US2362270A - Viscosity reducing - Google Patents

Viscosity reducing Download PDF

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Publication number
US2362270A
US2362270A US44370942A US2362270A US 2362270 A US2362270 A US 2362270A US 44370942 A US44370942 A US 44370942A US 2362270 A US2362270 A US 2362270A
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United States
Prior art keywords
coke
oil
gas
line
vessel
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Charles E Hemminger
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Standard Oil Development Co
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Standard Oil Development Co
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Priority to US36386640A priority Critical
Application filed by Standard Oil Development Co filed Critical Standard Oil Development Co
Priority to US44370942 priority patent/US2362270A/en
Priority to GB13016/42A priority patent/GB559026A/en
Application granted granted Critical
Publication of US2362270A publication Critical patent/US2362270A/en
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Application status is Expired - Lifetime legal-status Critical

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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/28Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid material
    • C10G9/32Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid material according to the "fluidised-bed" technique

Description

N 1944- c. E. HEMMINGER VISCOSITY REDUCING Original Filed Nov. 1, 1940 .SEPARA 7'02 \/CYCLONE T 7 E t w u m G G 6 0% f r m 6 *4 w f 2 a 0 m a a m @P 3 twuwirl T n R k m if m 2 W i R H 5 MN I wnw m m m 6 t M a J 6 w All a lNAET .DISPEPJ/ON CHAMBER ST AM LINE Patented Nov. 7, 1944 VISCOSITY REDUCING Charles E. Hemminger, Westfield, N. J., assignor to Standard Oil Development Company, a corporation of Delaware Original application November 1, 1940, Serial No. 363,866. Divided and this application May 20, 1942, Serial No. 443,709

'6 Claims.

The present application is a division of my copending application, Serial Number 363,866 filed November 1, 1940.

The present invention relates to improvements in the art of treatingheavy hydrocarbon oils thermally for the purpose of converting them into relatively lower boiling range hydrocarbons. For example, the present invention includes processes such as the viscosity reducing or reduced crude petroleum oils to produce gas oil which may be cracked either thermally or catalytically in order to produce gasoline.

My present process involves the viscosity reducing of a relatively high boiling range hydrocarbon in the presence of heated coke to form a gas oil which may find use as a charging stock in a cracking operation. Generally speaking at first, my process involves heating a reduced crude petroleum oil (i. e., a residuum remaining after distilling from the crude oil, the constituents boiling up to say 850 F.) and discharging it into a reaction vessel in the form of a spray where it contacts a solid granulated material having a size of 50 to 400 mesh, with 100 to 200 mesh preferred, such material being for example, petroleum coke, which granulated material is heated to a temperature of about 900-1200 F.

The main object of my invention is to produce gas oil, together with some gasoline and permanent gas from a reduced petroleum crude oil, by heating the reduced crude petroleum oil to high temperatures and thereafter spraying it into an environment containing granulated or ground heated coke.

Another object of my present invention is to reduce the viscosity of a crude petroleum oil in bination of apparatus elements in which my in I vention may be carried into practical effect.

Referring in detail to the drawing, a reduced crude, such as an east Texas residuum from which 75% of the original crude has been removed by distillation, is discharged into the system through line I, the reduced crude being preferably heated to a temperature of 850-950 F. From 11110 I the heated oil is discharged into a manifold 4 disposed in reaction vessel 6. The manifold 4 contains a plurality of nozzles l through which the heated oil is discharged into the interior of vessel 5 in the form of a spray.

' There is also present in reaction vessel 5 a quantity of coke C, as will more fully appear hereafter, thesaid coke having a temperature of about 900-1200 F. Steam is introduced into reactor 5 through line 2. The linear velocity of the oil vapors above the point of oil introduction is from .1 to 4 ft. per second, with 1 to 2 ft. per second preferred. The amount of coke introduced in the vessel should be from 0.5 to 5 times the weight of oil with 1:1 ratio preferred. The heated oil remains resident in reaction vessel 5 for a period of from 5 seconds, whereupon the said oil undergoes distillation and chemical reaction to form 520% gasoline, 642% by weight of coke, 2-5% of gas, and the remainder gas oil, the foregoing percentages being based on the original charging stock. The vapors produced as a result of the viscosity reducing operation are withdrawn from reaction vessel 5 through conduit 0 and are discharged into cyclone separator I0 in which cyclone separator the coke both formed and added is separated from the vapors and thereafter withdrawn through conduit l2. The vapors, on the other hand, are withdrawn from cyclone separator I0 through line I4, and these vapors may be fractionated to produce a gas oil, together with gasoline and normally gaseous hydrocarbons in equipment not shown. The coke in line I2 is discharged into an elutriator l5 and therein dispersed in a gas, such as steam, flue gas, CO: etc. introduced into said elutriator through line Hi. The velocity of the gas passing through i5 is such as to permit heavier or larger particles thereof to settle out and be withdrawn from elutriator I5 through line 20, while the steam or other gas carrying the coke dispersed therein, is discharged into line 22 and thereafter discharged into vessel 24 through line 23.- In vessel 24 the coke containing volatile materials, such as liquid or gaseous'adsorbed hydrocarbons, is subjected to the influence of active combustion. In one modification air is discharged from line 30 into line 23 and thereafter forced into vessel 24 where the coke is at a temperature of from about 900-1200 F. and the air at about atmospheric temperature, combustion of adsorbed hydrocarbons, such as gas oil, tar, and the like, is caused in vessel 24. Excess heat may be removed by cooling tubes 26. It is preferred that the velocity of the suspension in vessel 24 be less than 4 ft. per second, say 3 ft, per sec- 2 a aseaavo nd, although higher velocities may be used. The gaseous products of combustion pass upwardlya through vessel 24 toward the outlet at the top thereof, and thereafter are withdrawn from the vessel 24 through line 32. These vapors' containing coke dispersed therein are discharged into cyclone separator 40 where the coke is separated irom the gases and thereafter discharged through lines 45 and 48 into a dispersion chamber 80. The line 45 isa standpipe and in order to fluidize the catalyst flowing therethrough, a. gas is discharged into 45 through taps 48. (This gas may be steam, a normally gaseous hydrocarbon, due gas, or any material which will serve to import to the coke in line 48 flow characteristics resembling a liquid. The coke in vessel 60 is dispersed by means of steam or some other gas introduced in dispersion chamber 68 through line 69 and thereafter the suspension is forced through line H! into reaction vessel 8.

Referring to cyclone separator 48 in which, as indicated, the burned or revivified coke material is separated from the gases, the flue gas separated from the coke is withdrawn from the system through line as. if desired, cyclone separators it and it may be supplemented by additional cyclone separators in order to remove more connpletely the coke from the hydrocarbon vapors or the products oi combustion.

As an alternate, instead of coke other powdered to materials, such as pumice, silica, alumina, etc., may be used, or an active catalyst such as "Super-= filtrol may be employed. The latter is desirable from the viewpoint that it gives a gasoline oi high octane number, but the coke formation is to high. When using material other than coke, the said material is not removed through line 20, and almost all the coke formed is burnt in vessel 24, the excess heat over that used in the system being removed by a heat transfer medium and/or 40 feed oil in tubes 26.

To recapitulate, my invention comprises a 1 method of viscosity reducing a hydrocarbon oil by spraying oil continuously into a reaction zone containing finely powdered material, suchas:

ground coke, and thereafter separating the reaction vapors from the catalyst, regenerating the coke or the like and returning it to the onstream operation.

Moreover, the invention is not limited to petro- What I claim is: a,

1. The method of reducing the viscosity of a petroleum residuum oil which comprises heating the said oil to a temperature 01' from about 850 F.-950 F., spraying said oil into a viscosity reducing zone containing powdered coke in suspension, permitting the suspension of coke and oil-vapors to flow concurrently upward in the reaction zone, withdrawing the suspended coke and oil vapors from said reaction zone separating the powdered coke from the gases and vapors which are formed in and added to the said zone, suspending the powdered coke in an inert gas, conducting the suspension to a regeneration zone where adsorbed hydrocarbons contained in the coke are burned, separating the regeneration gases from the powdered coke and returning the powdered coke in heated condition to the first named zone for for use in the process.

2. The process set forth in claim 1, in which a portion oi the coke is continuously removed from the system.

3. The method set forth in claim 1, in which it) per cent to 30 per cent by volume of steam is prm ent in the first-ed zone.

e. The method set iorth in claim. 1, in which the particle size or the coke is less than 59 mesh 5. The method of converting heavy petrole oil residues into substantial quantities of oil boil ing substantially within the gasoline and gas cit range, which comprises heating the said heavy oil to a temperature substantially within the range of about Skid-950 F. and injecting it into a conversion zone, simultaneously and separately injecting a suspension or heated powdered coke into said conversion zone, permitting the coke and the oil to remain within said zone for a sur ficlent period of time to effect the desired con= version, withdrawing the reaction products sub stantially in vapor form from said conversion zone, together with added coke and formed coke suspended therein, separating the coke i'rom the vapors, suspending the separated coke in a regeneration gas containing free 0838 charging the last-named suspension into a regeneration zone where it is subjectedto tem= peratures suillciently high to cause combustion or at least partial liquid p hydrocarbons adsorbed by the coke, separating the regenerated coke from the regeneration gases, resuspending the regenerated coke in a gasiionn substance and recycling it to the conversion zone substantially unccoled.

6. The method set forthin claim 5 in which the charging oil is ied to the conversion zone in n. can.

US44370942 1940-11-01 1942-05-20 Viscosity reducing Expired - Lifetime US2362270A (en)

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GB13016/42A GB559026A (en) 1942-09-15 1942-09-15 Improvements in or relating to the thermal conversion of hydrocarbon oils

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Cited By (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2423813A (en) * 1943-04-15 1947-07-08 Socony Vacuum Oil Co Inc Apparatus for handling contact masses
US2423850A (en) * 1945-05-14 1947-07-15 Shell Dev Process for effecting catalytic conversions with finely divided catalysts
US2428715A (en) * 1944-09-08 1947-10-07 Pure Oil Co Catalytic cracking of hydrocarbons
US2431462A (en) * 1942-11-17 1947-11-25 Standard Oil Dev Co Catalytic treatment of hydrocarbons
US2434843A (en) * 1946-01-29 1948-01-20 Socony Vacuum Oil Co Inc Method for hydrocarbon conversion in presence of particle form catalysts
US2456796A (en) * 1944-09-28 1948-12-21 Lummus Co Hydrocarbon coking
US2490798A (en) * 1942-12-30 1949-12-13 Standard Oil Dev Co Apparatus and process for catalytic reactions
US2503291A (en) * 1945-03-14 1950-04-11 William W Odell Process of promoting reactions in a fluidized bed comprising a plurality of catalysts
US2543884A (en) * 1947-08-12 1951-03-06 Standard Oil Dev Co Process for cracking and coking heavy hydryocarbons
US2598058A (en) * 1950-01-06 1952-05-27 Universal Oil Prod Co Continuous conversion and coking of heavy liquid hydrocarbons
US2600078A (en) * 1948-08-25 1952-06-10 Lummus Co Heat transfer pebble
US2606144A (en) * 1949-12-10 1952-08-05 Universal Oil Prod Co Fluidized conversion and coking of heavy petroleums
US2608569A (en) * 1946-08-22 1952-08-26 Standard Oil Dev Co Removal of carbon from hydrocarbon synthesis catalyst
US2608526A (en) * 1946-12-14 1952-08-26 Standard Oil Dev Co Coking of carbonaceous fuels
US2623010A (en) * 1949-09-24 1952-12-23 Lummus Co Oil coker
US2623817A (en) * 1946-04-03 1952-12-30 Standard Oil Dev Co Production of fuel gases
US2624696A (en) * 1949-10-08 1953-01-06 Lummus Co Continuous carbonization of coal and oil mixtures
US2631981A (en) * 1948-07-10 1953-03-17 Sinclair Refining Co Rejection of inactive material from a fluidized catalyst regenerator
US2642340A (en) * 1946-05-10 1953-06-16 Standard Oil Dev Co Production of oxygen
US2654698A (en) * 1950-05-03 1953-10-06 Consolidation Coal Co Low-temperature distillation of coal
US2661324A (en) * 1950-02-25 1953-12-01 Universal Oil Prod Co Conversion of heavy hydrocarbonaceous materials in the presence of subdivided coke
US2662050A (en) * 1949-03-16 1953-12-08 Kellogg M W Co Catalytic conversion of hydrocarbons
US2700642A (en) * 1951-05-08 1955-01-25 Standard Oil Dev Co Coking of heavy hydrocarbonaceous residues
US2707702A (en) * 1949-10-15 1955-05-03 Sinclair Refining Co Art of coking
US2709676A (en) * 1951-05-05 1955-05-31 Exxon Research Engineering Co Production of coke agglomerates
US2717867A (en) * 1949-11-26 1955-09-13 Kellogg M W Co Hydrocarbon conversion
US2719115A (en) * 1950-05-11 1955-09-27 Sinclair Refining Co Method of coking hydrocarbon oils
US2719114A (en) * 1950-02-25 1955-09-27 Universal Oil Prod Co Cracking and coking of heavy hydrocarbon oils in the presence of subdivided material
US2758073A (en) * 1952-09-04 1956-08-07 Exxon Research Engineering Co Fluidized solids distillation process
US2779719A (en) * 1954-04-21 1957-01-29 Exxon Research Engineering Co Quench-elutriator vessel
DE969325C (en) * 1953-07-28 1958-05-22 Exxon Research Engineering Co Method and apparatus for the conversion of high boiling oils to lower boiling products
US2844521A (en) * 1952-10-23 1958-07-22 Exxon Research Engineering Co High temperature coking for chemical production
US2847365A (en) * 1954-04-21 1958-08-12 Exxon Research Engineering Co Coking process and apparatus
US2856346A (en) * 1953-07-21 1958-10-14 Exxon Research Engineering Co Instrumentation for fluid coking of heavy hydrocarbon oils and the like
US2878891A (en) * 1953-10-05 1959-03-24 Exxon Research Engineering Co Loop separator for gases and solids
US2885343A (en) * 1953-07-01 1959-05-05 Hydrocarbon Research Inc Conversion of hydrocarbons
US2885344A (en) * 1953-07-01 1959-05-05 Hydrocarbon Research Inc Conversion of hydrocarbons
US2888395A (en) * 1954-03-29 1959-05-26 Universal Oil Prod Co Hydrocarbon conversion process in the presence of hydrogen produced in the process
US2889267A (en) * 1953-12-31 1959-06-02 Exxon Research Engineering Co Process for cracking oil
US2895904A (en) * 1954-03-15 1959-07-21 Exxon Research Engineering Co Fluid coking process
US2905733A (en) * 1954-12-24 1959-09-22 Exxon Research Engineering Co Combination process for producing olefins from heavy oils
US2913396A (en) * 1953-10-28 1959-11-17 Hydrocarbon Research Inc Contact carrier for hydrocarbon conversion
US2944007A (en) * 1956-12-05 1960-07-05 Exxon Research Engineering Co Solids system for transfer line coking of residua
US2952356A (en) * 1954-04-12 1960-09-13 Exxon Research Engineering Co Control of particle size distribution in fluid coking of petroleum oils
US2953518A (en) * 1957-05-20 1960-09-20 Texaco Inc Coking oil with a fluidized bed of calcium oxide
US2983671A (en) * 1951-05-10 1961-05-09 Gulf Research Development Co Pyrolytic conversion of hydrocarbons with recovery of coke
US3033779A (en) * 1953-07-01 1962-05-08 Hydrocarbon Research Inc Conversion of hydrocarbons with fluidized solid particles in the presence of combustion gases containing hydrogen
US4062760A (en) * 1976-04-20 1977-12-13 Exxon Research And Engineering Company Dry fines recycle in a coking process

Cited By (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2431462A (en) * 1942-11-17 1947-11-25 Standard Oil Dev Co Catalytic treatment of hydrocarbons
US2490798A (en) * 1942-12-30 1949-12-13 Standard Oil Dev Co Apparatus and process for catalytic reactions
US2423813A (en) * 1943-04-15 1947-07-08 Socony Vacuum Oil Co Inc Apparatus for handling contact masses
US2428715A (en) * 1944-09-08 1947-10-07 Pure Oil Co Catalytic cracking of hydrocarbons
US2456796A (en) * 1944-09-28 1948-12-21 Lummus Co Hydrocarbon coking
US2503291A (en) * 1945-03-14 1950-04-11 William W Odell Process of promoting reactions in a fluidized bed comprising a plurality of catalysts
US2423850A (en) * 1945-05-14 1947-07-15 Shell Dev Process for effecting catalytic conversions with finely divided catalysts
US2434843A (en) * 1946-01-29 1948-01-20 Socony Vacuum Oil Co Inc Method for hydrocarbon conversion in presence of particle form catalysts
US2623817A (en) * 1946-04-03 1952-12-30 Standard Oil Dev Co Production of fuel gases
US2642340A (en) * 1946-05-10 1953-06-16 Standard Oil Dev Co Production of oxygen
US2608569A (en) * 1946-08-22 1952-08-26 Standard Oil Dev Co Removal of carbon from hydrocarbon synthesis catalyst
US2608526A (en) * 1946-12-14 1952-08-26 Standard Oil Dev Co Coking of carbonaceous fuels
US2543884A (en) * 1947-08-12 1951-03-06 Standard Oil Dev Co Process for cracking and coking heavy hydryocarbons
US2631981A (en) * 1948-07-10 1953-03-17 Sinclair Refining Co Rejection of inactive material from a fluidized catalyst regenerator
US2600078A (en) * 1948-08-25 1952-06-10 Lummus Co Heat transfer pebble
US2662050A (en) * 1949-03-16 1953-12-08 Kellogg M W Co Catalytic conversion of hydrocarbons
US2623010A (en) * 1949-09-24 1952-12-23 Lummus Co Oil coker
US2624696A (en) * 1949-10-08 1953-01-06 Lummus Co Continuous carbonization of coal and oil mixtures
US2707702A (en) * 1949-10-15 1955-05-03 Sinclair Refining Co Art of coking
US2717867A (en) * 1949-11-26 1955-09-13 Kellogg M W Co Hydrocarbon conversion
US2606144A (en) * 1949-12-10 1952-08-05 Universal Oil Prod Co Fluidized conversion and coking of heavy petroleums
US2598058A (en) * 1950-01-06 1952-05-27 Universal Oil Prod Co Continuous conversion and coking of heavy liquid hydrocarbons
US2661324A (en) * 1950-02-25 1953-12-01 Universal Oil Prod Co Conversion of heavy hydrocarbonaceous materials in the presence of subdivided coke
US2719114A (en) * 1950-02-25 1955-09-27 Universal Oil Prod Co Cracking and coking of heavy hydrocarbon oils in the presence of subdivided material
US2654698A (en) * 1950-05-03 1953-10-06 Consolidation Coal Co Low-temperature distillation of coal
US2719115A (en) * 1950-05-11 1955-09-27 Sinclair Refining Co Method of coking hydrocarbon oils
US2709676A (en) * 1951-05-05 1955-05-31 Exxon Research Engineering Co Production of coke agglomerates
US2700642A (en) * 1951-05-08 1955-01-25 Standard Oil Dev Co Coking of heavy hydrocarbonaceous residues
US2983671A (en) * 1951-05-10 1961-05-09 Gulf Research Development Co Pyrolytic conversion of hydrocarbons with recovery of coke
US2758073A (en) * 1952-09-04 1956-08-07 Exxon Research Engineering Co Fluidized solids distillation process
US2844521A (en) * 1952-10-23 1958-07-22 Exxon Research Engineering Co High temperature coking for chemical production
US3033779A (en) * 1953-07-01 1962-05-08 Hydrocarbon Research Inc Conversion of hydrocarbons with fluidized solid particles in the presence of combustion gases containing hydrogen
US2885344A (en) * 1953-07-01 1959-05-05 Hydrocarbon Research Inc Conversion of hydrocarbons
US2885343A (en) * 1953-07-01 1959-05-05 Hydrocarbon Research Inc Conversion of hydrocarbons
US2856346A (en) * 1953-07-21 1958-10-14 Exxon Research Engineering Co Instrumentation for fluid coking of heavy hydrocarbon oils and the like
DE969325C (en) * 1953-07-28 1958-05-22 Exxon Research Engineering Co Method and apparatus for the conversion of high boiling oils to lower boiling products
US2878891A (en) * 1953-10-05 1959-03-24 Exxon Research Engineering Co Loop separator for gases and solids
US2913396A (en) * 1953-10-28 1959-11-17 Hydrocarbon Research Inc Contact carrier for hydrocarbon conversion
US2889267A (en) * 1953-12-31 1959-06-02 Exxon Research Engineering Co Process for cracking oil
US2895904A (en) * 1954-03-15 1959-07-21 Exxon Research Engineering Co Fluid coking process
US2888395A (en) * 1954-03-29 1959-05-26 Universal Oil Prod Co Hydrocarbon conversion process in the presence of hydrogen produced in the process
US2952356A (en) * 1954-04-12 1960-09-13 Exxon Research Engineering Co Control of particle size distribution in fluid coking of petroleum oils
US2779719A (en) * 1954-04-21 1957-01-29 Exxon Research Engineering Co Quench-elutriator vessel
US2847365A (en) * 1954-04-21 1958-08-12 Exxon Research Engineering Co Coking process and apparatus
US2905733A (en) * 1954-12-24 1959-09-22 Exxon Research Engineering Co Combination process for producing olefins from heavy oils
US2944007A (en) * 1956-12-05 1960-07-05 Exxon Research Engineering Co Solids system for transfer line coking of residua
US2953518A (en) * 1957-05-20 1960-09-20 Texaco Inc Coking oil with a fluidized bed of calcium oxide
US4062760A (en) * 1976-04-20 1977-12-13 Exxon Research And Engineering Company Dry fines recycle in a coking process

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