US3170865A - Method of retarding deposition of coke in petroleum furnaces - Google Patents

Method of retarding deposition of coke in petroleum furnaces Download PDF

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Publication number
US3170865A
US3170865A US124353A US12435361A US3170865A US 3170865 A US3170865 A US 3170865A US 124353 A US124353 A US 124353A US 12435361 A US12435361 A US 12435361A US 3170865 A US3170865 A US 3170865A
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United States
Prior art keywords
petroleum
coke
furnace
furnaces
deposition
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Expired - Lifetime
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US124353A
Inventor
James B Allen
Douglas K Layne
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Dow Silicones Corp
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Dow Corning Corp
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Publication date
Priority to NL277655D priority Critical patent/NL277655A/xx
Priority to NL120318D priority patent/NL120318C/xx
Application filed by Dow Corning Corp filed Critical Dow Corning Corp
Priority to US124353A priority patent/US3170865A/en
Priority to GB25468/62A priority patent/GB958098A/en
Priority to DED39317A priority patent/DE1188235B/en
Application granted granted Critical
Publication of US3170865A publication Critical patent/US3170865A/en
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Expired - Lifetime legal-status Critical Current

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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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/28—Organic compounds containing silicon
    • 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
    • C10B43/00—Preventing or removing incrustations
    • C10B43/14—Preventing incrustations
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
    • C10G9/16—Preventing or removing incrustation

Definitions

  • the furnaces employed for heating the petroleum are tube furnaces in which the petroleum passes through a series of tubes, which tubes are heated to temperatures of 500 to 1000 F. At this temperature the petroleum cracks, but is maintained in liquid form by the high temperature and high pressures employed. The liquid product then passes out of the tube furnace into a second stage where it may be either allowed to solidify as in the case of coke preparation, or it may be burned as in the preparation of carbon black, or the liquid may be put through some other process.
  • the deposition of coke in the tube reduces the rate of flow of the petroleum, thereby subjecting it to the extremely high temperatures for longer than the desired time. This tends to increase the rate of deposition of the coke and thereby complicated the problem.
  • the deposition of coke introduced a hazard due to the weakening of the tube walls.
  • the siloxane can be introduced into the petroleum at any time prior to passage through the furnace. Furthermore, the siloxane can be mixed with the petroleum in any convenient manner.
  • the preferred method is to dilute the silxone with an inert solvent, such as a hydrocarbon solvent. In general, the preferred concentration is from one part siloxane to 30 parts solvent to one part silxone per 50 parts solvent.
  • the siloxane is introduced continuously into the petroleum, however, the rate of introduction need not be constant. In other words, during the initial part of an operation one may introduce the siloXane at the rate of parts per million based on the weight of the petroleum while during the latter part of an operation one may reduce the siloxane to 3 parts per million.
  • methylsiloxane which is in fluid form can be employed in this invention.
  • the term in fluid form means that the siloxane can be either a fluid per se at room temperature or it has been rendered fluid by the introduction of a solvent.
  • methylsiloxane includes those polysiloxanes in which all of the hydrocarbon substituents on the silicon are methyl radicals and it also includes those siloxanes in which some of the substituents are methyl radicals, whereas the other substituents are hydrogen, or hydrocarbon radicals such as ethyl, phenyl, B-phenylpropyl, fl-phenylethyl, or vinyl.
  • the physical structure of the siloxane is immaterial so long as it is in fluid form.
  • the viscosity of the siloxane can range from less than one cs. to non-flowing gums.
  • the siloxane has terminal organic groups or terminal hydroxyl groups or whether it is linear, cyclic or branched in molecular configuration.
  • Example 1 This example illustrates the utility of the method of this invention to prevent coke buildup in a coking furnace employing petroleum residium.
  • the petroleum residium was passed through a pipe line into a coking furnace where it was heated to a temperature of 900 F.
  • the molten residium was then passed through a second line into a cooling tank where the coke was allowed to solidify.
  • a dimethylpolysiloxane of 12,500 cs. was introduced into the petroleum residium prior to passage through the cracking furnace at a rate of 10 parts per million.
  • the siloxane was introduced continuously by dissolving it in kerosene to a concentration of one part of siloxane to 50 parts kersene and then pumping the solution into the petroleum line at a suificient rate to give the desired concentration of siloxane in the petroleum residium.
  • the furnace operated for 8 months without any shutdown due to the deposition of coke in the tubes.
  • the furnace had to be shutdown at least about every three months for the cleaning or replacement of the tubes.
  • Example 2 Equivalent results are obtained when petroleum is passed through a vaporizer furnace and heated at a temperature of 900 F. and the effluent gases thereafter burned to form carbon black.
  • Example 3 Equivalent results are obtained when the following siloxanes are employed in the process of Example 1:
  • a method of extending the furnace life in petroleum furnaces by preventing, or decreasing coke accumulation in the furnace which comprises mixing with the petroleum prior to heating in the furnace from .1 to 100 parts per million of a polyrnethylsiloxane in fluid form, based on the weight of the petroleum.
  • silox-ane is a polydimethylsiloxane.
  • a method of extending the furnace life of petroleum tube furnaces by preventing or decreasing coke accumulation in the furnace which comprises mixing with the petroleum prior to heating in the furnace from .1 to 100 parts per million of a polymethylsiloxane in fluid form, based on the weight of the petroleum.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Silicon Polymers (AREA)

Description

United States Patent 3,170,865 METHOD OF RETARDHNG DEPOSITION 0F COKE IN PET'RQLEUM FURNAES James E. Allen, Houston, and Douglas K. Layne, Arlington, Tern, assignors to Dow Corning Corporation, Midland, Mich, a corporation of Michigan No Drawing. Filed July 17, 1961, Ser. No. 124,353 3 (Ilaims. (Cl. 208-48) One of the continuing problems in the petroleum refining industry is the deposition of coke in furnaces where the petroleum is heated to temperatures above the cracking temperature of that material. This is done in many phases in the refining and preparation of petroleum products.
Usually the furnaces employed for heating the petroleum are tube furnaces in which the petroleum passes through a series of tubes, which tubes are heated to temperatures of 500 to 1000 F. At this temperature the petroleum cracks, but is maintained in liquid form by the high temperature and high pressures employed. The liquid product then passes out of the tube furnace into a second stage where it may be either allowed to solidify as in the case of coke preparation, or it may be burned as in the preparation of carbon black, or the liquid may be put through some other process.
The problem which has heretofore been unsolved has been that in spite of the high temperature and pressure employed in the tube furnaces, there was a deposition of solid carbonaceous material on the walls of the tubes. This deposition continues at a suflicient rate so that it seriously interferes with the flow of petroleum through the furnace. In fact, often the deposition was so rapid that the furnace would have to be shutdown after 30 days operation, or at the most after three months operation in order to clean out the tubes. Most of the time the deposition of the coke was so severe that it was cheaper to merely replace the tubes rather than clean them out.
Furthermore, the deposition of coke in the tube reduces the rate of flow of the petroleum, thereby subjecting it to the extremely high temperatures for longer than the desired time. This tends to increase the rate of deposition of the coke and thereby complicated the problem. In addition, the deposition of coke introduced a hazard due to the weakening of the tube walls.
Applicants have found unexpectedly that this deposition of coke in petroleum furnaces can be prevented, or greatly retarded by mixing with the petroleum prior to introduction into the furnace from .1 to 100 parts per million of a methylpolysiloxane, in fluid form, based upon the weight of the petroleum.
The siloxane can be introduced into the petroleum at any time prior to passage through the furnace. Furthermore, the siloxane can be mixed with the petroleum in any convenient manner. The preferred method is to dilute the silxone with an inert solvent, such as a hydrocarbon solvent. In general, the preferred concentration is from one part siloxane to 30 parts solvent to one part silxone per 50 parts solvent. The siloxane is introduced continuously into the petroleum, however, the rate of introduction need not be constant. In other words, during the initial part of an operation one may introduce the siloXane at the rate of parts per million based on the weight of the petroleum while during the latter part of an operation one may reduce the siloxane to 3 parts per million.
Any methylsiloxane which is in fluid form can be employed in this invention. The term in fluid form" means that the siloxane can be either a fluid per se at room temperature or it has been rendered fluid by the introduction of a solvent. The term methylsiloxane includes those polysiloxanes in which all of the hydrocarbon substituents on the silicon are methyl radicals and it also includes those siloxanes in which some of the substituents are methyl radicals, whereas the other substituents are hydrogen, or hydrocarbon radicals such as ethyl, phenyl, B-phenylpropyl, fl-phenylethyl, or vinyl.
The physical structure of the siloxane is immaterial so long as it is in fluid form. Thus the viscosity of the siloxane can range from less than one cs. to non-flowing gums. Furthermore, it is immaterial whether the siloxane has terminal organic groups or terminal hydroxyl groups or whether it is linear, cyclic or branched in molecular configuration.
The following examples are illustrative only and should not be construed as limiting the invention which is properly delineated in the appended claims.
Example 1 This example illustrates the utility of the method of this invention to prevent coke buildup in a coking furnace employing petroleum residium.
The petroleum residium was passed through a pipe line into a coking furnace where it was heated to a temperature of 900 F. The molten residium was then passed through a second line into a cooling tank where the coke was allowed to solidify. During operation of the apparatus a dimethylpolysiloxane of 12,500 cs. was introduced into the petroleum residium prior to passage through the cracking furnace at a rate of 10 parts per million. The siloxane was introduced continuously by dissolving it in kerosene to a concentration of one part of siloxane to 50 parts kersene and then pumping the solution into the petroleum line at a suificient rate to give the desired concentration of siloxane in the petroleum residium.
The furnace operated for 8 months without any shutdown due to the deposition of coke in the tubes. When the apparatus Was operated without employing the siloxane the furnace had to be shutdown at least about every three months for the cleaning or replacement of the tubes.
Example 2 Equivalent results are obtained when petroleum is passed through a vaporizer furnace and heated at a temperature of 900 F. and the effluent gases thereafter burned to form carbon black.
Example 3 Equivalent results are obtained when the following siloxanes are employed in the process of Example 1:
That which is claimed is: l. A method of extending the furnace life in petroleum furnaces by preventing, or decreasing coke accumulation in the furnace which comprises mixing with the petroleum prior to heating in the furnace from .1 to 100 parts per million of a polyrnethylsiloxane in fluid form, based on the weight of the petroleum.
2. The method of claim 1 in which the silox-ane is a polydimethylsiloxane.
3. A method of extending the furnace life of petroleum tube furnaces by preventing or decreasing coke accumulation in the furnace which comprises mixing with the petroleum prior to heating in the furnace from .1 to 100 parts per million of a polymethylsiloxane in fluid form, based on the weight of the petroleum.
References Cited by the Examiner UNITED STATES PATENTS 2,908,624 10/59 Johnson et a1. 208-48 2,968,616 1/61 Bernard 260-4482 OTHER REFERENCES Silicones, New Tools for Petroleum Operations, F. L. Resin, Oil and Gas Journal, Aug. 2, 1954, page R-1l15.
10 ALPHONSO D. SULLIVAN, Primary Examiner.
MILTON STERMAN, Examiner.

Claims (1)

1. A METHOD OF EXTENDING THE FURNACE LIFE IN PETROLEUM FURNACES BY PREVENTING, OR DECREASING COKE ACCUMULATION IN THE FURNACE WHICH COMPRISES MIXING WITH THE PETROLEUM PRIOR TO HEATING IN THE FURNACE FROM .1 TO 100 PARTS PER MILLION OF A POLYMETHYLSILOXANE IN FLUID FORM, BASED ON THE WEIGHT OF THE PETROLEUM.
US124353A 1961-07-17 1961-07-17 Method of retarding deposition of coke in petroleum furnaces Expired - Lifetime US3170865A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
NL277655D NL277655A (en) 1961-07-17
NL120318D NL120318C (en) 1961-07-17
US124353A US3170865A (en) 1961-07-17 1961-07-17 Method of retarding deposition of coke in petroleum furnaces
GB25468/62A GB958098A (en) 1961-07-17 1962-07-03 Method for retarding a deposition of coke in petroleum furnaces
DED39317A DE1188235B (en) 1961-07-17 1962-07-05 Method of preventing coke from being deposited in petroleum processing furnaces

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US124353A US3170865A (en) 1961-07-17 1961-07-17 Method of retarding deposition of coke in petroleum furnaces

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DE (1) DE1188235B (en)
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3249535A (en) * 1963-07-08 1966-05-03 Dow Corning Method of retarding paraffin clogging in petroleum containers
DE2613787A1 (en) * 1975-04-07 1976-10-21 British Petroleum Co PROCESS FOR FORMING A PROTECTIVE FILM ON A SUBSTRATE SURFACE FILLED AGAINST COK FORMATION
US4009095A (en) * 1973-11-09 1977-02-22 Uop Inc. Mixed-phase fluid distribution for packed chambers
US4098678A (en) * 1977-08-22 1978-07-04 Schwarzenbek Eugene F Cracking catalyst activity maintenance for catalytic cracking process
US4410418A (en) * 1982-03-30 1983-10-18 Phillips Petroleum Company Method for reducing carbon formation in a thermal cracking process
US4511405A (en) * 1982-09-30 1985-04-16 Reed Larry E Antifoulants for thermal cracking processes
US6228253B1 (en) 1997-06-05 2001-05-08 Zalman Gandman Method for removing and suppressing coke formation during pyrolysis

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5420006A (en) * 1977-07-15 1979-02-15 Yurika Kogyo Kk Method of preventing foaming of heavy oil

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2908624A (en) * 1955-12-02 1959-10-13 Nat Aluminate Corp Process of inhibiting deposition of organic substances in heat exchangers and the like operating at elevated temperatures
US2968616A (en) * 1955-11-17 1961-01-17 Pure Oil Co Method of inhibiting scale formation by non-hydrolyzing organopolysiloxane

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2968616A (en) * 1955-11-17 1961-01-17 Pure Oil Co Method of inhibiting scale formation by non-hydrolyzing organopolysiloxane
US2908624A (en) * 1955-12-02 1959-10-13 Nat Aluminate Corp Process of inhibiting deposition of organic substances in heat exchangers and the like operating at elevated temperatures

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3249535A (en) * 1963-07-08 1966-05-03 Dow Corning Method of retarding paraffin clogging in petroleum containers
US4009095A (en) * 1973-11-09 1977-02-22 Uop Inc. Mixed-phase fluid distribution for packed chambers
DE2613787A1 (en) * 1975-04-07 1976-10-21 British Petroleum Co PROCESS FOR FORMING A PROTECTIVE FILM ON A SUBSTRATE SURFACE FILLED AGAINST COK FORMATION
US4099990A (en) * 1975-04-07 1978-07-11 The British Petroleum Company Limited Method of applying a layer of silica on a substrate
US4098678A (en) * 1977-08-22 1978-07-04 Schwarzenbek Eugene F Cracking catalyst activity maintenance for catalytic cracking process
US4410418A (en) * 1982-03-30 1983-10-18 Phillips Petroleum Company Method for reducing carbon formation in a thermal cracking process
US4511405A (en) * 1982-09-30 1985-04-16 Reed Larry E Antifoulants for thermal cracking processes
US6228253B1 (en) 1997-06-05 2001-05-08 Zalman Gandman Method for removing and suppressing coke formation during pyrolysis

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NL277655A (en)
DE1188235B (en) 1965-03-04
GB958098A (en) 1964-05-13

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