divided into carbon. dispersed and closely associated with carbon and at least partially bonded to carbon; per mole of carbon present in the carbonaceous material at a rate of approximately LO mole/hour. When steam is supplied to the gasification, the carbon is heated at about 550°C and about 1 atm. At least about 0.2 mole/hour of water vapor gas per mole of carbon present in the prime material. Carbonaceous material with a sulfurization rate. (4) Claim (1) or (2) or ( 3) carbonaceous material. (5) Claim (1) or (2) or (3) in which the iron group metal component is cobalt. ) carbonaceous materials. (6) The iron group metal component in the carbonaceous material contains approximately 10% by weight or less of iron. The carbonaceous material according to claim (1) or (2) or (3). (7) Claims in which the iron group metal component constitutes about 5 to about 25 parts by weight of the carbonaceous material. The carbonaceous material of (1) or (2) or (3). (8) Carbon from a gas mixture consisting of carbon monoxide and hydrogen in the presence of an iron group metal initiator Claims fil or Fi(2+ or (3) carbonaceous material. (9) The carbon precipitation is carried out at a temperature in the range of about 300 to about 700°C for at least about 1 atmosphere. The carbonaceous material according to claim (8), which is carried out at a pressure of about 100 ml. III. The carbon precipitation occurs at a temperature of at least about 550°C and in the presence of cobalt. The carbonaceous material according to claim (8), wherein the carbonaceous material is also treated at a pressure of 1 atmosphere. Uυ The precipitation occurs at a temperature of about 500°C or less, in the presence of nickel, at least about 1 The carbonaceous material according to claim (8), which is carried out at atmospheric pressure. a2 The carbonaceous material according to claim (8), which supports the iron group metal initiator. a3 If the substance is fibrous, it is measured by gas adsorption and the carbonaceous substance is Claim +11 or (2) having a total surface area in the range of 100 to about 300 m2 ) or (3) carbonaceous material. α4 Claims further including a carrier for the substance (carbonaceous material). αS The carbonaceous material according to claim (2), further comprising a carrier for the material. αe The carbonaceous material according to claim (3), further comprising a carrier for the material. αη Claim (1) or (2 or (3) or I or a9 or α e carbonaceous material and gasifying at least some of the carbon in the carbonaceous material. a sufficient amount of water vapor at a pressure of at least about 1 atmosphere and a temperature in the range of about 550°C to about 700°C. A method consisting of reacting at a temperature of (119 gasification products and the carbonaceous material at a temperature in the range of about 400 to about 500 °C) further contacting at a pressure of at least about 1 atmosphere. Method. a9 The method according to claim αη, wherein the iron group metal component is nickel. ■ The method as claimed, wherein the iron group metal component is cobalt. (2υ The method according to claim fil, wherein the iron group metal component is nickel. ■ The method according to claim 08, wherein the iron group metal component is cobalt. (2) Claims in which the iron group metal component contains about 10% by weight or less of iron (2) the method of. (c) Claims in which the iron group metal component contains about 10% by weight or less of iron: 0 seconds the method of. (2) The claimed or (1 second method.. (to) Claim a' wherein the molar ratio of feed steam to gasified carbon is at least about 3. ; h or method 08. About 95% to about 99.9% by weight of carbon, about 0.1% to about 1% by weight of hydrogen, and residual nickel iron group metal selected from the group consisting of cobalt, cobalt, nickel alloys, and cobalt alloys. a main phase containing Iron constitutes approximately 30% by weight or less of the iron group metal component, and iron, nickel, and cobal At least one iron group member selected from the group consisting of cobalt alloys, nickel alloys, and cobalt alloys. A main phase consisting of at least 50% by weight of metal components and nodules consisting of carbon. A carbonaceous material consisting of a small dispersed phase is produced when the ratio of feed steam to gasified carbon is thermodynamically balanced. With water vapor in excess of the amount necessary for equilibrium and a pressure in the range of about 1 to about 10 atm. A method comprising contacting at a temperature in the range of 00°C. (To) The steam gasification product and the carbonaceous material are heated at a temperature in the range of about 500 to about 550°C. further contacting at a temperature in the range of about 1 to about 10 atmospheres. Range (b) method. Claims @ or (to) the method, wherein the tetrairon group metal component is cobalt. (7) A claim that the iron group metal component of the carbonaceous material contains about 10 - or less weight of iron. Range (b) or (to) method. Gl) claims where the molar ratio of water vapor to gasified carbon is greater than about 3; )the method of. (b) The presence of the initiator containing the iron group metal component in the gas stream consisting of carbon monoxide and hydrogen. The carbonaceous material is produced by precipitating carbon at The claimed method is carried out at a temperature in the range of 50 to about 700°C and a pressure of at least about 1 atmosphere. Range @ or (to) method. (To) The ratio of steam to gasified carbon supplied to the carbonaceous material is substantially the amount required for thermodynamic equilibrium. about 550 to about 700 degrees Celsius at a pressure in the range of about 10 to about 100 atmospheres. Avoid contact at temperatures in the range of The carbonaceous material contains about 95% to about 99.9% by weight of carbon and about 0.1% to about 1% by weight of hydrogen. The remainder is selected from the group consisting of nickel, cobalt, nickel alloys, and cobalt alloys. a main phase consisting of an iron group metal component; Iron constitutes approximately 30% by weight or less of the iron group metal component, and iron, nickel, and cobalt at least one iron group metal selected from the group consisting of , nickel alloy, and cobalt alloy. The main phase consists of at least 50% by weight of the genus component and carbon and fine nodules. with a small phase dispersed in Containing method. (To) The steam gasification product and the carbonaceous material are heated at a temperature in the range of about 500 to about 550°C. further contacting at a temperature and pressure ranging from about 10 to about 100 atmospheres. Range Q method. (g) The method according to claim 33 or (b), wherein the iron group metal component is nickel. (7) The iron group metal component in the carbonaceous material contains approximately 10% by weight or less of iron. The method according to claim 33 or □. On Claims (to) or where the molar ratio of feed steam to gasified carbon is about 3 or less; (b) method. ■ - Initiator containing the iron group metal component is extracted from a gas stream consisting of carbon oxide and hydrogen. The carbonaceous material is produced by precipitating carbon in the presence of carried out at a temperature in the range of 400 to about 525°C and a pressure in the range of about 1 to about 100 atmospheres. Claim 33 or (to) the method. (to) Nickel, cobalt, nickel alloy, near +1 F alloy. at least one iron group metal initiator selected from the group consisting of carbon monoxide and hydrogen; About 25 to about 50% of the initial combustion heat of the fuel gas is converted into carbon by contacting with the fuel gas. form a carbonaceous material containing from about 55 to about 98% by weight. of carbon and about 0. Hydrogen and nickel, cobalt in an amount of 1 to about 1% by weight at least one iron group metal selected from the group consisting of , Futsukeru alloy, and cobalt alloy. The iron group metal component contains less than about 60% by weight of iron. Then, the carbonaceous material is separated from the fuel gas, and the carbonaceous material is separated from the fuel gas, and the carbonaceous material is separated from the fuel gas and 75% of carbonaceous material is left in the fuel gas, and the carbonaceous material is heated to a temperature in the range of about 550 to about 700°C. from about 40 to about 80 carbon in the carbon material at a temperature of at least about 1 atmosphere and a pressure of at least about 1 atmosphere. The depleted fuel gas is converted into energy by contacting it with enough water vapor to gasify it. - a method of generating electricity or producing water vapor by using it as a source. t4G Product obtained from steam gasification with additional carbonaceous material about 300 to about 50% Claim C (l) contacted at a pressure of at least about 1 atmosphere at a temperature in the range of Method. lυ A small amount of carbon-poor carbonaceous material produced by the Ω reaction between the carbonaceous material and water vapor. by reacting at least a portion of it with a gaseous mixture of -a-carbon and hydrogen. Claim c39 or 4, in which carbon is further deposited on a carbon-poor carbonaceous material the method of. t43 Selected from the group consisting of nickel, cobalt, nickel alloy, and cobalt alloy at least one iron group metal initiator in contact with a fuel gas consisting of carbon monoxide and hydrogen. The fuel gas contains about 25 to about 50% of the initial heat of combustion in the form of carbon. forming a carbonaceous material containing from about 55% to about 98% by weight of carbon and carbonaceous material; and hydrogen and nickel, cobalt, nickel alloys in an amount of about 0.1 to about 1% by weight. , at least one iron group metal component selected from the group consisting of cobalt alloys. , the iron group metal component still contains less than about 30% iron by weight, and the carbonaceous material is separated from the fuel gas, and approximately 50 to 75% of the initial combustion heat is transferred to the fuel gas. the carbonaceous material at a temperature in the range of about 550°C to about 700°C. Required to gasify about 40 to about 80 inches of carbon in the carbonaceous material at a pressure of 1 atmosphere. The depleted fuel gas is used as an energy source by contacting with water vapor in an amount exceeding the required amount. A method consisting of using water to generate electricity or produce water vapor. (43) the product obtained from steam gasification with additional carbonaceous material from about 300 to about 550 14. The method of claim 13, wherein the contacting is carried out at a pressure of at least about 1 atmosphere at a temperature in the range of .degree. 1141 Carbon-poor carbonaceous material produced by the reaction between the carbonaceous material and water vapor reacting at least a portion of the hydrogen with a gaseous mixture of carbon monoxide and hydrogen. Claim 14, wherein carbon is further deposited on the carbon-poor carbonaceous material. 143 methods. (c) Claim m dimension (2), or (3), or θ Yu or a9, or or 11 carbonaceous materials in the carbonaceous material at a temperature in the range of about 550 to about 700°C. charcoal by contacting it with sufficient water vapor to gasify about 40% to about 80% of the carbon in the charcoal. The carbon-poor carbonaceous material is treated with carbon monoxide and water. Further carbon is added onto the carbon-poor carbonaceous material by reacting with a gaseous mixture consisting of a method consisting in precipitating out elements and thus forming carbon-rich carbonaceous substances. ■ The carbon-rich carbonaceous material is mixed with water vapor at a temperature in the range of about 550 to about 700℃ Further reaction is performed to remove about 40 to about 80% of the carbon in the carbon-rich carbonaceous material. Characteristic Claims l! 9 ways.