US3140241A - Processes for producing carbonaceous materials - Google Patents

Processes for producing carbonaceous materials Download PDF

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US3140241A
US3140241A US821137A US82113759A US3140241A US 3140241 A US3140241 A US 3140241A US 821137 A US821137 A US 821137A US 82113759 A US82113759 A US 82113759A US 3140241 A US3140241 A US 3140241A
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temperature
coal
shapes
oxygen
heating
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Work Josiah
Robert T Joseph
John H Blake
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FMC Corp
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FMC Corp
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Priority to NL130819D priority Critical patent/NL130819C/xx
Priority to NL252579D priority patent/NL252579A/xx
Application filed by FMC Corp filed Critical FMC Corp
Priority to US821137A priority patent/US3140241A/en
Priority to FR829685A priority patent/FR1259299A/fr
Priority to LU38797D priority patent/LU38797A1/xx
Priority to DE19601421258 priority patent/DE1421258C/de
Priority to BE591859A priority patent/BE591859A/fr
Priority to AT188762A priority patent/AT244901B/de
Priority to GB21162/60A priority patent/GB926213A/en
Priority to CS388660A priority patent/CS155126B2/cs
Priority to SE9785/63A priority patent/SE308502B/xx
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L9/00—Treating solid fuels to improve their combustion
    • C10L9/02—Treating solid fuels to improve their combustion by chemical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B49/00—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
    • C10B49/02—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge
    • C10B49/04—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge while moving the solid material to be treated
    • C10B49/08—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge while moving the solid material to be treated in dispersed form
    • C10B49/10—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge while moving the solid material to be treated in dispersed form according to the "fluidised bed" technique
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/08—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form in the form of briquettes, lumps and the like

Definitions

  • This invention relates to processes for producing physically strong, carbonaceous material from coals of any rank from and including anthracite to lignite, including such carbonaceous material which is chemically reactive.
  • rank is used herein in the sense commonly used in the coal industry, namely, to distinguish coals of different characteristics.
  • the major source of metallurgical carbon has long been the coke produced by the various high-temperature coke oven processes. Smelters of iron, phosphorus, zinc, lead, tin, silicon and others are users of such coke. These ovens require increasingly expensive and sparsely located coking coals. Marketable supplies of coke breeze and similar by-product sizes of coke formerly available from captive coke ovens are dwindling because the sintering process has enabled producers of such coke to utilize these materials (breeze and other sizes of coke) to advantage in their own operations.
  • the by-product coke oven presents undesirable operational characteristics in that it requires extensive equipment for blending and sizing coals, entailing difficulties and a high degree of maintenance.
  • varying degrees of agglomeration adversely affect the process.
  • the temperature within the coke ovens (whether they are of the by-product, bee-hive or other varieties) varies over the period of reaction time as well as throughout the oven. This results in products whose characteristics difier widely from charge to charge as Well as within a given charge.
  • the period of time required for reaction is measured in terms of many hours. In by-product coke ovens, this period may range from 16 to 48 hours.
  • metallurgical cokes produced in high temperature ovens have relatively low compressive strength (in the region of 500 to 800 pounds per square inch) and low abrasion resistance (roughly 50% to 70% .as determined by ASTM tumbler index).
  • Thees products also have a low density (caused, no doubt, by rapid and irregular heating rates) and low reactivity (caused by excessive exposure to elevated temperatures).
  • This controlled chemical reactivity is manifest by unexpectedly high reaction rates of this product with gases such as oxygen, steam, carbon dioxide, chlorine, etc.
  • a product herein called calcinate
  • FIG. 1 shows, for purpose of exemplification and to facilitate a better understanding of this invention, a box diagram of the sequence of steps of the process resulting in the compressed coke shapes, and
  • FIG. 2 is a flow sheet showing a preferred arrangement of equipment for carrying out such process.
  • chemically reactive carbonaceous material is produced from coal of all ranks from lignite through anthracite by a procedure involving the following stages:
  • coal if not already finely divided, is ground, for example, in a hammer mill, to a particle size small enough to be readily fluidized.
  • This step must be carried out within a certain temperature range which varies from coal to coal, which is dependent, in part at least, on the time the parent coal is subjected to such temperatures, and which is limited by the distinguishable phenomena hereinafter set forth.
  • the upper temperature limit regardless of time, is that temperature above which the distilling vapors form tar when condensed.
  • the lower temperature limit is that temperature at which contained moisture is evolved from the parent coals.
  • the moisture content of the parent coal is reduced to limits found necessary for proper operation of the carbonizing stage, usually to 2% or less;
  • the coking and caking tendencies of the parent coals are destroyed by a small addition and/ or recombination of oxygen, derived from the parent coal or the atmosphere in which this stage is conducted, to form carboxylic groups as are found in humic acids.
  • This stage which results primarily in effective catalyzing of the coal, is hereinafter and in FIG. 1, referred to as the catalyzing Stage.
  • the products are referred to as Catalyzed Coal.
  • this 3rd stage is to carry on that type of polymerization which is promoted and directed by the catalysts (presumed to be formed in the catalyzing stage) in such a manner that a substantial portion of the parent coal constituents are retained in a form of the parent coal structure while, at the same time, an amount of these constituents (predicated on the predetermined environment of this stage) is evolved as vapors which may be condensed to form tars and gases for use in subsequent demands of the process.
  • This stage effects a reduction in what is conventionally called the volatile combustible matter (VCM) in the parent coal.
  • VCM volatile combustible matter
  • the necessary heating rates and residence times may be achieved by introducing the catalyzed coal into a fluid bed reactor where the temperature rise is effected practically instantaneously, and where the residence time of the catalyzed coal in this environment is controlled by the desired physical and chemical properties of the product.
  • longer residence times, for a given temperature produce higher densities but lower reactivities.
  • Higher temperatures for a given, but shorter, residence time produces higher reactivities but lower densities.
  • the properties imparted to the product char from this stage bear on and reflect directly in the products from the succeeding stages.
  • the heat for this stage is best obtained from combustion of such a portion of the catalyzed coal particles as is needed to supply the heat demands of the reaction, and control of this combustion is effected by admitting only that amount of oxygen (preferably as air) as will maintain this prescribed level of combustion.
  • this stage is referred to as the carbonizing Stage and the solid product from this stage is referred to as Char.
  • this treatment may or may not be employed.
  • the char is subjected, preferably immediately, to further heating to reduce the remaining volatile content in the char to a 3% maximum.
  • This when effected in a fluidized bed with combustion of a portion of the char to provide the desired temperature, must be done in an atmosphere containing no more of such active gases as will produce the heat and no more carbon dioxide than will be produced by the combustion of that part of the char particles necessary to supply the heat demanded by this reaction.
  • calcined particles are pyrophoric and should be handled in transport by procedures that will prevent undesirable oxidation.
  • this stage is referred to as the Calcining Stage and the product from this stage is referred to as Hot Calcinate.
  • the hot calcinate is immediately and rapidly cooled to a temperature at which subsequent blending with the binder is effected, or to below 400 F., or to the temperature at which the calcinate is to be used when the calcinate is to be utilized as such. If used at a lower temperature, such cooling may be effected by introducing the hot calcinate into a fluid bed maintained at the temperature to which the calcinate is to be cooled, or accomplishing this stepwise by use of two or more fluid beds if heat economy so dictates. The effect of such cooling is to reduce loss of product by oxidation upon contact with air and, at the same time, to maintain the structure of carbon surface by preventing this oxidation.
  • this stage is referred to as the Cooling Stage, and the product from this stage is referred to as the Calcinate.
  • the chemically reactive carbonaceous material or calcinate thus produced may be utilized as such, for example, as raw material for water gas or other gas reactions in the place of coal or coke, or for effecting the reduction of ores as in sintered iron processes. It is remarkably strong, abrasive-resistant, homogeneous, of
  • calcined particles are pyrophoric and should be handled in transport by procedures that will prevent undesirable oxidation.
  • the calcinate is mixed with a binder (preferably the tar produced in carbonizing the parent coal after this tar has been treated by heat and air-blown to a prescribed softening point hereinafter disclosed) in such a manner that all the calcinate particles are surfacecoated with the binder, a minimum of absorption occurs, and the calcinate and binder are so intermingled that subsequent processing causes co-polymerization of the binder and calcinate.
  • a binder preferably the tar produced in carbonizing the parent coal after this tar has been treated by heat and air-blown to a prescribed softening point hereinafter disclosed
  • Blending Stage This stage, which effects the blending of binder and calcinate, is hereinafter and in FIG. I referred to as the Blending Stage and the product is referred to as the Blended Material.
  • the blended material is subjected to a compacting operation to form any shape demanded (as by briquetting, extrusion or any similar process) wherein the applied pressure on the blended mass is of such magnitude that the shape, when freed from the mold or die, will retain its form and be capable of withstanding abuse and handling at normal and elevated temperatures.
  • This product is pyrophoric and unstable and consequently should not be stored.
  • Green Shapes briquettes, extrusions, etc.
  • the green shapes from the forming stage are subjected to further processing by heating in an oxygencontaining atmosphere until co-polymerization of the binder and calcinate have been completed.
  • the residence time and temperature are interrelated. This curing can be accomplished at room temperature in a matter of days, or at elevated temperatures, hereinafter given, in a matter of 60 to minutes. Longer times at elevated temperatures affect the strength adversely. Accelerators can be used to reduce the time.
  • the minimum quantity of oxygen required in the curing atmosphere is 2.5% by volume; more can be used, if desired, up to a maximum of 21% under the conditions hereinafter set forth.
  • this curing stage is to promote maximum polymerization, presumably by peroxide or hydroperoxide catalyzation, between the binder and calcinate and thereby prevent formation of coke from the binder alone.
  • This co-polymerization apparently acts to decrease the vapor pressure of the binder-calcinate system to such a level that, in the subsequent stage, coke is' formed from the co-polymers preferentially to distillation of the high vapor pressure components of the original binder.
  • This product is pyrophoric.
  • this stage is referred to as the Curing Stage and the product from this stage is referred to as Cured Shapes (briquettes, extrusions, etc.). 7
  • a secondary detrimental effect of such side reactions is the partial consumption of individual shapes causing undesirable non-uniformity of size and surface.
  • This treatment must take place at a temperature sufficient to reduce the volatile combustible content of the final product to 3.0% or less.
  • the time necessary to accomplish these aforementioned ends is dependent on the temperature andis the time necessary for the coking reaction to reach that stage of completion at which the coke shapes have the desired strength.
  • the heat for this reaction is preferably supplied by direct contact with hot inert gases (for example, carbon monoxide or hydrocarbon gases produced in earlier stages) as in a shaft or on a moving grate.
  • hot inert gases for example, carbon monoxide or hydrocarbon gases produced in earlier stages
  • any other means of raising these cured shapes to the temperatures dictated by the specifications for the final product may be used.
  • Such means may be direct or indirect, as by gas contact or by radiation from externally heated walls, or by direct radiation sources.
  • the shapes after having been subjected to the hightemperature treatment, must be cooled, preferably but not necessarily in the same apparatus, but in any case in an atmosphere free from reactive gases, as previously described, to such a temperature that harmful and yieldconsuming reactions with reactive gases do not take place.
  • this stage is referred to as the Coking Stage and the product from this stage is referred to as Coke Shapes (briquettes, extrusions, etc.).
  • These shapes are exceptionally uniform in that the product, from boundary to boundary, is a homogeneous entity, as indicated visually by optical microscopy and chemically by the uniform, homogeneous consumption of the shape from all dimension in any reactive medium.
  • These shapes have a high strength (denoted by resistance to compressive pressures on a 1%" diameter x high cylindrical form) of at least 3000 pounds, a high bulk density, exceptional resistance to abrasion, and unusually high surface area for such high strength.
  • the chemical reactivity depends on the process conditions. Thus, coke shapes of desired chemical reactivity, many times that of high-temperature coke, can be produced. Coke shapes as reactive or more chemically reactive than highly active coconut charcoal have been produced. By coking at elevated temperatures, hereinafter disclosed, coke shapes of high strength and low chemical reactivity result.
  • the coal if not already of the required finely divided size, may be ground by any standard grinding and sizing technique to produce a natural distribution particle size, substantially all of which passes a No. 8 mesh screen and at least 95% of which is retained on a No. 325 mesh screen and with a minimum quantity of fines of a size which would escape from the cyclone of the fluidizing bed reactors. This is reading accomplished by grinding in a hammer mill.
  • a volume of oxygen at or near the lower limit of this range is employed, e.g., from 1% to 8% by volume; for coking coals, a volume of oxygen in the upper part of this range is used, e.g., from 8% to 20% by volume.
  • concentration of oxygen used will be that optimum quantity of oxygen which will add to the coal matrix and thus provide a source of oxygen for catalyst formation and inhibition of agglomerating tendencies if present, without causing an uncontrolled combustion in this catalyzing stage or in the later stages of the process.
  • the fluid bed is normally maintained at a temperature of 250 F. to 500 F.; for coal possessing caking and coking characteristics, in order to promote the secondary effect of destroying these characteristics, the bed is maintained at a temperature of 500 F. to 800 F.
  • the maximum of the range is that point in temperature at which hydrocarbon vapors, the tar precursors, i.e., tarforming vapors, begin to be evolved.
  • the lower limit is that temperature necessary to reduce the moisture con- 8 tent to 2% or less, or, in the case of coal with less than 2% moisture, that temperature at which oxygen can be added to the coal matrix.
  • the parent coal may be introduced into a cold fluid bed and subjected to a gradual rise in temperature to the range indicated.
  • the parent coal is introduced continuously into a fluid bed maintained at the desired temperature at which destructive deformation of the coal particles does not take place and wherein the heating rate will be of shock or instantaneous magnitude, for 1 second or less.
  • the coal particles When heating the coal particles under fluidizing conditions, the coal particles should remain in the fluid bed for an average residence time of at least 5 minutes, and preferably from 5 minutes to 3 hours. This catalyzing may be accomplished in times as low as 10 minutes, or as high as minutes, Without the occurrence of deleterious effects on the final product.
  • the temperature of catalyzation within the ranges given, bears an inverse relationship to the residence time. In catalyzation of non-coking coals at temperatures in the lower portion of the range of 250 F. to 500 F., the times should be in the upper portion of the residence range. On the otherhand, when operating at the higher temperatures, near 500 F., the residence time should be in the lower portion of this time range.
  • the fluidizing medium desirably steam or flue gas diluted with air or oxygen, is introduced at a pressure of from 2 to 30 p.s.i.g.
  • the fluidizing medium is introduced at a velocity to give the desired boiling bed conditions, e.g., from about 0.5 to 2 feet per second superficial velocity.
  • Heating of the finely divided coal particles in the fluidized bed may be effected by burning a small portion of the coal, by sensible heat introduced in the fluidizing medium, or by indirect heat exchange.
  • the finely divided coal particles may be subjected to heating in a dispersed phase, i.e. dispersed in a suitable gaseous medium (e.g., flue gas, nitrogen, or carbon dioxide containing oxygen, within the limits heretofore prescribed) of suflicient velocity to maintain the particles in the dispersed phase rather than in the dense phase, as in a fluidized bed.
  • a suitable gaseous medium e.g., flue gas, nitrogen, or carbon dioxide containing oxygen, within the limits heretofore prescribed
  • THE CARBONIZING STAGE Carbonization is carried out by subjecting the catalyzed coal particles to a further heat-treatment in a fluidized bed where the heat requirements are supplied, preferably, by the oxidation of a limited amount of the catalyzed coal or of the hydrocarbon vapors derived therefrom.
  • This oxidation is controlled by the admission of only that 9 amount of oxygen necessary to produce the desired temperature level.
  • This oxygen is admitted to the bed in the form of air as a component of the fluidizing medium, the remainder of which may be steam, nitrogen, flue gas, carbon dioxide, carbon monoxide, or any gas which is not reactive with the catalyzed coal in this stage.
  • heat may be supplied externally by use of heat exchangers.
  • the catalyzed coal particles may be heated under conditions:
  • Optimum conditions of the carbonizing stage will vary from coal to coal and may be determined for each rank of coal processed by prior laboratory evaluation in benchscale apparatus.
  • the lower limit of temperature is that temperature at which the activated coal begins to evolve tar forming vapors in quantity and this temperature is the same as the upper limit of the catalyzing stage for any given coal, i.e. 800 F. for coking coals, and 500 F. for non-coking coals.
  • the upper limit of temperature is that temperature above which the expanding coal particles form cracks, fissures and bubbles to such an extent that retraction to the size and shape of the original coal particle cannot occur.
  • This upper temperature limit is approximately ll50-1200 F.
  • the oxygen-containing fluidizing gas should enter the bed at a temperature not much below the temperature of the fluidized bed and not more than 20 F. above this temperature; if this fiuidizing medium is introduced at a much lower'temperature than the bed, more of the catalyzed coal and hydrocarbon vapors will have to be burned in order to supply the heat necessary to raise the fluidizing medium to bed temperature, thereby reducing product yields. If oxygen-containing fluidizing gases enter the bed at a temperature of more than 20 F. above the temperature of the bed, weak non-uniform char results.
  • the fluidizing medium is introduced at such superficial velocities as will effect the desired fluidization pattern, usually 0.5 to 2 feet per second and, desirably, at pressures consistent with the smooth operation of the Whole process, e.g., 2 to 30 p.s.i.g., preferably about 5 p.s.i.g.
  • the material in the bed is maintained at the aforementioned bed temperature for to 60 minutes.
  • the residence time at this point is a source of control of the chemical reactivity and other characteristics of the finalcalcinate or massive shape and is determined by the specification set for the final calcinate or massive shape derived from the calcinate.
  • sufficient binder is produced to supply the needs of massive formation. With anthracites such is not the case; the carbonization step partially de-gases and conditions the anthracite structure for further treatment in succeeding stages of the process.
  • the carbonization may be carried out as a continuation of a batch-operated catalyzing step wherein, particles being catalyzed having been held at the desired temperature for the specified residence time, the temperature of the bed is raised as rapidly as the reaction of the oxygen content of the fluidizing medium with the bed will achieve carbonization temperatures.
  • this carbonization may be carried out by continuously feeding the catalyzed coal from the catalyzing stage directly into a '10 fluid bed maintained at the carbonizing temperatures as previously described. In this case the heat transfer rates within the bed are of such a magnitude as to effect instantaneous shock heating of the particles.
  • That controlled portion of the coal constituents which is evolved as gas and vapor from the coal particles may be processed to produce tars and gas for use in the process.
  • the vapors may be cooled by direct contact with a recycling water spray to such a temperature that about of the vapors are condensed to tar.
  • the uncondensed 20% goes forward through conventional heat exchangers and is cooled to about 40 F. above the cooling medium temperature which circulates indirectly over the heat exchange surfaces at which temperature some further condensation takes place.
  • the two condensates are combined to give the total wet tar which is allowed to settle, and the water is decanted to leave a decanted tar of about 4%6% moisture content.
  • the gas and vapor stream may be cooled by direct spray, or, conventionally, through indirect heat exchangers to such temperatures as will totally condense the tar precursors to tar and allow only the normally non-condensable gases, such as methane, etc., to leave the heat exchangers. This results in a total condensate, not separate fractions. This total condensate is then decanted in the manner heretofore described.
  • Blowing the decanted tars so formed simultaneously dehydrates the tar to a water content of 0.5% and increases the tar viscosity to the desired softening point.
  • a softening point within the range of to 225 F. preferably to F. (ASTM Ring and Ball) is satisfactory for use as the binder.
  • This blowing is accomplished by the injection of air through a suitable sparger into the decanted tar.
  • This tar is maintained at a temperature above the condensation temperature of the steam, but below that point at which distillation of the tar light ends exceeds approximately 5%.
  • the retained light ends are converted to binder of proper viscosity during the blowing treatment.
  • This viscosity increase may be accomplished by incorporating catalysts into the tar after dehydration.
  • Suitable catalysts are organic peroxides, such as benzoyl peroxide, inorganic catalysts such as sulfuric acid, boron trifluoride or its complexes, aluminum chloride, etc.
  • the usable catalyst concentration may vary from 0.1% to 2% depending on the tar, the catalysts and the viscosity range desired.
  • the residence times of the char in this stage are dictated by the specification of the final product and are more or less dependent on the operating temperature. At minimum temperature, sufficient residence time to reduce the volatile combustible matter to 3% is required. Practically, this limit is 10 minutes at about 1400 to 1500 F. and should. not be less than 7 minutes even at 1800" F.
  • the fiuidizing atmosphere necessary in this stage should be free of reactive gases such as carbon dioxide or steam. Oxygen can be tolerated only in such an amount as is demanded by that oxidation rateof the char necessary to supply the heat demands of this stage. This oxygen is most practically obtained from air introduced as part of the otherwise chemically inert fiuidizing medium, and the concentration of air for this purpose in these entering gases shall not exceed 70%.
  • the remaining components of the fiuidizing medium may be carbon monoxide, hydrogen, nitrogen and flue gas in which carbon dioxide and water have been reduced to carbon monoxide and hydrogen by. previously passing the flue gas over a bed of hot carbon, or otherwise.
  • This fluidizing medium should be introduced at such pressures as are consistent with smooth operation of the fluidization process; a range from 0 to 30 p.s.i.g., preferably about 2 p.s.i.g., is satisfactory.
  • the velocity of this medium should be consistent with a proper fiuidizing pattern, or the same as in the carbonization stage, e.g., 0.5 to 2 ft. per second.
  • the heating may be accomplished as a continuation of the catalyzing and carbonizing stages, in the same batch-operated fluidized bed reactor, by raising the temperature of the bed to the desired calcining range, and holdingthe bed at that range until calcination has been completed.
  • the hot char may be introduced continuously and directly to a fluidized bed operating at the specified calcining temperature.
  • the rate of heat transfer in the fluid bed is of such magnitude as to eifect shock or instantaneous heating of the char to calcining temperature.
  • the calcinate produced by observing the conditions hereinabove described has the essential structure and apparent density of the parent coal particles.
  • the calcinate must be cooled rapidly and immediately to prevent loss of reactivity.
  • This cooling desirably, is effected in one or more fluidized beds, preferably two, in which the fiuidizing medium also serves as the cooling medium and in which the heat transfer rate is of such magnitude as to effect instantaneous cooling.
  • Suitable cooling media are flue gas, nitrogen, or carbon monoxide, introduced at a temperature to effect the desired cooling and at a velocity to effect the desired fluidization. The velocity may be substantially the same as that employed during the carbonization of calcination treatments. Cooling atmospheres containing appreciable amounts of oxygen, water vapor or carbon dioxide should be avoided because, in view of the highly reactive nature of the calcined char, such atmospheres may result in deleterious effects on the calcinate.
  • the calcinate is employed in producing massive shapes, it is cooled 'to a temperature approximately 30 to 60 F., preferably about 50 F. above the softening point (previously described) of the bituminous binder employed in the forming operation and used without appreciable time delay or exposure to air.
  • the calcinate When producing calcinates for use as such, the calcinate must be cooled to approximately room temperature for storage or transport unless immediately used in high-temperature applications. This calcinate is pyrophoric; hence, if stored, it should be stored in a nonexidizing atmosphere so that it will not catch fire.
  • the highly reactive calcinate In order to produce massive shapes such as briquettes, extrusions, castings, etc., the highly reactive calcinate must be cooled to the proper temperature, 30 to 60 F. above the ASTM Ring and Ball softening point (100 to 225 F.) of the binder employed.
  • the calcinate is mixed with the prepared binder, which is introduced at the proper mixing temperature, as heretofore specified, in proportions of from %90% calcinate to 25%l0% binder. The percentages are based on the'weight of the total mix.
  • the optimum ratio for dry calcinate to binder is determined by laboratory tests to give the strongest prodnot consistent with high yields. If too much binder is used, the unneeded portion will distill out; if too little is used, the shapes will disintegrate in curing and coking, with attendant high losses due to the production of fines.
  • Preferred binders are coal tar pitch or pitches produced by the condensation of tars from the gases evolved during the carbonization and subsequent dehydration and oxidation of the resultant tar to produce pitches having a softening point of from to 225 F. (ASTM Ring and Ball as described). High-temperature or low-temperature coal tar pitches are satisfactory.
  • Formingv to shapes can be carried out in any conventional briquetting or pelleting equipment to produce briquettes, or pellets of any desired shape.
  • the briquetting equipment may be molds or rolls in which the mixture is subjected to pressure.
  • extrusion equipment may be used to extrude the mixture in the form of rods of any prescribed cross-section, and the rods may be cut into desired lengths to produce the shapes required.
  • Surface-tension pelletizing equipment can, of course, be used.
  • the size and form of the shapes will be dictated by THE CURING STAGE
  • the shapes so formed from this calcinate and binder blend are pyrophoric and unstable and cannot be stored in bulk. They are moved directly to the curing stage wherein the co-polymerization is initiated and sustained by subjecting the green shapes to treatment with, or without, heat in an atmosphere containing from 2.5% to 21% oxygen.
  • the composition of this atmosphere may be achieved by use of 100% air at low temperatures and low bed heights or by dilution of the air with gases (e.g., carbon monoxide, nitrogen, flue gas containing little or no water vapor, or carbon dioxide) which are inert to the shapes and to the volatile hydrocarbonaceous components of that portion of the binder which is substantially unreacted.
  • gases e.g., carbon monoxide, nitrogen, flue gas containing little or no water vapor, or carbon dioxide
  • thisco-polymerization is achieved at the maximum reaction temperature consistent with the amount and nature of the binder and yet below the ignition point of the volatile hydrocarbonaceous components of the binder which may exist in combustible concentrations (outside the massive shape).
  • the temperature must not exceed 50 F. below the coking point of the binder as determined in the ASTM distillation by that point at which the coke begins to appear on the side of the distillation flask.
  • Such coking of the binder must be avoided since that'quantityof binder which forms coke during curing reduces, directly, the amount of co-polymerization of the binder and calcinate'.
  • These co-polymers form the' homogeneous precursors of the chemically uniform, physically strong, coke briquettes.
  • Curing has been effected at room temperature in 100% air (20% oxygen) by holding the shapes under such conditions for 4 days with the shapes so distributed that the heat generated is readily dissipated.
  • Curing is practically and preferably accomplished by subjecting the. green shapes to an atmosphere of 2.5 21% by volume of oxygen at maximum temperature (450-500 F.) for, 90 to 180 minutes, preferably about 2 hours.
  • the curing conditions that must be maintained for an acceptable product are a function of oxygen concentration in the curing atmosphere, temperature of the curing environment, thickness or heightof the bed of massive shapes, and the rate at which heat is introduced and removed from the bed. Oxygen is needed in this stage as the catalyst or catalytic raw material. If the green shapes are subjected to temperatures above the softening point of the unreacted binder in concentrations o'fbxyg'e'n below 2.5%, disintegration of the shapes takes place at an extremely rapid rate.
  • This catalytic effect of oxygen may be enhanced, if so desired, by the addition of other catalysts during the 14 curing process.
  • Such catalysts may be incorporated in the green shapes before curing. Such incorporation may be made in gaseous, solution or solid form during blending, or in gaseous or solution form in the curing atmosphere.
  • Suitable catalysts are boron trifluoride and its complexes, aluminum chloride, hydrogen peroxide,
  • phosphoric acid etc.
  • the amount of such catalyst employed may be from 0.1% to 5% based on the weight of the shapes.
  • Maximum or near maximum strengths result, for example, with the boron trifluoride complexes and aluminum chloride in about 60 minutes curing time. In the case of hydrogen peroxide or phosphoric acid, minutes curing time gives maximum strength briquettes.
  • the velocity of the curing atmosphere passing through the bed of green massive shapes is a function of the THE COKING STAGE
  • the cured shapes are subjected to coking at temperatures and times of such magnitude as to insure the reduction of the volatile combustible content (VCM) to a value below 2%.
  • VCM volatile combustible content
  • this treatment eifects an increase in strength and helps create that degree of reactivity specified for the end product. This is normally accomplished at temperatures above l500 F. for at least 5 minutes in an atmosphere such as that hereinafter disclosed.
  • a minimum time of 15 minutes is required; at 1700 F., a minimum time of 10 minutes is required.
  • coking can be continued for about one hour without loss of reactivity.
  • coking can be continued for about 40 minutes without loss of reactivity.
  • Flue gas passed through an incandescent bed of carbon to reduce the carbon dioxide content to below 10% by volume is a desirable medium for supplying coking heat to the shapes.
  • Hydrogen, carbon monoxide, nitrogen, hydrocarbon gases, and the tar-free gases generated in the calciner may be used for this purpose.
  • This stage results in coke formation from the copolymerized binder and calcinate in the cured shape to produce a chemically and physically uniform carbon structure in the final product.
  • the coking may be effected in a coking kiln, desirably, a vertical kiln, into the top of which the cured shapes are introduced and gravitate downward countercurrenlt to the hot gases.
  • the coking may be effected on a traveling grate passing through a suitable furnace.
  • the coked briquettes are cooled to a temperature (about 500 F.) at which exposure to air is not detrimental, or to a lower temperature, if desired.
  • Such cooling may be effected by passing cooling gas over or through a bed of coked shapes.
  • This gas must be substantially free of carbon dioxide, water vapor and oxygen. Desirably, it is effected in the lower portion of the shaft kiln, in the upper portion of which the cured shapes are coked.
  • the resultant briquettes withstand crushing pressures of at least 3000 pounds per square inch, remain stable under all operating and storage conditions, are exceptionally resistant to abrasion, and possess other desirable properties; by observing the necessary conditions herein disclosed, briquettes of desired chemical reactivity result, including briquettes which react uniformly and are eminently satisfactory for use in metallurgical furnaces, such as blast and phosphorus furnaces.
  • FIG. 2 shows a preferred arrangement of equipment for practicing the process of this invention
  • 1 indicates the pulverized coal feed to a screw conveyor 2 which discharges continuously into the catalyzer 3.
  • the catalyzer contains a fluidized bed 4 of the pulverized coal particles.
  • the fluidized bed 4 is activated by a hot gat stream 5 containing steam and air.
  • the hot gas stream 5 may be controlled to maintain the desired atmosphere in the catalyzer 3.
  • the catalyzer is equipped with an internal cyclone separator 6 through which gases evolved in the catalyzer are discharged through line 7.
  • the cyclone separator 6 also removes entrained coal particles from the gas and returns the particles to the fluidized bed 4.
  • the catalyzer 3 discharges coal continuously through line 8 into the carbonizer 9.
  • the carbonizer contains a fluidized bed 10 of the catalyzed coal particles.
  • a stream of hot air and inert gas 11 is supplied as the fluidizing medium.
  • the carbonizer 9 is equipped with an internal cyclone separator 12 through which gases evolved in the carbonizer are discharged.
  • a gas take-01f line 13 leads from the cyclone separator 12 to the condenser 30 hereinafter described.
  • the cylone separator 12 also removes char particles from the gas and returns the particles to the fluidized bed 10.
  • the carbonizer 9 discharges char continuously through line 14 into the calciner 15.
  • the calciner contains a fluidized bed 16 of the char particles.
  • a stream of hot air and inert gas 17 is supplied as the fluidizing medium.
  • the calciner is equipped with an internal cyclone separator 18 through which fuel gas evolved in the calciner 15 is discharged through line 19.
  • the cyclone separator 18 also removes char particles from the fuel gas and returns the particles to the fluidized bed 16.
  • the calciner 15 discharges calcined char continuously through line 20 into the cooler 21.
  • the cooler contains a fluidized bed 22 of calcined char particles fluidized by a stream of inert gas supplied through line 23.
  • the cooler is equipped with an internal cyclone separator 24 through which gases are discharged through line 25.
  • the cyclone separator also removes char particles from the gas and returns the particles to the fluidized bed 22.
  • the cooler 21 is also equipped with internal cooling coils 26 through which a suitable cooling medium may be circulated. Calcinate is continuously discharged from the cooler 21 through a rotary valve 27, then through a line 28 to the blender 29.
  • the tar recovery system comprises a condenser 30 supplied with a circulating cooling liquid to condense the tar and a portion of the Water vapor in the gas which enters the condenser 30 from line 13.
  • Fuel gas leaves the condenser through line 31.
  • Tarry condensate leaves the condenser 30 through line 32 and is discharged into the decanter 33.
  • Tar from the decanter is pumped through line 34 to the conditioner 35.
  • the conditioner is equipped with an agitator 36.
  • the tar in the conditioner can be heated while being agitated and is air blown by air introduced at 37 to remove moisture and raise the tar softening point. Excess gas is removed through line 38.
  • Tar binder is pumped from the bottom of the conditioner through line 39 to the blender 29.
  • the blender 29 discharges the calcinate-tar mixture through line 40 into the briquette former 41 which produces briquettes.
  • the briquettes are discharged onto conveyor 42 which communicates with the curing oven 43.
  • a stream of hot gas is recycled through the curing oven 15 by blower 44; this gas is heated in the gas heater 45.
  • the desired oxygen. content of the recycle gas is made up by supplying air through line 46. Waste gases evolved in the curing oven are discharged through line 47.
  • the cured briquettes are discharged continuously from the curing oven 43 into the coker 48.
  • the cured briquettes move slowly through the coker 48 through a flowing stream of inert reducing gas which is continuously removed from the coker by blower 49; the gas thus removed passes through the gas cooler 50.
  • the cooled gas reenters the coker through line 51 near the discharge end to cool the coked briquettes.
  • a portion of the cooled gas passes through a heater 52 and enters the coker through line 53. This gas maintains a high enough temperature to coke the cured briquettes entering the coker 48.
  • Fuel gas evolved in the coker is discharged through line 54.
  • the coked briquettes are discharged into a conveyor 55 and removed to storage.
  • coal was ground in a hammermill having a inch mesh screen to produce finely divided coal particles, 100% of which passed a No. 14 Tyler screen size, and of which was retained on a No. 325 Tyler screen size.
  • Examples I and II involved sub-bituminous coals identified in Table 1 which follows.
  • Type Pillow V briquettes Pressure, lbs/in. 20,000. Size of shapes, inches outside diameter x inches high %X% X /2 Curing:
  • Carbon Dioxide 4.1 Hydrocarbons 9.5. Nitrogen 68.2.
  • Examples IV and V involved bituminous coals, identified in Table 4 which follows and were carried out in the same general type of equipment used in Example I:
  • Heating value (ash free, gross B.t.u.) 10,757
  • the lignite was ground in a hammer mill and the finely divided lignite was then processed in the same general type of equipment as in Example I.
  • the conditions were as indicated in Table 6, which follows:
  • Fluidizing medium Superficial velocity, ft./sec- 0.65. Composition, volume percent- Oxygen 5.2. Nitrogen Steam 36.8. Calcining:
  • Fluidizing medium Superficial velocity, ft./sec 0.7. Composition, volume percent Oxygen 11.1. Nitrogen 88.9.
  • EXAMPLE VII This example involved processing of Reading Anthracite Coal having a moisture content of 4.2%, a volatile matter content (dry basis) of 4.5%, a fixed carbon content (dry basis) of 79.5%, and an ash content (dry basis) of 11.8%. All percentages are on aweight basis.
  • the anthracite coal was finely ground in a hammer mill to substantially the same particle size as the bituminous coals. It was then catalyzed in a catalyzer having an inside diameter of 1.5 inches by treatment in a fluid bed at a temperature of 350 F. for a residence time of 20 minutes employing a fluidizing medium containing 1.5% oxygen and 98.5% nitrogen at a superficial velocity of 0.4 foot per second.
  • the catalyzed coal particles were carbonized in a carbonizer having an inside diameter of 1.5 inches by treatment in a fluid bed at a temperature of 900 F. for a residence time of 20 minutes to produce char.
  • the fluidized medium used in this carbonizing stage was a mixture of 3.2 volume percent oxygen and 96.8 volume percent nitrogen, introduced at a superficial velocity of 0.4 foot per second.
  • the char was calcined in a fluid bed maintained in a calciner having an inside diameter of 1.5 inches.
  • the temperature of the bed was 1650 F.
  • the residence time was 20 minutes.
  • the fluidizing medium consisting of 100% nitrogen, was introduced into the fluid bed at a superficial velocity of 0.43 foot per second.
  • the calcinate was cooled to 200 F. by treatment in a fluid bed employing nitrogen as the fluidizing medium.
  • the cooled calcinate was mixed with a coal tar pitch having a softening point of 140 F. in the proportions of 15% pitch and 85% calcinate, the temperature of the constituents being approximately 160 F.
  • the pitch and calcinate were mixed for about 10 minutes, and then extruded under a pressure of about 20,000 pounds per square inch to produce shapes having an outside diameter of 1.125 inches and a height of 0.75 inch.
  • the cured shapes were then coked in a coking bed /1 inch high at a temperature of 1700 F. in an atmosphere consisting of 95 volume percent of nitrogen and 5 volume percent of hydrocarbons (e.g., methane), for 10 minutes.
  • hydrocarbons e.g., methane
  • the coke yield based on the dry weight of the coal was 85
  • the physical and chemical properties of the coke shapes produced in Examples I to VI inclusive, are given in Table 7 which follows.
  • ASG is the apparent specific gravity at 15 .5 C. calculated from the weight and dimensions of the coked extrusions or shapes;
  • ED is the bulk density, in pounds per cubic foot, determined by the procedure given in ASTM D-291;
  • TI is the Tumbler Index determined by the procedure given in ASTM D441;
  • RC is the resistance to crushing in lbs/in. determined by measuring the gauge reading at which a 1% inch x inch cylinder crushed under hydraulic pressure applied to its flat surface;
  • MH is the Mohs Hardness index measured using the standard Mohs Hardness scale
  • R is the resistivity in ohms/cmF/cm. measured using standard bridge techniques employing a test piece having a cross-sectional area of 1 cm. and a length of 1 cm.;
  • SAN is the surface area determined by the standard Brunauer, Emmett and Teller Method using nitrogen as the gas being absorbed;
  • SAW is the surface area determined by the standard Brunauer, Emmett and Teller Method using water vapor as the medium being absorbed;
  • AD is the absolute density as determined by Helium Sorption method
  • CRCO is the reactivity in carbon dioxide measured by the amount of coke, sized to pass through a 28-mesh Tyler screen, consumed in 1 hour in a stream of carbon dioxide at 900 C. and passed over the sample at a rate of 400 ml./min.;
  • CRH O is the reactivity in steam measured by the amount of coke, sized to pass through a 28-mesh Tyler screen consumed in 1 hour in a stream of steam at 825 C. and passed over the sample at a rate of 133 ml./rnin.
  • VM means volatile matter; the other abbreviations under Chemical Analysis are the chemical symbols or formulae for the elements and compounds identified thereby.
  • C/ H is the carbon to hydrogen weight ratio.
  • H /C is the hydrogen to carbon atom ratio.
  • procl- 40 every Case 0 6 pro 6 S 0 Xamp es o me us they were un1formly consumed and d1d not spall.
  • Examples VIII to XI difier from Example III in that the coking of the cured shapes was carried out under the different temperatures and curing times give in Table 9 using the same inert coking atmosphere in all examples. These examples show the effects of higher coking temperatures and longer coking times on the cured shapes and demonstrate that by coking the cured shapes at temperatures in excess of 1750 F., say at 2500 F. to 4000 F., for a long enough period of time, the length of which is inversely proportional to the temperature, products of low chemical reactivity and high strength result.
  • the RC (resistance to crushing) value of the product of Example III was 3800. This product had a crushing strength of 170 lbs., determined by ascertaining the number of pounds pressure required to crush a A; x /2 X inch pillow between jaws. Employing the same test procedure the crushing strength of the product of Example VIII was 185, of Example IX was 195, of Example X was 210 and of Example XI was 110.
  • the present invention provides a process for treating coals of any rank, in particular the cheap, widely available coals of non-coking quality, to produce a physically strong, carbonaceous product possessing essentially the same structure and apparent density as the parent coal.
  • the process of this invention may be practiced to produce chemically reactive carbonaceous products suitable for use, among other uses, as a metallurgical carbon.
  • the process of the present invention may also be carried out to produce carbonaceous products of high strength and having controlled chemical reactivity; thus, products of different reactivities from highly reactive (many times that of high temperature byproduct coke) to comparatively inert material and having desired predictable physical characteristics can be produced.
  • the present invention can be used to produce calcinate which is remarkably strong, abrasive-resistant, homogeneous, and exceptionally uniform in reaction with carbon dioxide, steam and oxygen.
  • This calcinate can be used as such, for example, as a raw material for water gas or other gas reactions in the place of coal or coke, or for eifecting the reduction of ores, as in sintered iron processes. It can be combined with a binder and the mixture compressed to produce a dense unit of any desired shape or size which is cured and coked as hereinabove disclosed to produce coke shapes possessing qualities rendering them eminently satisfactory for such uses as smelting of phosphorus and other ores, and carrying out chemical reactions. By processing under conditions herein disclosed, a high strength product of low chemical reactivity results; such products are suitable, among other uses, as a structural material in the chemical field.
  • a process of producing carbonaceous material which comprises heating non-coking coal particles to a temperature within the range of 250 F. to 500 F. in an atmosphere containing from 1% to 8% by-volume of oxygen for from 5 minutes to 3 hours to produce catalyzed coal particles conditioned so that in the next heating stage the content of hydrocarbonaceous matter in the coal is reduced; heating the catalyzed coal particles to a still higher temperature but not exceeding 1200 F. and maintaining them at said higher temperature for from 10 to 60 minutes to evolve vapors and produce char which has a markedly lower volatile combustible material content than the parent coal; and heating the char to a still higher temperature within the range of from 1400 F. to 1800 F. and maintaining the heated char at said higher temperature for a time interval to produce calcinate.
  • a process of producing carbonaceous shapes which comprises heating coal particles in the presence of from 1% to 20% by volume of oxygen to a temperature above 250 F. and below that at which substantial amounts of tar-forming vapors evolve for a time interval sufficient to reduce the water vapor content of the coal particles to not exceeding 2% by weight and produce catalyzed coal particles; heating the catalyzed coal particles to a still higher temperature and maintaining them at said higher temperature for a time interval sufficient to evolve substantially all tar-forming vapors in the catalyzed coal particles and produce char; heating the char to a still higher temperature and maintaining the heated char at said higher temperature for a time interval sufficient to produce hot calcinate; cooling said hot calcinate particles; blending said cooled calcinate particles with a bituminous binder; subjecting said blend to pressure to produce green shapes; curing the green shapes thus produced in an atmosphere containing oxygen to copolymerize the bituminous binder with the calcinate particles, without coking the binder, to produce cured shapes;
  • a process of producing carbonaceous shapes which comprises heating coal particles in the presence of from 1% to 20% by volume of oxygen to a temperature above 250 F. and below that at which substantial amounts of tar-forming vapors evolve for a time interval suflicient to reduce the water vapor content of the coal particles to not exceeding 2% by weight and produce catalyzed coal particles; heating the catalyzed coal particles to a still higher temperature and maintaining them at said higher temperature for a time interval suflicient to evolve substantially all tar-forming vapors in the catalyzed coal particles and produce char; heating the char to a still higher temperature and maintaining the heated char at said higher temperature for a time interval sufficient to produce hot calcinate having a volatile combustible material content not exceeding about 3% by weight, on a moisture and ash free basis; substantially instantaneously cooling said hot calcinate particles to a temperature of from 30 F.
  • a process of producing carbonaceous shapes which comprises heating non-coking coal particles to a temperature within the range of 250 F. to 500 F. in an atmosphere containing from 1% to 8% by volume of oxygen for from 5 minutes to 3 hous to produce catalyzed coal particles conditioned so that in the next heating stage the hydrocarbonaceous matter is reduced; heating the catalyzed coal particles to a still higher temperature but not exceeding 1200 F. and maintaining them at said higher temperature for from 10 to 60 minutes to evolve vapors and produce char which has a markedly lower volatile combustible material content than the parent coal; heating the char to a still higher temperature within the range of from 1400 F. to 1800 F.
  • a process of producing carbonaceous shapes which comprises heating coking coal particles to a temperature within the rang of 500 F. to 800 F. in an atmosphere containing from 8% to 20% by volume of oxygen for from minutes to 3 hours to produce catalyzed coal particles conditioned so that in the next heating stage the content of hydrocarbonaceous matter in the coal is reduced; heating the catalyzed coal particles substantially instantaneously to a still higher temperature but not exceeding l200 F. and maintaining them at said higher temperature for from 10 to 60 minutes to evolve vapors and produce char which has a markedly lower volatile combustible material content than the parent coal; heating the char to a still higher temperature within the range of from 1400 F. to 1800 F.
  • the method of producing chemically reactive carbonaceous material from non-coking bituminous coals which comprises heating for 5 minutes to 3 hours noncoking bituminous coal particles in an atmosphere containing from 1% to 8% by volume of oxygen to a temperature of from 250 F. to 500 F.; thereafter further heating the thus treated coal particles substantially instantaneously to a temperature of from 500 F. to l200 F. and maintaining the coal particles at said temperature for from 10 to 60 minutes; and thereafter substantially instantaneously heating the thus treated coal particles to a temperature of from 1400 F. to 1800 F. in an atmosphere substantially free of carbon dioxide and water vapor and maintaining them at said temperature for a time interval suflicient to reduce the volatile content to a maximum of about 3% by weight, on a moisture and ash free basis.
  • the method of producing physically strong, chemically reactive carbonaceous material from non-coking coals involving heating the non-coking coal particles in a first fluidized bed in an atmosphere containing from 1% to 8% by volume of oxygen to a temperature of from 250 F. to 500 F. for from 5 minutes to 3 hours; removing the thus heated coal particles from said first mentioned fluidized bed and introducing them into a second fluidized bed where they are heated to a temperature of from 500 F. to 1200 F. for from 10 to 60 minutes, said heating being effected in part at least by combustion of a portion of the coal; removing the thus heated coal particles from the second fluidized bed and introducing them into a third fluidized bed where they are heated to a temperature of from 1400 F. to 1800 F.
  • a fluidizing gas atmosphere consisting of flue gas substantially free of carbon dioxide, oxygen and water vapor; and thereafter withdrawing the thus heated finely divided coal particles and introducing them into a fourth fluidized bed where they are cooled by a fluidizing flue gas medium substantially free of carbon dioxide, oxygen and water vapor.
  • the method of producing physically strong, chemically reactive carbonaceous shapes from coal which comprises heating coal particles in an atmosphere containing from 1% to 20% by volume of oxygen to a temperature of from 250 F. to 800 F. for a time interval suflicient to produce catalyzed coal particles conditioned so that in the next heating stage the content of hydrocarbonaceous matter in the coal is reduced; thereafter substantially instantaneously heating the catalyzed coal particles to a still higher temperature but not exceeding l200 F. for a time interval suflicient to evolve vapors and produce char which has a markedly lower volatile combustible material content; thereafter substantially instantaneously heating the char to a temperature of from 1400" F. to 1800 F.
  • the method of producing physically strong, chemically reactive carbonaceous shapes from non-coking coals which comprises heating for 5 minutes to 3 hours non coking bituminous coal particles in an atmosphere containing from 1% to 8% by volume of oxygen to a temperature of from 250 F. to 500 F; thereafter further heating the thus treated coal particles substantially instantaneously to a temperature of from 500 F. to 1200 F. and maintaining the coal particles at said temperature for from 10 to 60 minutes; thereafter substantially instantaneously heating the thus treated coal to a temperature of from 1400 F. to 1800 F.
  • the method of producing physically strong, chemically reactive carbonaceous shapes from coking coals which comprises heating coal particles in a fluidized bed to a temperature of from 500 F. to 800 F. in an atmosphere containing from 8% to 20% by volume of oxygen; heating the thus treated coal particles for from to 60 minutes to a still higher temperature by introducing them into and maintaining them in a fluidized bed at a temperature not exceeding 1200 F.; thereafter heating the thus treated coal particles in another fluidized bed to a temperature of from 1400 F.
  • the method of producing physically strong, chemically reactive carbonaceous briquettes from coal which comprises heating non-coking coal particles in a first fluidized bed in an atmosphere containing from 1% to 8% by volume of oxygen to a temperature of from 250 F. to 500 F said coal particles being subjected to said heating in said fluidized bed for an average residence time of at least 5 minutes; removing the thus heated coal particles from said first mentioned fluidized bed and introducing them into a second fluidized bed where they are heated to a temperature of from 500 F. to 1200 F. for from 10 to 60 minutes; introducing the fluidizing gas into the second fluidized bed at a temperature not below and within 20 F.
  • the method of producing physically strong, carbonaceous briquettes from coal which comprises heating coal particles in a first fluidized bed in an atmosphere containing from 1% to 20% oxygen to a temperature of from 250 F. to 800 F. for from 5 minutes to 3 hours; removing the thus heated coal particles from said first mentioned fluidized bed and introducing them into a second fluidized bed where they are heated to a temperature not exceeding 1200 F. for from 10 to 60 minutes, said heating being effected in part at least by combustion of a portion of the coal; introducing fluidizing flue gas into the second fluidized bed at a temperature not less than that of the bed temperature; removing the thus heated coal particles from the second fluidized bed and introducing them into a third fluidized bed where they are heated to 1400 F. to 1800 F.
  • a fluidizing gas atmosphere consisting of flue gas substantially free of carbon dioxide and water vapor; thereafter withdrawing the thus heated coal particles and introducing them into a fourth fluidized bed Where they are cooled by a fluidizing flue gas medium to a temperature not exceeding 400 F., said cooling medium being substantially free of carbon dioxide, oxygen and water vapor; mixing the cooled carbonaceous material with a bituminous binder in the proportions of 75% to 90% by weight of reactive carbonaceous material to 10% to 25 by weight of binder; briquetting the resultant mixture; curing the briquettes by passing them through a heating zone at a temperature of from 450 F. to 500 F.
  • bituminous binder is obtained from the tar condensed out of the gases evolved during the heating of said coal particles in the second mentioned fluidized bed and has a softening point of from F. to 225 F.
  • a method for. the conversion of coals of any rank from anthracite to lignite into pitch-bonded carbon products possessing high mechanical strength comprises the following steps: step 1, heating the coal in pulverized form in a mildly oxidizing atmosphere at a temperature below that at which substantial amounts of tar-forming vapors evolve and above that at which water, when present, vaporizes, to produce a product which is non-agglomerating in step 2; step 2, heating the product of step 1 to a temperature at which evolution of tar-forming vapors takes place at a rate insuificient to cause permanent swelling, distortion and disruption of the product of step 1, said heating being for a time interval long enough to effect substantially complete removal of tar-forming vapors and materially reduce the volatile matter but not long enough to impair the pyrophoric reactivity of the product of step 2; step 3, heating the product of step 2 to admirs a temperature not exceeding 1800 F.
  • step 4 in an atmosphere containing only sufiicient oxygen for the coal particles to reach said heating temperature and for a period of time to effect reduction of the volatile content of the product of step 2 to less than about 3% by Weight, on a moisture and ash free basis, without substantial impairment of the pyrophoric reactivity of the product of step 3; step 4,
  • step 3 lending the product of step 3 with pitch in amount suflicient to coat the product of step 3 and produce a mechanically strong product when subjected to compression; step 5, compressing the blended product of step 4; step 6, curing the compressed product of step by rapid heating in a mildly oxidizing atmosphere at a temperature sufiicient to cause copolyrnerization of the pitch binder and the product of step 3 to take place; and, step 7, coking the product of step 6 at a temperature exceeding 1500 F. in an inert atmosphere for a time interval to produce a high strength product having the desired chemical reactivity.
  • a method for the conversion of coals of any rank from anthracite to lignite into pitch-bonded carbon products possessing high mechanical strength and high chemical reactivity comprises the following steps; step 1, heating the coal in pulverized form in a mildly oxidizing fluidizing atmosphere at a temperature below that at which substantial amounts of tar-forming vapors evolve and above that at which water, when present, vaporizes, to produce a product which is non-agglomerating in step 2; step 2, heating the product of step 1 in a fiuidizing atmosphere containing oxygen to a temperature causing evolution substantially all of tar-forming vapors at a rate insufiicient to cause permanent swelling, distortion and disruption of the Product of step 1, said heating being for a time interval long enough to materially reduce the volatile matter but not long enough to impair the pyrophoric reactivity of the product of step 2; step 3, heating the product of step 2 to a temperature not exceeding 1800 F.
  • step 4 blending the product of step 3 with pitch in amount sufficient to coat the product of step 3 and produce a mechanically strong product when subjected to compression; step 5, compressing the blended product of step 4; step 6, curing the compressed product of step 5 by rapid heating in a mildly oxidizing atmosphere at a temperature below that at which coking of the pitch binder takes place but sutficient to cause copolymerization of the pitch binder and the product of step 3 to take place; and, step 7, heating the product of step 6 to a temperature not exceeding 1750 F. in an inert atmosphere to produce a coke product of high mechanical strength and high chemical reactivity.
  • a method for the conversion of coals of any rank from anthracite to lignite into pitch-bonded carbon products possessing high mechanical strength comprises the following steps: step 1, heating the coal in pulverized form in a mildly oxidizing fiuidizing atmosphere at a temperature below that at which substantial amounts of tar-forming vapors evolve and above that at which water, when present, vaporizes, to produce a product which is non-agglomerating in step 2; step 2, heating the product of step 1 in a fiuidizing atmosphere containing oxygen to a temperature causing evolution substantially all of tar-forming vapors at a rate insufficient to cause permanent swelling, distortion and disruption of the product of step 1, said heating being for a time interval long enough to materially reduce the volatile matter but not long enough to impair the pyrophoric reactivity of the product of step 2; step 3, heating the product of step 2 to a temperature not exceeding 1800 F.
  • step 4 blending the product of step 3 with pitch in amount sufiicient to coat the product of step 3 and produce a mechanically strong product when subjected to compression; step 5, compressing the blended product of step 4; step 6, curing the compressed product of step 5 by rapid heating in a mildly oxidizing atmosphere at a temperature below that at which coking of the pitch binder takes place but sufiicient to cause copolymerization of the pitch binder and the product of step 3 to take place; and, step 7, heating the product of step 6 to a temperature within the range of 1750 F. to 4000 F. for a time interval to produce a high strength product of low chemical reactivity.
  • step 5 the blended product of step 4 is heated to a temperature not exceeding 50 F. below the coking point of the pitch binder.
  • step 1 heating coal particles in the presence of oxygen to a temperature above 250 F. and below that at which substantial amounts of tar-forming vapors evolve to produce a product which is non-agglomerating in step 2; step 2, heating the product of step 1 to a higher temperature at which tar-forming vapors are evolved, and maintaining said heated particles at said higher temperature for a time interval suflicient to effect polymerization of the heated coal particles and evolution therefrom of substantially all vapors which condense as tars, producing a char of markedly lower volatile combustible material content than the parent coal and substantially free of tar-forming vapors; step 3, heating the char of step 2 to a still higher temperature for a time interval sufiicient to produce calcined char particles; step 4, cooling the product of step 3; step 5, blending said cooled product from step 4 with a bituminous binder; step 6, compressing said blend to produce green shapes; step 7, curing the green shapes in
  • the process of producing carbonaceous shapes which comprises heating coal particles in the presence of from 1% to 20% by volume of oxygen to a temperature above 250 F. and below that at which substantial amounts of tar-forming vapors evolve for a time interval suflicient to produce catalyzed coal particles; heating the catalyzed coal particles to a still higher temperature at which tar-forming vapors are evolved and maintaining said heated particles at said higher temperature for a time interval sufiicient to effect polymerization of the heated coal particles and evolution therefrom of substantially all tar-forming vapors, producing a char of markedly lower volatile combustible material content than the parent coal and substantially free of tar-forming vapors; heating the char to a still higher temperature and maintaining said heated char at said higher temperature for a time interval sufficient to produce calcined char particles; cooling said calcinate particles; blending said cooled calcinate particles with a bituminous binder; compressing said blend to produce green shapes; curing the green shapes in an oxidizing atmosphere
  • step 1 heating coal particles in the presence of oxygen to a temperature above 250 F. and below that at which substantial amounts of tar-forming vapors evolve; step 2, heating the product of step 1 to a higher temperature at which tar-forming vapors are evolved, and maintaining said heated particles at said higher temperature for a time interval sufficient to eflfect polymerization of the heated coal particles and evolution therefrom of substantially all of said tar-forming vapors, producing a char of markedly lower volatile combustible material content than the parent coal and substantially free of tar-forming vapors; and step 3, separately removing the tar-forming vapors evolved in step 2 and the char produced in step 2 and heating the char produced in step 2 out of contact with said tarforming vapors evolved in step 2 to a still higher temperature for a time interval sufiicient to produce calcined char particles.
  • step 1 rapidly heating the coal particles in an oxygen-containing atmosphere to a temperature (1) above 250 F.
  • step 2 rapidly heating the product of step 1 to a temperature to cause evolution of condensible tar vapors at a rate insufiicient to cause destructive deformation of the coal particles and continuing said heating until said evolution of condensible tar-forming vapors is substantially complete thereby producing a pyrophoric char substantially free of tar-forming vapors; step 3, separately removing the condensible tar-forming vapors formed in step 2 and the char produced in step 2 and heating the char produced in step 2 out of contact with said tarforming vapors evolved in step 2 to a still higher temperature to produce calcined char particles having a volatile combustible material content below about 3% by weight of the char particles as produced in step 3; and step 4, cooling the products of step 3 to below 400 F
  • step 1 heating coal particles in the presence of oxygen to a temperature above 250 F. and below that at which substantial amounts of tar-forming vapors evolve to produce a product which is non-agglomerating in step 2; step 2, heating the product of step 1 to a higher temperature at which tar-forming vapors are evolved, and maintaining said heated particles at said higher temperature for a time interval suflicient to effect polymerization of the heated coal particles and evolution therefrom of substantially all vapors which condense as tars, producing a char of markedly lower volatile combustible material content than the parent coal and substantially free of tar-forming vapors; and step 3, separately removing the tar-forming vapors evolved in step 2 and the char produced in step 2 and heating the char produced in step 2 out of contact with said tar-forming vapors evolved in step 2 to a still higher temperature not exceeding 1800 F. for a residence time not exceeding ten minutes to produce calcined char particles having

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US821137A US3140241A (en) 1959-06-18 1959-06-18 Processes for producing carbonaceous materials
FR829685A FR1259299A (fr) 1959-06-18 1960-06-10 Procédés d'obtention de matières carbonées physiquement résistantes
LU38797D LU38797A1 (en)) 1959-06-18 1960-06-11
DE19601421258 DE1421258C (de) 1959-06-18 1960-06-13 Verfahren zur Herstellung von Form koks aus Kohlen behebiger Art
BE591859A BE591859A (fr) 1959-06-18 1960-06-14 Procédés d'obtention de matières carbonées physiquement résistantes
AT188762A AT244901B (de) 1959-06-18 1960-06-14 Verfahren zur Herstellung von mechanisch festen Koksstücken
GB21162/60A GB926213A (en) 1959-06-18 1960-06-16 Improvements in and relating to the production of physically strong carbonaceous material from coal
CS388660A CS155126B2 (en)) 1959-06-18 1960-06-16
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Cited By (23)

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DE2244714A1 (de) * 1971-09-15 1973-03-22 Fmc Corp Verfahren zur herstellung von formkoks
US3725034A (en) * 1971-11-01 1973-04-03 Fmc Corp Method of producing carbon and iron-containing briquettes
FR2284663A1 (fr) * 1974-09-14 1976-04-09 Werner Wenzel Procede d'amelioration de la consistance du coke
US3968052A (en) * 1971-02-11 1976-07-06 Cogas Development Company Synthesis gas manufacture
JPS51106101A (en) * 1975-02-19 1976-09-20 Centro Speriment Metallurg Kairyoshitaseiseikookusunoseiho
US3992266A (en) * 1975-07-24 1976-11-16 Inland Steel Company Recovery of coal fines from preheater
US3996108A (en) * 1973-04-09 1976-12-07 Fmc Corporation Briquetting of reactive coal calcinate with high-temperature coke oven pitch
US4022668A (en) * 1974-07-03 1977-05-10 Centro Sperimentale Metallurgico S.P.A. Process for the production of formed coke
US4108731A (en) * 1973-11-29 1978-08-22 Centro Sperimentale Metallurgico S.P.A. Coke production
US4139416A (en) * 1975-01-21 1979-02-13 Centro Sperimentale Metallurgico S.P.A. Carbonaceous material with high characteristics of surface area and activity and process for producing the same
US4148692A (en) * 1977-08-26 1979-04-10 Bethlehem Steel Corporation Process for producing low reactivity calcined coke agglomerates
US4260456A (en) * 1979-05-29 1981-04-07 Tosco Corporation Single retort manufacturing technique for producing valuable char and gases from coke
US4287023A (en) * 1979-08-23 1981-09-01 Phillips Petroleum Co. Waste heat recovery
US4288293A (en) * 1980-04-14 1981-09-08 Fmc Corporation Form coke production with recovery of medium BTU gas
US4303415A (en) * 1980-09-29 1981-12-01 Lubille Energy Development Co., Ltd. Gasification of coal
US4461627A (en) * 1981-12-18 1984-07-24 Hitachi, Ltd. Upgrading method of low-rank coal
US4557733A (en) * 1984-11-05 1985-12-10 Peabody Development Company Formcoke process
US4602917A (en) * 1985-04-22 1986-07-29 Fmc Corporation Formcoke having modified bituminous binder
US4698067A (en) * 1985-06-24 1987-10-06 Fmc Corporation Formcoke having modified bituminous binder
US5236468A (en) * 1992-03-19 1993-08-17 J. S. Mccormick Company Method of producing formed carbonaceous bodies
WO2008138478A3 (de) * 2007-05-09 2009-02-26 Siemens Vai Metals Tech Gmbh Verfahren zur herstellung von formlingen
CN113621393A (zh) * 2021-07-21 2021-11-09 武汉钢铁有限公司 挥发分为18～22％的焦煤的分类配用方法
US12006219B2 (en) 2019-03-12 2024-06-11 University Of Wyoming Thermo-chemical processing of coal via solvent extraction

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US4362532A (en) * 1981-08-11 1982-12-07 Conoco Inc. Production of blast furnace coke via novel briquetting system
EP4179041A4 (en) * 2020-07-13 2024-08-07 OCS IP Pty Ltd. ORGANIC CARBONIZATION SYSTEM AND METHOD THEREFOR

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US1943291A (en) * 1931-02-04 1934-01-16 Arthur V Abbott Process for the low temperature distillation of coal
US2164933A (en) * 1934-11-07 1939-07-04 Maurel Invest Corp Process of baking fuel briquettes
US2582712A (en) * 1947-05-17 1952-01-15 Standard Oil Dev Co Fluidized carbonization of solids
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US2805189A (en) * 1950-05-25 1957-09-03 Standard Oil Co Method of heating and fluidizing for a carbonization process
US2815316A (en) * 1952-01-18 1957-12-03 American Cyanamid Co Process of treating coal
US2869992A (en) * 1957-01-02 1959-01-20 Exxon Research Engineering Co Preliminary heating of fluid coke briquettes
US3001237A (en) * 1956-12-31 1961-09-26 James D Hedges Method of making carbon articles
US3018227A (en) * 1957-01-22 1962-01-23 Consolidation Coal Co Preparation of formcoke
US3051629A (en) * 1958-07-07 1962-08-28 Consolidation Coal Co Preparing metallurgical fuel briquets from non-caking coal by preshrinking char
US3070515A (en) * 1957-05-06 1962-12-25 Consolidation Coal Co Fluidized low temperature carbonization of caking bituminous coal

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US2734851A (en) * 1956-02-14 smith
US1943291A (en) * 1931-02-04 1934-01-16 Arthur V Abbott Process for the low temperature distillation of coal
US2164933A (en) * 1934-11-07 1939-07-04 Maurel Invest Corp Process of baking fuel briquettes
US2582712A (en) * 1947-05-17 1952-01-15 Standard Oil Dev Co Fluidized carbonization of solids
US2805189A (en) * 1950-05-25 1957-09-03 Standard Oil Co Method of heating and fluidizing for a carbonization process
US2815316A (en) * 1952-01-18 1957-12-03 American Cyanamid Co Process of treating coal
US3001237A (en) * 1956-12-31 1961-09-26 James D Hedges Method of making carbon articles
US2869992A (en) * 1957-01-02 1959-01-20 Exxon Research Engineering Co Preliminary heating of fluid coke briquettes
US3018227A (en) * 1957-01-22 1962-01-23 Consolidation Coal Co Preparation of formcoke
US3070515A (en) * 1957-05-06 1962-12-25 Consolidation Coal Co Fluidized low temperature carbonization of caking bituminous coal
US3051629A (en) * 1958-07-07 1962-08-28 Consolidation Coal Co Preparing metallurgical fuel briquets from non-caking coal by preshrinking char

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3968052A (en) * 1971-02-11 1976-07-06 Cogas Development Company Synthesis gas manufacture
DE2244714A1 (de) * 1971-09-15 1973-03-22 Fmc Corp Verfahren zur herstellung von formkoks
US3725034A (en) * 1971-11-01 1973-04-03 Fmc Corp Method of producing carbon and iron-containing briquettes
US3996108A (en) * 1973-04-09 1976-12-07 Fmc Corporation Briquetting of reactive coal calcinate with high-temperature coke oven pitch
US4108731A (en) * 1973-11-29 1978-08-22 Centro Sperimentale Metallurgico S.P.A. Coke production
US4022668A (en) * 1974-07-03 1977-05-10 Centro Sperimentale Metallurgico S.P.A. Process for the production of formed coke
FR2284663A1 (fr) * 1974-09-14 1976-04-09 Werner Wenzel Procede d'amelioration de la consistance du coke
US4139416A (en) * 1975-01-21 1979-02-13 Centro Sperimentale Metallurgico S.P.A. Carbonaceous material with high characteristics of surface area and activity and process for producing the same
JPS51106101A (en) * 1975-02-19 1976-09-20 Centro Speriment Metallurg Kairyoshitaseiseikookusunoseiho
US3992266A (en) * 1975-07-24 1976-11-16 Inland Steel Company Recovery of coal fines from preheater
US4148692A (en) * 1977-08-26 1979-04-10 Bethlehem Steel Corporation Process for producing low reactivity calcined coke agglomerates
US4260456A (en) * 1979-05-29 1981-04-07 Tosco Corporation Single retort manufacturing technique for producing valuable char and gases from coke
US4287023A (en) * 1979-08-23 1981-09-01 Phillips Petroleum Co. Waste heat recovery
US4288293A (en) * 1980-04-14 1981-09-08 Fmc Corporation Form coke production with recovery of medium BTU gas
US4303415A (en) * 1980-09-29 1981-12-01 Lubille Energy Development Co., Ltd. Gasification of coal
US4461627A (en) * 1981-12-18 1984-07-24 Hitachi, Ltd. Upgrading method of low-rank coal
US4557733A (en) * 1984-11-05 1985-12-10 Peabody Development Company Formcoke process
US4602917A (en) * 1985-04-22 1986-07-29 Fmc Corporation Formcoke having modified bituminous binder
US4698067A (en) * 1985-06-24 1987-10-06 Fmc Corporation Formcoke having modified bituminous binder
US5236468A (en) * 1992-03-19 1993-08-17 J. S. Mccormick Company Method of producing formed carbonaceous bodies
WO2008138478A3 (de) * 2007-05-09 2009-02-26 Siemens Vai Metals Tech Gmbh Verfahren zur herstellung von formlingen
US20100133723A1 (en) * 2007-05-09 2010-06-03 Wilhelm Fingerhut Method for producing moldings
US9090844B2 (en) 2007-05-09 2015-07-28 Siemens Vai Metals Technologies Gmbh Method for producing moldings
US12006219B2 (en) 2019-03-12 2024-06-11 University Of Wyoming Thermo-chemical processing of coal via solvent extraction
CN113621393A (zh) * 2021-07-21 2021-11-09 武汉钢铁有限公司 挥发分为18～22％的焦煤的分类配用方法
CN113621393B (zh) * 2021-07-21 2022-11-01 武汉钢铁有限公司 挥发分为18～22％的焦煤的分类配用方法

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DE1421258B1 (de) 1972-09-21
NL252579A (en)) 1900-01-01
SE308502B (en)) 1969-02-17
AT244901B (de) 1966-02-10
CS155126B2 (en)) 1974-05-30
FR1259299A (fr) 1961-04-21
GB926213A (en) 1963-05-15
NL130819C (en)) 1900-01-01
BE591859A (fr) 1960-10-03
LU38797A1 (en)) 1960-08-11

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