US3878051A - Desulfurizing coke with phosgene or a mixture of carbon monoxide and chlorine - Google Patents

Desulfurizing coke with phosgene or a mixture of carbon monoxide and chlorine Download PDF

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Publication number
US3878051A
US3878051A US393576A US39357673A US3878051A US 3878051 A US3878051 A US 3878051A US 393576 A US393576 A US 393576A US 39357673 A US39357673 A US 39357673A US 3878051 A US3878051 A US 3878051A
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coke
desulfurizing
chlorine
mixture
carbon monoxide
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US393576A
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English (en)
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Raymond H Long
Morgan C Sze
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Priority to US393576A priority Critical patent/US3878051A/en
Priority to GB5310373A priority patent/GB1449627A/en
Priority to DE2366396A priority patent/DE2366396C1/de
Priority to CA186,266A priority patent/CA1009171A/en
Priority to DE2357736A priority patent/DE2357736C2/de
Priority to JP13160873A priority patent/JPS5336841B2/ja
Priority to FR7341620A priority patent/FR2207863B1/fr
Priority to NL7316073A priority patent/NL7316073A/xx
Priority to IT7062673A priority patent/IT1055545B/it
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Publication of US3878051A publication Critical patent/US3878051A/en
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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
    • 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
    • C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material

Definitions

  • the coke may be admixed with a ferruginous material 17 Claims, 1 Drawing Figure Aqueous Solution of Ground ferric Sulfate and/or ferruginous l Blender l SulfurlcAcrd Material I l Dryer l--1 L J l 1 l l Solid or liquid 1 f Ground 1 carbonaceous erruglnous W .7 m..
  • This invention relates to the desulfurization of coke. and more particularly to a new and improved process for producing a coke having a sulfur content of less than 0.85%.
  • an object of the present invention is to provide a process for providing desulfurized coke.
  • Another object of the present invention is to provide a desulfurized coke having a sulfur content of less than 0.5%.
  • a further object of this present invention is to provide a process capable of producing a desulfurized coke having a sulfur content of less than 0.5% which is prepared from fecdstocks having both high and low sulfur contents.
  • the drawing is a simplified schematic flow diagram illustrating processing steps of the present invention.
  • a process for desulfurizing coke wherein the coke is contacted with a desulfurizing gas. with or without the presence of other additives, at a temperature from about l200F. to about l800F. for a time sufficient to produce a coke having a sulfur content of no greater than 0.85%. and preferably no greater than 0.5%.
  • the desulfurizing gas is either a mixture of carbon monoxide and chlorine or phosgene, and generally also includes a diluent gas. such as nitrogen. in order to minimize the concentration of phosgene (phosgene is also generated when using a mixture of carbon monoxide and chlorine). It is to be understood, however, that a diluent gas need not be present although the use of a diluent is preferred.
  • oxygen can also be present in the gas. In employing a mixture of carbon monoxide and chlorine, the relative proportions of the two materials can vary over a wide range. in that it is believed that the desulfurization is effected by in situ generation of phosgene.
  • the ratio of one of the two components to the other ranges from about 0.5:1 to 1.5:l.
  • the relative proportions can be outside such atypical range in that in situ phosgcne generation can occur outside such ranges, although such an operation is not preferred.
  • the coke which is to be desulfurized is produced from a petroleum feedstock
  • the coke is mixed with a desulfurizing amount of a ferruginous material (iron. oxide of iron or mixtures thereof). as a desulfurizing additive.
  • a ferruginous material iron. oxide of iron or mixtures thereof.
  • the coke is derived from coal containing pyrites. i.e.. pyrites is present in an amount of at least 0.5%. by weight, of the coal. at ferruginous material need not be employed. but in some cases. improved results are obtained by the use of a desulfurizing amount of a ferruginous material.
  • a ferruginous material is also used in effecting the desulfurization.
  • the ferruginous material is either iron and/or an oxide of iron (ferrous oxide and/or ferric oxide) and such ferruginous material may be employed in an impure state.
  • the ferruginous material may be added as taconite fines. iron ore. iron. etc.
  • the ferruginous material, if employed. is in a finely divided state. e.g.. a particle size of l00 mesh with 50% or more being 325 mesh and is present in an amount to provide a ferruginous material to coke weight ratio of from 5:95 to 25:75. and preferably from l0z90 to l5z85.
  • the coke in addition to the ferruginous material. if employed. the coke is admixed with a desulfurizing amount of promoting additive which is either sulfuric acid. ferric sulfate or mixtures thereof in that the presence of such an additive has been found to promote desulfurization of the coke with the desulfurizing gas.
  • the sulfuric acid and/or ferric sulfate additive is generally employed in an amount from about 1% to about 8%, and preferably in an amount from about 3% to about 8%. all by weight. based on coke. In some cases. i.e.. cokes of higher sulfur content produced from petroleum feedstocks. in order to achieve the desired amount of desulfurization, it may be necessary to use sulfuric acid and/or ferric sulfate as a promoting additive in order to produce the desired degree of desulfurization.
  • the desulfurization is effected in a reducing atmosphere at a coke temperature from l200F. to l800F. and preferably at a temperature from I400F. to 1800F.. with a temperature of 1500F. being generally preferred.
  • the furnace or oven in which the desulfurization is effected is generally at a temperature which is l00F. higher than the temperature of the coke).
  • the desulfurization with phosgene or a mixture of carbon monoxide and chlorine can not be effectively employed at coke temperatures in the order of l900F. and higher and. accordingly. in general. the temperature of the coke does not exceed l8()0F.
  • the coke is maintained at the desulfurization temperature for a time sufticient to reduce the sulfur content of the coke to no greater than 0.85%. and preferably no greater than 0.5%
  • the precise time required for such desulfurization will vary with the amount of sulfur originally present in the coke and the distribution, as to type. of the sulfur; i.e.. pyritic. sulfate, sulfide, or organic. ln general, the time is at least one-half hour. with the time period generally not exceeding 16 hours.
  • the required desulfurization time is in the order of l to 8 hours.
  • the coke which is desulfurized in accordance with the present invention may be a coke produced from any one of a wide variety of carbonaceous coking feed stocks. including both liquid feedstocks derived from either petroleum sources. such as reduced crudes. gilsonite. tar sand bitumens and the like or coal sources. such as coal tar pitch or coal tar and solid feedstocks. such as coal.
  • the ferruginous material and/or promoting additive. if employed. may be admixed with the coking feedstock prior to coking or may be admixed with the coke product from a coking process.
  • the coke. is then contacted with the dcsulfurizing gas (phosgene or a mixture of carbon monoxide and chlorine).
  • the dcsulfurizing gas phosgene or a mixture of carbon monoxide and chlorine
  • the ferruginous material is preferably pugged or sprayed with an aqueous solution of the promoting additive and the ferruginous material then mixed with the coking feedstock or coke.
  • the coking feedstock is a solid or the ferruginous material is added to a previously produced coke.
  • a mixture of the carbonaceous material and ferruginous material may be sprayed or pugged with an aqueous solution of the promoting additive.
  • a liquid carbonaceous feedstock may be coked in a delayed or fluid coker. as known in the art, or in a carbonizer; e.g.. an indirect-fired kiln type carbonizer. as known in the art.
  • Coal may be carbonized
  • the invention will be further described with respect to the accompanying drawing which schematically indicates various procedures for practising the present invention.
  • Solid or liquid carbonaceous coking feed may be premixed with. if employed. ground ferruginous material or a ferruginous material which has been previous mixed with an aqueous solution of ferric sulfate and/or sulfuric acid and dried. The carbonaceous feed is then coked or carbonized. and if the ferruginous material has been added to the coking feedstock. or is not required. e.g.. some coals. the coke is desulfurized with phosgene or a mixture of carbon monoxide and chlorine in a desulfurization unit.
  • the coke produced in the coke production unit does not include ferruginous material and a ferruginous material is to be added.
  • the coke is ground and blended with ground ferruginous material or ferruginous material which has been previously blended with an aqueous solution of ferric sulfate and/or sulfuric acid and dried.
  • the coke including the ferruginous material is then desulfurized by contact with phosgene or a mixture of carbon monoxide and chlorine.
  • the desulfurized coke is then washed and dried for use as a low sulfur coke or the washed and dried coke is ground and subjected to magnetic separation to produce a low-sulfur. low ash coke.
  • Coal 100 percent 10 mesh is contacted with the gaseous reactantin a fixed bed in a tubular reactor as wherein the ash content of the coke should be less than one percent, the coke after desulfurization is washed reported in Table ll.
  • the coal is Illinois N0. 6 having and magnetically separated to meet the necessary 4.177( sulfur and the space velocities are in the order of l to 3. Run 4 is not effected in accordance with the invention.
  • the present invention is particularly advantageous in that a coke having a sulfur content of no greater than 0.85%, and preferably no greater than 0.5%, may be produced from a wide variety of feedstocks having a. wide variety of sulfur contents including those having sulfur contents of 4 percent or greater.
  • the process of the present invention is capable of providing greater than 90% desulfurization of feedstocks having sulfur contents of 4% and greater.
  • the desulfurized coke from the above treatment may be burned directly as a pulverized fuel with the potential of satisfying anti-pollution requirements with no further precautions.
  • some benefit may derive from first washing the coke to remove any residual water soluble additives from the coke. lfa lowash fuel is required, magnetic separation will effect the elimination of residual ferruginous materials.
  • a process for desulfurizing coke comprising:
  • a desulfurizing gas comprising a member selected from the group consisting of phosgene and a mixture of carbon monoxide and chlorine, said contacting being effected at a coke temperature from l200F. to l800F. for a time sufficient to produce a coke with a sulfur content of no greater than 0.85%.
  • said coke being admixed with a ferruginous material comprising a member selected from the group consisting of oxides of iron, iron and mixtures thereof for desulfurizing a coke prepared from petroleum and non-pyrites containing coal feedstocks.
  • ferruginous material is present in a ferruginous material to coke weight ratio from 5:95 to 25:75.
  • ferruginous material admixed with coke has a particle size of mesh with at least 50% being 325 mesh.
  • ferruginous material has a particle size of 100 with at least 50% being 325 mesh.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Coke Industry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Industrial Gases (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
US393576A 1972-11-24 1973-08-31 Desulfurizing coke with phosgene or a mixture of carbon monoxide and chlorine Expired - Lifetime US3878051A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
US393576A US3878051A (en) 1972-11-24 1973-08-31 Desulfurizing coke with phosgene or a mixture of carbon monoxide and chlorine
GB5310373A GB1449627A (en) 1972-11-24 1973-11-15 Process for desulphurizing coke
CA186,266A CA1009171A (en) 1972-11-24 1973-11-20 Process for producing low sulfur fuel
DE2357736A DE2357736C2 (de) 1972-11-24 1973-11-20 Verfahren zur Entschwefelung von Koks
DE2366396A DE2366396C1 (de) 1972-11-24 1973-11-20 Verfahren zum Herstellen von entschwefeltem Koks aus Kohle
JP13160873A JPS5336841B2 (cs) 1972-11-24 1973-11-22
FR7341620A FR2207863B1 (cs) 1972-11-24 1973-11-22
NL7316073A NL7316073A (cs) 1972-11-24 1973-11-23
IT7062673A IT1055545B (it) 1973-08-31 1973-12-07 Procedimento per la desolforazione del coke

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US30947072A 1972-11-24 1972-11-24
US393576A US3878051A (en) 1972-11-24 1973-08-31 Desulfurizing coke with phosgene or a mixture of carbon monoxide and chlorine

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US3878051A true US3878051A (en) 1975-04-15

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US393576A Expired - Lifetime US3878051A (en) 1972-11-24 1973-08-31 Desulfurizing coke with phosgene or a mixture of carbon monoxide and chlorine

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US (1) US3878051A (cs)
JP (1) JPS5336841B2 (cs)
CA (1) CA1009171A (cs)
DE (2) DE2366396C1 (cs)
FR (1) FR2207863B1 (cs)
GB (1) GB1449627A (cs)
NL (1) NL7316073A (cs)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4118200A (en) * 1977-07-08 1978-10-03 Cato Research Corporation Process for desulfurizing coal
US4137050A (en) * 1978-03-31 1979-01-30 Standard Oil Company (Ohio) Coal desulfurization
US4264568A (en) * 1978-02-13 1981-04-28 Tosco Corporation Method for easily removing zinc from carbon black contaminated with zinc
US4466362A (en) * 1982-03-03 1984-08-21 Massachusetts Institute Of Technology Method of removing sulfur and other contaminants from the coal in coal-oil slurries
US4511362A (en) * 1983-08-26 1985-04-16 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Fluidized bed desulfurization

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3933596A (en) * 1974-04-01 1976-01-20 The Lummus Company Desulfurization of coke
FR2449119A1 (fr) * 1979-02-16 1980-09-12 Continental Oil Co Procede de preparation de coke de petrole de qualite superieure par cokefaction retardee
DE2914225C2 (de) * 1979-04-09 1983-01-13 Carl Still Gmbh & Co Kg, 4350 Recklinghausen Verfahren zur Erhöhung der Festigkeit von Hüttenkoks
DE2914306C2 (de) * 1979-04-09 1982-10-21 Carl Still Gmbh & Co Kg, 4350 Recklinghausen Verfahren zur Verminderung des Schwefelgehaltes in Koks
FR3138379B1 (fr) 2022-07-29 2024-06-14 Psa Automobiles Sa Goulotte de cablage pour pre fixation d’une batterie automobile
FR3144790A1 (fr) 2023-01-06 2024-07-12 Psa Automobiles Sa Dispositif de maintien d’une piece sur un sous ensemble apres montage

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2657118A (en) * 1950-09-21 1953-10-27 Aluminium Lab Ltd Method of purifying carbonaceous material
US2698777A (en) * 1951-01-26 1955-01-04 Aluminum Lab Ltd Procedure for treating solid material with gas at high temperature
US2793172A (en) * 1954-07-23 1957-05-21 Exxon Research Engineering Co Integrated fluid coke desulfurization process
US3009781A (en) * 1957-02-23 1961-11-21 Shawinigan Chem Ltd Process for preparation of carbon disulphide and for the desulphurization of coke
US3387941A (en) * 1965-03-23 1968-06-11 Carbon Company Process for desulfurizing carbonaceous materials

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE244646C (de) * 1910-06-30 1912-03-14 Simpson William Speirs Verfahren zum Entschwefeln von Kohle beim Destillieren im Vakuum.
AT69286B (de) * 1913-06-05 1915-07-10 Anton Fingerland Verfahren zur Herstellung von schwefelarmen Koks.
FR646439A (fr) * 1927-05-16 1928-11-12 Procédé de distillation des combustibles solides
US2201050A (en) * 1928-08-11 1940-05-14 Oberle Grace Process for producing carbonaceous material
FR739942A (cs) * 1931-07-30 1933-01-19
DE670964C (de) * 1933-09-15 1939-01-28 Erdoel Akt Ges Deutsche Verfahren zum Entaschen von Koks mineralischer Kohlen
DE638055C (de) * 1933-11-26 1936-11-09 Carl Still G M B H Verfahren zum Herstellen von schwefelarmem Koks
DE1266722B (de) * 1954-07-23 1968-04-25 Exxon Research Engineering Co Verfahren zur Entschwefelung von Petrolkoks im Wirbelbett
US2824047A (en) * 1955-08-11 1958-02-18 Consolidation Coal Co Desulfurization of carbonaceous solid fuels
ES388092A1 (es) * 1971-02-09 1973-05-01 Patronato De Investigacion Cie Procedimiento de desulfuracion del coque por tratamiento previo del carbon con reactivos oxidantes gaseosos.
DE2117504C3 (de) * 1971-04-10 1979-06-21 Texaco Development Corp., New York, N.Y. (V.St.A.) Verfahren zur Reinigung von Petrolkoks

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2657118A (en) * 1950-09-21 1953-10-27 Aluminium Lab Ltd Method of purifying carbonaceous material
US2698777A (en) * 1951-01-26 1955-01-04 Aluminum Lab Ltd Procedure for treating solid material with gas at high temperature
US2793172A (en) * 1954-07-23 1957-05-21 Exxon Research Engineering Co Integrated fluid coke desulfurization process
US3009781A (en) * 1957-02-23 1961-11-21 Shawinigan Chem Ltd Process for preparation of carbon disulphide and for the desulphurization of coke
US3387941A (en) * 1965-03-23 1968-06-11 Carbon Company Process for desulfurizing carbonaceous materials

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4118200A (en) * 1977-07-08 1978-10-03 Cato Research Corporation Process for desulfurizing coal
US4264568A (en) * 1978-02-13 1981-04-28 Tosco Corporation Method for easily removing zinc from carbon black contaminated with zinc
US4137050A (en) * 1978-03-31 1979-01-30 Standard Oil Company (Ohio) Coal desulfurization
US4466362A (en) * 1982-03-03 1984-08-21 Massachusetts Institute Of Technology Method of removing sulfur and other contaminants from the coal in coal-oil slurries
US4511362A (en) * 1983-08-26 1985-04-16 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Fluidized bed desulfurization

Also Published As

Publication number Publication date
NL7316073A (cs) 1974-05-28
DE2357736C2 (de) 1982-02-04
DE2357736A1 (de) 1974-05-30
JPS5336841B2 (cs) 1978-10-05
FR2207863A1 (cs) 1974-06-21
CA1009171A (en) 1977-04-26
DE2366396C1 (de) 1982-07-08
FR2207863B1 (cs) 1977-06-10
JPS4998401A (cs) 1974-09-18
GB1449627A (en) 1976-09-15

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