Classifications

• • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L9/00—Treating solid fuels to improve their combustion
  • C10L9/10—Treating solid fuels to improve their combustion by using additives
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S44/00—Fuel and related compositions
  • Y10S44/905—Method involving added catalyst

Definitions

• coke has been made from coking coals in by-product or beehive ovens; the coke is obtained as a mass which is discharged from the furnace in the form of lumps or irregular shape.
• the coke In handlingparticularly in shipping-the edges and corners of these lumps break off as fines, which cause difiiculty in maintaining bed porosity in the blast furnace, and rapid plugging of the dust-collecting systems associated therewith.
• the fines produced are relatively coarse and are airborne With difficulty in normal handling. This tendency to produce fines is generally tested according to the American Society for Testing and Materials method ASTM D294-64, called the Tumbler Test.
• Results are reported as the hardness factori.e., the weight of the coke sample that is retained on the A" standard sieve after tumbling.
• the hardness factor i.e., the weight of the coke sample that is retained on the A" standard sieve after tumbling.
• any coke that degrades in handling to a size that will pass through the A" standard sieve is removed by in-transit screening as the coke moves from the supply dump to the skip car for charging to the blast furnace, so that the hardness factor measures the coke available for actual charging to the furnace.
• This invention aims to produce a glanz carbon coating on reactive form coke during processing subsequent to the formation of the green briquettes from the hydrocarbons which are evolved during the operation, Without the need for adding hydrocarbon vapors from outside sources.
• this objective is attained by processing briquettes of reactive form coke after formation in the presence of a catalyst metal, or a salt thereofmost preferably tin or zincad 'acent the surface of the briquettes; the hydrocarbon vapors coming out of the briquettes are cracked at the surface to deposit thereon a thin film of glanz carbon covering the entire surface and filling the surface pores up to about 5 microns in size.
• the resultant coated reactive form coke is nondusting and even nonsmutting. Since the coating occurs simultaneously with curing or calcination, no additional process step With attendant cost is involved.
• the process is applicable to other form cokes, and improved briquettes result.
• this invention is designed to control a problem which seems to be unique with the carbonaceous briquettes made in accordance with U.S. Pats. 3,140,241 and 3,140,242.
• a reactive calcinate is made by catalyzing coal particles by heating in the presence of added oxygen (U.S. Pat. 3,140,241) or oxygen in the coal (U.S. Pat. 3,140,242) to a temperature above 250 F.
• Reactive form coke withstands the ASTM Tumbler Test better than conventional coke, but after long rail shipments and bulk handling produce the serious dusting problem hereinabove referred to.
• glanz carbon on the surface of the briquettes is an excellent way of overcoming this dusting problem, provided sufiicient glanz carbon is produced to coat substantially the entire surface and to fill the very fine (5 micron) pores.
• sufiicient glanz carbon is produced to coat substantially the entire surface and to fill the very fine (5 micron) pores.
• the hydrocarbon distilled from the briquettes during coking does not ordinarily produce glanz carbon on the surface; it is necessary to have a volume concentration of hydrocarbons in the gases surrounding the coking briquettes to produce a useful glanz carbon film.
• the metal need be present in only trace quantities, and may be derived from metal or a metal salt. It can be added in any convenient fashion. It cannot be added to the briquetting mix-metal in the interior of the briquette forms glanz carbon there, which prevents reaction between binder and solid, essential to get nonspalling briquettes. However, it can be added to the briquettes after forming and be present during curing. For example, if
• the briquettes are cured in the presence of pieces of tin plate or galvanized iron, enough metal is volatilized into the gas stream passing over the briquette surfaces to produce a glanz carbon film on subsequent coking.
• the same elfect is obtained by spraying the green briquette surfaces, before curing, with as little as 5 10 parts by weight of stannous chloride per part by weight of briquette.
• Another method of getting the same effect is to hang strips of asbestos paper, carrying tin or zinc chloride, in the curing oven; enough volatilizes to get the desired effect.
• the catalyst may also be present in the coking oven with the same results.
• the invention is applicable to form coke briquettes made by briquetting ordinary nonreactive coal chars with bituminous binders, followed by coking with or without an intermediate curing step in the presence of oxygen.
• the resultant coated briquettes have the advantage of a clean nondusting surface, but their basic problem of nonuniform burning, with resultant spalling, is not overcome.
• EXAMPLE 1 Two-inch briquettes were prepared in pilot operation from a green mix of Elkol-Adaville calcinate and raw tar, produced in commercial operation, using 15% of binder as per instruction in U.S. Pat. 3,184,293. These briquettes were treated with a tin solution containing g. of stannous chloride (10%) per 100 ml. of solution. This tin solution was applied with a 5 mm. wide glue brush to an area of approximately 5 mm. square on the horizontal surface of the briquettes. One brush stroke was used on each briquette, and the amount of stannous chloride applied could not be measured on a standard three-beam balance to the second decimal place. The briquettes weighed 300 g.
• the coating persisted through carbonization at 1750 F. in a nitrogen gas atmosphere. On cooling, these briquettes were abraded by rubbing together. The hard, dense coating caused no dust and appeared to be polished by the rubbing.
• the untreated counterparts were dusty, dirty to touch, and produced a black streak on a white cloth surface. When rubbed together, they produced a cloud of airborne dust that persisted for up to 60 minutes.
• EXAMPLE 2 Four briquettes from the same parent sample as Example l were placed in the curing oven, described in Example 1, along with a strip of asbestos sheeting 1" wide and 12" long which had been stroked once with a A" wide glue blush dipped in a 10% stannous chloride solution. On curing and coking as in Example 1, the hard, dense, abrasion-resistant coating, previously described, developed and persisted.
• the test used to determine the dusting potential of carbonized briquettes was developed to stimulate the amount of fines and dust that develops when briquettes are handled and transported from the point of production to the point of use. In practice, it has been found that up to 2% of the weight of the carbonized briquettes may be abraded away in the car. However, this high figure is peculiar to the Weakest product from commercial production. For that product of normal strength, an abrasion figure of 0.5% is much more realistic.
• the test developed is called the Vibration Test and is performed in the following manner. One hundred grams (to the nearest whole briquette) of carbonized briquettes are charged to a 5" diameter 10 mesh laboratory sieve with a 2" high wall.
• the sieve is attached to a vibrator such as the Vita- Surge SPN 74207, which moves the screen at 60 cycle frequency between A; and A" in horizontal direction.
• the test is run for 30 minutes when the fines generated are totalized and weighed.
• These composite fines are screened through a 325 mesh sieve (44 microns), andthe amount passing the sieve expressed as weight percent of the charged briquettes is called the dust index.
• EXAMPLE 4 One hundred fifty grams of 2" x 2" x 1" briquettes were treated with p.p.m. of stannous chloride out of a 10% solution. These briquettes were cured and carbonized as with other examples described herein. On testing for dust index, these briquettes did not abrade, and no particles smaller than 44 microns (325 mesh sieve size) were formed. The control counterpart showed a dust index of 0.25% by weight.
• EXAMPLE 5 Approximately 200 pounds of 2" x 2" x 1" pillow briquettes, made from a Polish coal of high rank, via the method of U.S. Pat. 3,184,293, were cured in the presence of the metallic tin contained in the coating of approximately 250" square of tin-coated steel (six l-gallon can lids) for minutes at 450 to 500 F. in a continuous pilot unit whose capacity was 200 pounds per hour. The operation of this unit is such that heated air passes through the Weight of briquettes charged in a basket that is moving in an insulated section of an oven held at the reaction temperature.
• the untreated control counterpart had a comparable dust index on this modified tumbler test of 21% by weight of the charge and produced a dust cloud of about 20 cubic feet which persisted for almost 60 seconds.
• the can lids used in curing were partially coated with hard brittle pitch.
• the quality of the carbonized briquettes in both cases was excellent, with crushing resistance for the control sample of 1,200 pounds and for those cured in the presence of tin at 1,450 pounds. No chemical evidence of tin on the briquette surface could be detected.
• EXAMPLE 6 Ten cured briquettes were treated with stannous chloride as in Example 4, and Were then coked at 1750 F. The briquettes were covered with a silvery-gray glanz carbon coating, and had much improved dusting qualities.
• the method of treating uncoked form coke briquettes which are otherwise susceptible to excessive dusting on abrasion to substantially reduce the dusting by producing a hard dense glanz carbon coating which substantially fills the '5 micron pores adjacent the surface of the briquettes and forms a coating over the larger pores, which comprises heating the briquettes to at least curing temperatures in the presence, adjacent the surfaces of the briquettes, of catalytic quantities of an element of the group consisting of tin and zinc.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Combustion & Propulsion (AREA)
• Materials Engineering (AREA)
• Solid Fuels And Fuel-Associated Substances (AREA)
• Catalysts (AREA)
• Manufacture And Refinement Of Metals (AREA)

Applications Claiming Priority (1)

Publications (1)

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Family Applications (1)

Country Status (24)

Cited By (3)

• 1971
  • 1971-04-19 US US00135379A patent/US3725019A/en not_active Expired - Lifetime
• 1972
  • 1972-03-13 CA CA136,931A patent/CA947503A/en not_active Expired
  • 1972-03-14 ZA ZA721744A patent/ZA721744B/xx unknown
  • 1972-03-16 AU AU40064/72A patent/AU456968B2/en not_active Expired
  • 1972-04-07 FR FR7212353A patent/FR2133613B1/fr not_active Expired
  • 1972-04-10 SU SU1774340A patent/SU415888A3/ru active
  • 1972-04-14 AT AT325472A patent/AT358520B/de not_active IP Right Cessation
  • 1972-04-15 PL PL1972154760A patent/PL75371B1/pl unknown
  • 1972-04-17 YU YU01025/72A patent/YU102572A/xx unknown
  • 1972-04-17 GB GB1772572A patent/GB1381325A/en not_active Expired
  • 1972-04-17 LU LU65174D patent/LU65174A1/xx unknown
  • 1972-04-17 EG EG151/72A patent/EG10713A/xx active
  • 1972-04-17 BE BE782232A patent/BE782232A/xx unknown
  • 1972-04-18 HU HUFA908A patent/HU163532B/hu unknown
  • 1972-04-18 CS CS722603A patent/CS190365B2/cs unknown
  • 1972-04-18 TR TR17132A patent/TR17132A/xx unknown
  • 1972-04-18 JP JP3836672A patent/JPS5312921B1/ja active Pending
  • 1972-04-18 DE DE2218765A patent/DE2218765C3/de not_active Expired
  • 1972-04-19 ES ES401919A patent/ES401919A1/es not_active Expired
  • 1972-04-19 NL NL7205278A patent/NL167720C/xx not_active IP Right Cessation
  • 1972-04-19 BR BR2383/72A patent/BR7202383D0/pt unknown
  • 1972-04-19 AR AR241572A patent/AR200110A1/es active
  • 1972-04-19 RO RO7200070605A patent/RO62423A/ro unknown
  • 1972-04-19 SE SE7205135A patent/SE373382B/xx unknown

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