[go: up one dir, main page]

WO1983001949A1 - Procedes de production de combustible a partir de materiaux solides - Google Patents

Procedes de production de combustible a partir de materiaux solides Download PDF

Info

Publication number
WO1983001949A1
WO1983001949A1 PCT/US1981/001584 US8101584W WO8301949A1 WO 1983001949 A1 WO1983001949 A1 WO 1983001949A1 US 8101584 W US8101584 W US 8101584W WO 8301949 A1 WO8301949 A1 WO 8301949A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal
carbon
carbides
carbide
fuel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1981/001584
Other languages
English (en)
Inventor
Robert D Waldron
Dale D Hammih
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to AU80062/82A priority Critical patent/AU8006282A/en
Priority to PCT/US1981/001584 priority patent/WO1983001949A1/fr
Priority to EP82900290A priority patent/EP0094936A1/fr
Publication of WO1983001949A1 publication Critical patent/WO1983001949A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/907—Oxycarbides; Sulfocarbides; Mixture of carbides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/50—Agglomerated particles
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases

Definitions

  • fuel precursors While the principal volatile products of conversion of carbide “fuel precursors” are hydro ⁇ carbons, they may be accompanied by various lesser amounts of hydrogen, carbon monoxide, carbon dioxide and compounds containing carbon, hydrogen and oxygen (and/or additional elements).
  • fuel precursor shall designate a compound capable of generating all such volatiles where used for fuel or non-fuel purposes.
  • Another further object of the present invention is to provide a process for the manufacture of fuel precursors, which process uses substantially less power per unit derived fuel energy than the ⁇ calcium carbide-acetylene system, which can be operated at substantially lower temperatures, and for which the mineral residue (oxide-hydroxide) generated
  • OMPI fro the fuel gas conversion stage can be readily and economically recycled to manufacture more fuel precursor.
  • Still another object of the present invention is to provide a fuel precursor which may be stored or stockpiled safely without undue fire hazard or deterioration due to air exposure or other factors, to provide an economical reserve capacity for accommodating short term or seasonal fluctuations in fuel demand or supply requirements during scheduled or unscheduled interruptions in manufacture of fuel precursor.
  • Yet another object of this invention is to provide a continuous process for the manufacture of fuel precursor and a conversion process for hydro ⁇ carbon generation which may be rapidly adjusted to meet utility demand loads.
  • a further object of the invention is to provide mineral carbide fuel precursors which are convertible to fuel gases or liquids.
  • Yet a further object of the present invention to provide fuel precursors from which sulfur and other noxious or undesirable impurities introduced by the coal or other raw materials during manufacture of the precursors can be substantially reduced or removed easily to provide environmentally clean gaseous or liquid fuels.
  • Yet another object of the invention is to provide fuel precursors capable of generating high yields of unsaturated hydrocarbons, such as olefins and acetylenes, which are useful for manufacture of polymers and other valuable chemical products.
  • BRIEF DESCRIPTION OF THE DRAWING Figure 1 is a schematic representation of a process for producing fuel precursors (solid).
  • Figure 2 is a schematic representation of a process for converting the fuel precursors into useful fuel gases or liquids. DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • the classification of carbides into “salt-like” compounds and “metal-like” compounds is most useful in describing their general properties.
  • Salt-like or ionic carbides are electrical insulators with thermophysical properties similar to oxides and usually showing little tendency toward defect structures. They are generally reactive toward water or dilute acids, are reducing agents at elevated temperatures and tend to dissolve in fused salt systems. These carbides are usually formed from the more basic metals such as alkali, alkaline earth, and aluminum family elements.
  • metal ⁇ like carbides are electrical conductors with thermo ⁇ physical properties similar to metals and usually showing an appreciable tendency toward defect structures.
  • OMPI V IPO behave principally like ionic carbides but are electrical conductors, apparently due to lower than normal chemical valence and close metal-metal atomic distances in the crystal structure.
  • metallic carbides of first transition series elements such as vanadium, chromium, manganese, iron, cobalt and nickel behave in most characteristics like metallic or interstitial carbides, but are more reactive or corrodible by water or dilute acids, apparently resulting from atomic size defects in the crystal structure.
  • a classification of carbides on the basis of thermodynamic stability is useful in indicating possible methods of preparation, precautions in storage and handling and reactivity at various temperatures. It is convenient to use five categories which may be designated as highly stable, stable, metastable, marginally unstable, and highly unstable.
  • the highly stable carbides are limited to interstitial carbides of the transition elements which have negative heats of formation in excess of -(25)Kcal/mole°C and which are extremely hard, refractory, and chemically inert. Examples include TiC, ZrC, TaC, NbC, and the like. Tungsten carbides, boron carbide and silicon carbide have lower heats of formation but have similar properties and should probably be included in this group.
  • the stable carbides include those carbides with negative free energies of formation at all temperatures from room temperature to 1200°C or more except those carbides included in the first group.
  • carbides of the alkaline earth metals except magnesium
  • aluminum certain higher carbides of chromium, manganese and the rare earth metals.
  • Metastable carbides are those compounds which are thermodynamically stable with respect to free metal and carbon at some elevated temperature but, even though unstable at ambient temperatures, can be quenched and preserved indefinitely at low or ambient temperatures. Examples include Mn C,
  • the marginally unstable carbides include carbides of iron, cobalt and nickel which are slightly less stable than the corresponding metal and graphite but which are also storable for indefinite periods at room temperature.
  • the last class, highly unstable carbides consists of the carbides that cannot be formed from the elements, but may only be prepared by lower temperature indirect processes from carbon compounds. These include the carbides of magnesium, zinc, copper, silver, etc. If their heats of formation are too positive, they may be subject to explosive decomposition.
  • the salt-like or ionic carbides normally hydrolyze to yield a single hydrocarbon characteristic of the carbide and on that basis may be classified as acetylides, ethanides or allylide ⁇ corresponding to acetylene, methane or allylene as the hydrolytic reaction product.
  • the metal-like carbides are for the most part substantially chemically inert at low temperatures, but some may be hydrolyzed (corroded), yielding a mixture of hydrocarbons and various amounts of hydrogen, oxides of carbon, etc., depending on the conditions of hydrolysis.
  • the excess metallic atoms are capable of reducing the water to form neutral hydrogen atoms which can then directly reduce carbon atoms or react with unsaturated hydrocarbons or chemical intermediates such as methylene groups (CH 2 ).
  • the hydrolysis reactions of these compounds are consistent with treating them as solid solutions of
  • OMPI_ ionic carbides in excess free metal or alloys of metal and hydrolyzable carbide.
  • the hydrolysis product of carbides formed from metallic elements of small ionic radii such as aluminum and beryllium consists primarily of methane and the product formed from the lower carbide of magnesium, with Mg 2 C 3 forming allylene (methylacetylene). Most of the remaining ionic carbides yield acetylene upon hydrolysis.
  • OMPI - fraction x of the carbon atoms yields hydrocarbons on hydrolysis, with a fraction 1-x appearing as free carbon.
  • -V represents the valence of the carbon atom.
  • V 4 for pure methane formers
  • V 3 for ethane formers
  • V 2 for methylene or ethylene formers
  • V 1 for acetylene formers.
  • the carbon content then contains Vx equivalents which are balanced by an equal number of metal ionic equivalents.
  • the balance of the metal atoms can be considered as neutral metal.
  • the total number of metallic equivalents after hydrolysis is given by Z V where V is the average valence of lowest metallic states of constituent elements stable in the presence of water.
  • the difference ZV-Vx represents the excess reducing power which appears as hydrogen in reaction products. We may thus write the over-all reaction as:
  • the specific heating value of the fuel gas depends on the distribution of carbon atoms between methane and higher hydrocarbons with 2, 3 or more carbon atoms per molecule.
  • the specific heating value of the fuel gas depends on the distribution of carbon atoms between methane and higher hydrocarbons with 2, 3 or more carbon atoms per molecule.
  • the heat of combustion per mole of carbon is nearly the same for both systems, but the heat of combustion per unit volume (gas mole) is 50% greater in the second case.
  • Mn ⁇ C the average number of carbon atoms per hydrocarbon molecule obtained on hydrolysis equals 1.45. Energy Balance for Synthetic Fuels
  • All of the existing or proposed processes for producing hydrocarbons and/or carbon monoxide and hydrogen from carbonaceous sources may be considered as a sum of individual chemical reactions in which all reactants other than carbon and oxygen enter in a cyclic manner, emerging in the same compounds as they enter.
  • the potential heating value upon complete combustion is equal to 94.05 Kcal/gram mole (169.29 KBTU/lb mole) which may be taken as the theoretical input energy unless other forms of energy are also consumed.
  • a fraction f will be recovered as useful fuel gases and the fraction 1 - f will be burned or otherwise lost to supply process heat.
  • the useful output heat is then given by: out he he o co H « H «
  • ⁇ H is the average heat of combustion of a_ p c er mole (with hydrocarbons CmHn rewritten as
  • net and gross heat ratios For processes that use metallic carbides as chemical intermediates, two other thermal figures of merit are useful, namely, net and gross heat ratios, where the net heat ratio is the ratio of heat of combustion of fuel gases produced to the heat of combustion of the carbide, and the gross heat ratio is the ratio of the sum of the heat of fuel gas combustion plus heat of conversion (hydrolysis) to the heat of combustion of the carbide.
  • the oxidation of the metallic component is considered to be carried to the valence state normally found after hydrolysis.
  • Table I shows heats of combustion and net heat ratios for various carbides.
  • the net heat ratios are generally above .8-.9, except for the ionic carbides which yield methane on hydrolysis.
  • A1.C 3 has a net heat ratio of .618 while Be 2 C has a value of .585, which are both too low for efficient synthetic fuel processes.
  • the remaining carbides are members of the alloy or metal-like carbide class.
  • Interstitial alloy carbides such as Mn_C, Fe.,C and related carbides of higher carbon content
  • Rare earth or actinide carbides such as cerium, thorium, or uranium carbides.
  • the first class (interstitial alloy carbides) contains metals whose oxides are easily reducible, but their heating values per unit weight are low and their reactivity toward water or steam is low in some cases. In addition, they are difficult to prepare free of excess metal, which usually requires an acidic medium to effect hydrolysis.
  • the second class (rare earth or actinide carbides) is more reactive, but the metallic elements are difficult to reduce.
  • transition metal carbides In the usual methods of forming the transition metal carbides from molten metal and carbon, it is often difficult to prepare the carbides completely free from an excess metal-rich phase. This phase can be more resistant to action of water or steam.
  • sufficient reactive metal Ca, Mg, Al, Zn
  • the corrodibility is enhanced allowing easier hydrolysis. It also tends to lower the melting point of the alloy, permitting synthesis at a lower temperature.
  • Slightly higher energy values per pound of fuel precursor can be achieved by hydrolyzing carbides of higher carbon content, such as Mn_C 3 , Cr 7 C 3 , or Cr 3 C 2 .
  • carbides especially the chromium compounds,are quite resistant to hydrolysis.
  • reactive metals such as Mg, Al, Zn, or Ca
  • chromium or vanadium do not form trichromium or trivanadium carbides
  • compounds may be formed by substituting one aluminum atom, as Cr 2 AlC or V 2 A1C which have a high potential energy value per pound. These compounds can also form solid solutions with the (Fe, Mn) 3 C system.
  • cerium or lanthanum dicarbides or se ⁇ quicarbides REC_ or RE 2 C 3 have the best potential as a fuel precursor of previously reported carbides, where
  • RE represents a rare earth metal. Similar compounds formed from Misch-metal or unseparated Rare Earth metals and carbon have a lower system cost for fuel generation. We have discovered that by alloying the
  • calcium, strontium, barium, bismuth, lead, and tin are candidates, but the alkaline earth
  • OMPI metals do not offer appreciable savings in energy.
  • solubility of smaller ions such as zinc or iron or manganese can be enhanced by co-dissolving a larger than normal ion such as barium.
  • the processes in the first group are exothermic, supplying their own reaction heat, but require prior reduction - of metal oxides to metals.
  • the most applicable method within the first group is governed by the phase diagram of the system involved; however, methods based on solid state transformations
  • Method 1C could yield pure carbide in principle, but for practical configurations, the desired product will be mixed with a metal rich phase. This condition will also be found for method ID.
  • a peritectic freezing process is the most favorable method of synthesizing the desired carbide.
  • Pure Fe 3 C is marginally unstable but may be produced by peritectic freezing at temperatures above 1050°C.
  • Fe-Mn alloys up to about 80% Mn may form carbides by peritectic freezing at temperatures which drop as the Mn content increases.
  • molten (Fe-Mn) alloy with dissolved carbon may be modified by additions of metallic calcium, aluminum, magnesium or zinc with the following results:
  • Peritectic freezing yields a trimetal carbide M 3 C whose metallic atoms consist predominantly of Fe and Mn, but with lesser amounts of low melting point metals.
  • OMPI metal/carbon ratios may commonly occur in these alloy carbide systems without changing the general behavior or advantageous properties of such systems.
  • These may conveniently be formed by partial peritectic freezing of M 3 C with equilibrium metal rich phases, then adding additional powered carbon and completing solidification followed by aging or curing at temperatures of 400-700°C.
  • Pure La 2 C 3 or Ce 2 C 3 may be produced by peritectic freezing at temperatures above 800°C.
  • Misch-metal alloy with dissolved carbon can yield E 2 C 3 by peritectic freezing above 750°C.
  • the carbides formed upon partial or total freezing plus the interstitial metal rich phase retain the reactivity toward water or steam shown by the pure lanthanide carbides or metals.
  • the energy of reduction of the metallic alloy is lower than for the pure lanthanide system equivalent to a given amount of carbon.
  • the higher rare earth carbides EC 2 may be formed congruently from the melt at extremely high temperatures, peritectically at intermediate temperature or by solid state transformation. I have found that the dicarbides EC 2 may be conveniently prepared by first forming the modified sesquicarbides, RE 2 C 3 as previously described. By mixing excess (powdered) carbon with a partially frozen peritectic mixture consisting of a liquid metal-rich phase in equilibrium with crystalline carbide, and then cooling, a 3 phase solid mass is obtained which will slowly convert to a structure containing predominantly dicarbide if maintained at elevated temperatures (400-700°C. ).
  • the metal-like carbides can be considered to be an "alloy" between excess metal and an ionic carbide where the ionic carbide would contain metal ions in a normal valence state and carbon has a nominal valence of -4 for most carbides whose structure leads to large C-C bond distances and a valence of -1 for acetylides where C-C distances below 1.3 A are found between isolated pairs of carbon atoms.
  • Metastable carbides such as Fe 3 C or Mn 3 C tend to partially revert to metal and carbon which gives a higher than expected H 2 content on hydrolysis. From 10 to 15% or more of the total carbon content may revert to free carbon.
  • the rare earth carbides on hydrolysis behave as acetylides with excess reducing agents; they may be viewed as alloys between excess rare earth and hypothetical REC 3 .
  • the hydrogen evolved by the ex ⁇ cess metal partially reduces the acetylene and partially appears as H 2 .
  • the metal-like carbides generally produce lesser amounts of various other hydrocarbon molecules as a result of secondary reactions of intermediate or primary hydrolysis products.
  • step 3 Mixing said carbon-saturated molten metal with excess finely divided coke or char and maintaining such mixture at temperatures above the freezing point of the molten metal until a major fraction of the mixture has been converted to carbide compounds. 4. Removing the carbide material formed in step 3, along with various amounts of molten metal-rich solution and optionally some unconverted carbon in fine particulate form and holding said mixture at some lower temperature at which the remaining molten material solidifies, or alternatively becomes so viscous that migration of carbon or carbide particles is inhibited, until further conversion processes to form carbides are essentially complete.
  • Fig. 1 is a schematic representa ⁇ tion or flow diagram of a process for producing solid metallic carbides which can be converted, by chemical reaction, to fuel gases or liquids.
  • Raw materials for the process are raw carbonaceous materials, and one or more metal oxides or hydroxides which may be largely supplied as recycled material from the gas generation stage of the process.
  • the raw carbonaceous material is reduced in particle size in crusher 16, to dimensions which will at least pass a 10 mesh screen. All of the entering carbonaceous material is pyrolyzed to remove a large portion of its constituent volatiles, although conditions in pyrolyzer 18 need not be controlled to achieve complete coking or devolatization. Thus, pyrolysis is advantageously accomplished below normal coking temperatures of about 2000°F. Rather, the raw, crushed carbonaceous materials are subjected only to a pyrolyzing temperature of about 750-1250°F., preferably 900-1100°F. for a time sufficient to remove from 80 to 95% by weight of the volatiles therein.
  • Partial vacuum for example, at pressures in the range pf 2 to 8 psia
  • pyrolyzing temperature be sufficiently high that the partial pressure of water be kept sufficiently low to convert to oxides the major proportion of dehydratable
  • ____ OMPI starting material hydroxides in subsequent steps of the process.
  • Water driven off in pyrolyzer 18 can be reintroduced into the process as steam.
  • Volatile gases with fuel value may be used to supply over-all process heat by combustion in the plant, mixed with hydrolytic process gas to augment output, or marketed as a separate fuel gas.
  • a portion of the pyrolyzed carbonaceous material continues on to the mixer 20 for admixture with the metallic oxide/hydroxide materials.
  • the balance of the pyrolyzed carbonaceous material is directed to synthesizer 26 where it is used to form the solid mixed metallic carbide hydrocarbon gas precursor elements.
  • the metallic oxide/hydroxide raw materials are passed directly to one or more crushers 12, 14 where they are reduced in particle size for ease of handling and to enhance subsequent processing, and then to mixer 20.
  • the particle size of the crushed metal compounds is by no means critical, it is preferred that they pass a 20 mesh screen.
  • mixer 20 the ambient temperature metal oxide/hydroxide materials are thoroughly mixed, as by tumbling, with the relatively hot (800-900°F.) pyrolyzed carbonaceous material. If spent fuel precursors from which the fuel gas has already been generated are recycled, they would be crushed, if necessary, and then metered from supply 15 in appropriate proportions directly into mixer 20.
  • OMPI mixer 20 are conveyed through metering device 21 into reactor 22 where they are reduced to liquid metal at the reactor temperature of about 1400-2400°F.
  • a considerable quantity of heat must be supplied either by radiant energy or chamber walls heated by indirect combustion or by concurrent combustion of excess carbon inside the chamber as in a blast furnace.
  • the time of reaction will depend on heat transfer limita ⁇ tions but may be expected to require several hours for commercial size reduction chambers.
  • the metal oxides/hydroxides are reduced to free metal according to the reactions:
  • Any by-product carbon monoxide gas generated in reactor 22 from the reduction of the metallic compounds or from the residual volatiles in the carbonaceous material is directed to a scrubber (not shown) and then marketed as a fuel gas or used to supply process heat.
  • the composition exiting from reactor 22 is molten and consists primarily of liquid metal with dissolved carbon and an insoluble slag or impurity layer which may be separately drained and disposed.
  • the metallic layer then enters a heated blender/reservoir 24 which has the capability to store the molten composition and via meter 25 to control the quantity of composition which passes directly to synthesizer 26.
  • the balance of the molten composition is directed to a converter 28 which is maintained at approximately 1000°F. minimum temperature.
  • the composition is modified as necessary, with additional quantities of carbon from supply 29 or liquid metal from supply 27.
  • the material flow to synthesizer 26 can be controlled and stabilized in order that the composition of the mixed metallic carbides produced in the process can be held at selected levels.
  • synthesizer 26 Three separate materials flow streams enter synthesizer 26 — the pyrolyzed carbonaceous material from the pyrolyzer 18, the molten composition exiting the blender/reservoir 24, and the residual molten material from converter 28. Temperatures within synthesizer 26 are maintained in the range of 1600-2400°F. so that a portion of the materials therein readily react to form mixtures of ternary metallic carbides. Dwell time in the synthesizer is about 4 to 7 hours and, nominally, about 5 hours to obtain the peritectic mixture initially required to allow further processing to yield hydrocarbon precursor compositions. By controlling the input to the synthesizer as hereinbefore described and by continuously monitoring and sampling the product composition from the synthesizer, the desired mixture of modified metallic carbides can be controlled.
  • converter 28 additional carbon is added from supply 29 to react with molten metal-rich phase or alternatively to react with intermediate carbides to form carbides of higher carbon content either through solid state diffusion processes or by transmittal through a liquid metal film acting as a solvent.
  • the bulk of the output from converter 28 consisting of the desired mixed metallic carbides is drained into a compactor 30 where the product is compressed or otherwise formed into pellets, bricks or briquettes, preferably spherical or at least non-angular in configuration, of a size which can readily be handled and transported. Typical briquette sizes are in the range 1 to 9 inches in major dimension, although the size of the compacted fuel precursor is not critical.
  • the shaped fuel precursors cool rapidly to ambient temperature and may be stored in bin 32, packed for shipment or immediately used to generate fuels. Conversion of Precursors to Fuel Products
  • the mixed metallic carbide fuel precursors can be converted to fuels by the process which is schematically depicted in Fig. 2.
  • the input supply 38 to the conversion process is the fuel precursors hereinbefore produced in the process of Fig. 1, which precursors are metered from compactor 30 or bin 32 via hopper/feeder device 40 at a predetermined rate into conversion chamber 42.
  • the mixed metallic carbide fuel precursors are sprayed or otherwise contacted with water or steam to form the
  • - URE4 OMPI volatile fuel gases and the spent mixed metallic oxides or hydroxides exiting the converter are recycled to the fuel precursor production process.
  • additives such as odorizers, may be added to the fuel gas in the conversion chamber 42.
  • the conversion chamber is maintained at a temperature in the range 250-600°F., preferably 300-450°F. In this temperature range, temperatures are high enough that most metal hydroxides will be dehydrated and low enough that unwanted vapors, such as sulfur dioxide, hydrogen sulfide, etc., can be readily removed.
  • the reaction which forms the volatile fuels is exothermic, generating substantial quantities of reaction heat and necessitating a heat exchange system 44 in the chamber 42 to capture this heat of reaction.
  • coolant water is caused to flow through heat exchanger 44 to absorb and withdraw the excess reaction heat and to control the converter temperature to the desired range.
  • the coolant water may be converted to steam which can be transported through line 47 for use elsewhere.
  • the fuel precursors are moved through chamber 42 by a screw conveyor 45 and are sprayed from above with the water by sprayers 46.
  • the water is advantageously distilled water condensed from the steam line to avoid introducing dissolved minerals into the reduction stage during recycling.
  • the gas exiting chamber 42 through line 54 is a mixture of fuel gases or volatile fuels and water vapor which can be separated by conventional techniques in scrubbers 48.
  • a series of scrubber towers is preferably provided with appropriate conventional valving means (not shown) to permit gas flow through selected scrubber towers. In this manner, the towers can be taken off line and repacked with fresh adsorbants when necessary.
  • fuel precursor feed into and spent fuel precursor removal therefrom must pass through gas sealing mechanisms.
  • the spent fuel precursor consisting now predominantly of mixed metallic oxides, is passed into a storage pit 52 where any additionally generated volatiles can be collected prior to recycling the spent carbides to mixer 20 (see Fig. 1) as fuel precursor production input.
  • the fuels pass from the chamber 42 and from the spent fuel storage pit 52 through scrubbers 48 into a compressor stage 50 wherein the gas pressure is raised to a level suitable for distribution, for example, in gas mains. Liquid fuels may be removed at this stage if desired.
  • the compressor 50 also serves - as a mixer unit wherein the fuel gas can be admixed with an inert (e.g., nitrogen, carbon dioxide) or active (e.g., carbon monoxide) diluent gas prior to distribution through mains or otherwise.
  • an inert e.g., nitrogen, carbon dioxide
  • active e.g., carbon monoxide
  • Impurities present in the raw feed material may be removed at special points in the process by one
  • Silica, phosphorus, sulfur or other acidic impurities arising primarily from the carbonaceous input may be removed as a dross or slag in the reactor 22 being generally immiscible and floating on liquid metal layer. Additions of lime or magnesia in amount sufficient to combine with the acidic impurities may aid in separation of said impurities. Basic impurities such as alumina would usually combine with acidic impurities normally present in excess, but if necessary controlled additions of silica can be made to effect removal. 2. Impurities introduced into the synthesizer
  • Mixer 20 is charged with approximately 497 lb of mixed metal oxides (FeO and MnO) containing
  • the soft metal is preferably magnesium or magnesium zinc alloy and is present in the synthesizer chamber
  • Example 2 For the modified rare earth carbide system we have the following preferred compositions. Operation of the pyrolyzer would be essentially the same as for the Fe, Mn carbide system described in Example 1. Mixer 20 is charged with approximately
  • Synthesizer 26 is charged with approximately 280 lb of liquid metal from the reactor 22 with about 48 lb of carbon (total dissolved plus added carbon) to permit ultimate conversion to REC collapse and sufficient soft metal to provide an interstitial liquid metal film to retain fluidity to the reacting mixture and promote diffusion of the metallic atoms.
  • the soft metal is preferably magnesium or magnesium-lead- barium and/or zinc alloy and is present in the synthesizer chamber 26 in an amount equal to 5 to 40% by weight of the rare earth metal content. A majority of the soft metal is retained in synthesizer 26 and converter 28.
  • approximately 328 lb of mixed metallic carbides are reacted with about 54 lb of water or steam to provide approximately 54 lb of combined fuels plus hydrogen.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Catalysts (AREA)

Abstract

Procédé de production de précurseurs de combustible solide comprenant des carbures métalliques mélangés pouvant être agglomérés pour l'expédition ou le stockage en (32). Les agglomérés peuvent être convertis en combustibles gazeux ou liquides au moyen d'une réaction avec de l'eau ou de la vapeur. Les précurseurs peuvent en outre contenir des quantités minimes de métaux libres, de carbone n'ayant pas réagi ou d'autres impuretés. Les précurseurs de combustible contenant du carbure métallique sont préparés dans une série d'étapes comprenant la réduction d'un métal contenant des matières premières avec du carbone dans un réacteur (22) pour former un métal en fusion saturé par le carbone, lequel métal saturé est mélangé successivement à un excédant de charbon ou de charbon de bois pour former des carbures métalliques dans les récipients (26) et (28).
PCT/US1981/001584 1981-11-25 1981-11-25 Procedes de production de combustible a partir de materiaux solides Ceased WO1983001949A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU80062/82A AU8006282A (en) 1981-11-25 1981-11-25 Methods of producing fuels from solid materials
PCT/US1981/001584 WO1983001949A1 (fr) 1981-11-25 1981-11-25 Procedes de production de combustible a partir de materiaux solides
EP82900290A EP0094936A1 (fr) 1981-11-25 1981-11-25 Procedes de production de combustible a partir de materiaux solides

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1981/001584 WO1983001949A1 (fr) 1981-11-25 1981-11-25 Procedes de production de combustible a partir de materiaux solides

Publications (1)

Publication Number Publication Date
WO1983001949A1 true WO1983001949A1 (fr) 1983-06-09

Family

ID=22161530

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1981/001584 Ceased WO1983001949A1 (fr) 1981-11-25 1981-11-25 Procedes de production de combustible a partir de materiaux solides

Country Status (3)

Country Link
EP (1) EP0094936A1 (fr)
AU (1) AU8006282A (fr)
WO (1) WO1983001949A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4009219A (en) * 1975-04-28 1977-02-22 Tamers Murry A Total synthesis of benzene from non-hydrocarbon materials
US4137295A (en) * 1977-04-20 1979-01-30 Tamers Murry A Carbide production using molten metals as heat source
US4184852A (en) * 1975-12-22 1980-01-22 Russ James J Method for making methane from metal carbides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4009219A (en) * 1975-04-28 1977-02-22 Tamers Murry A Total synthesis of benzene from non-hydrocarbon materials
US4184852A (en) * 1975-12-22 1980-01-22 Russ James J Method for making methane from metal carbides
US4137295A (en) * 1977-04-20 1979-01-30 Tamers Murry A Carbide production using molten metals as heat source

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KOSOLAPOVA, Carbides - Properties, Production, and Applications, 1971, Plenum Press, New York-London, pages 41, 47-50, 74, 245, 246. *

Also Published As

Publication number Publication date
AU8006282A (en) 1983-06-17
EP0094936A1 (fr) 1983-11-30

Similar Documents

Publication Publication Date Title
US4310334A (en) Methods of producing fuels from solid materials
US6663681B2 (en) Method for the production of hydrogen and applications thereof
US4558027A (en) Catalysts for carbon and coal gasification
US6685754B2 (en) Method for the production of hydrogen-containing gaseous mixtures
US4704136A (en) Sulfate reduction process useful in coal gasification
US3607157A (en) Synthesis gas from petroleum coke
US4128624A (en) Method for introducing carbon into evacuated or pressurized reaction vessels and reaction products therefrom
ZA200306631B (en) Method for the production of hydrogen and applications thereof.
CN85108811A (zh) 矿物熔炼还原工艺和设备
CA1309589C (fr) Methode de production d'un gaz propre contenant de l'oxyde de carbone et de l'hydrogene
AU2002254101B2 (en) Method for the production of hydrogen and applications thereof
AU2002254101A1 (en) Method for the production of hydrogen and applications thereof
US4692172A (en) Coal gasification process
US4184852A (en) Method for making methane from metal carbides
Huo et al. Efficient reduction of electric arc furnace dust by CO/H2 derived from waste biomass: Biomass gasification, zinc removal kinetics and mechanism
CA1079476A (fr) Production de monoxyde de carbone a partir de substances carbonees et d'oxyde de zinc
CA1158016A (fr) Methodes de production de combustible a partir de substances solides
WO1983001949A1 (fr) Procedes de production de combustible a partir de materiaux solides
US2437815A (en) Process of magnesium production
EP0004456A1 (fr) Méthanisation de monoxyde de carbone sans séparation préalable des gaz inertes
US1786386A (en) Extraction of tin from ores or materials containing tin
US2928721A (en) Method for producing thorium tetrachloride
RU2233897C2 (ru) Способ получения алюминия и устройство для его осуществления
JPS62218524A (ja) 鉄鉱石、鉄鋼製造副生成物および排出物、又はその他の鉄酸化物含有物質から鉄を回収する方法
US2992891A (en) Treatment of uranium containing carbonaceous materials

Legal Events

Date Code Title Description
AK Designated states

Designated state(s): AU JP SU

AL Designated countries for regional patents

Designated state(s): AT CH DE FR GB LU NL SE