US3704333A - Thermal decomposition of organic compounds - Google Patents

Thermal decomposition of organic compounds Download PDF

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Publication number
US3704333A
US3704333A US65665A US3704333DA US3704333A US 3704333 A US3704333 A US 3704333A US 65665 A US65665 A US 65665A US 3704333D A US3704333D A US 3704333DA US 3704333 A US3704333 A US 3704333A
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US
United States
Prior art keywords
steam
alloy steel
silicon
protective film
alloy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US65665A
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English (en)
Inventor
Carl D Spangler Jr
Frederick J Radd
Louis H Wolfe
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Vista Chemical Co
ConocoPhillips Co
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Continental Oil Co
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Publication date
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Publication of US3704333A publication Critical patent/US3704333A/en
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Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006Controlling or regulating processes
    • B01J19/002Avoiding undesirable reactions or side-effects, e.g. avoiding explosions, or improving the yield by suppressing side-reactions
    • B01J19/0026Avoiding carbon deposits
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/04Thermal processes
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00Chemistry of hydrocarbon compounds
    • Y10S585/949Miscellaneous considerations
    • Y10S585/95Prevention or removal of corrosion or solid deposits

Definitions

  • the present invention relates generally to the thermal decomposition of organic compounds, and more particularly, but not by wa'y of limitation, to the thermal decomposition of organic compounds in contact with a heatresistant alloy steel.
  • the ethane is commonly charged to a pyrolysis furnace having alloy steel' heating tubes disposed thereinJWhile within the alloy steel heating tubes the ethane is subjected to high pyrolysis temperatures (1300 F. to '2000" F.) to yield the desired ethylene product.
  • alloy steels containing nickel and chromium in varying proportions are useful in constructing highly heat-resistant heating tubes for thermal decomposition furnaces.
  • heat-resistant alloy steel heating tubes ex'hibit longer performance lives than heating tubes formed of other materials, carburization and corrosion of the tubes and the deposition of coke therein has continued to be a problem.
  • Carburization of the tubes which is the diffusion of carbon into the alloy steel causing the formation of carbides, brings about the embrittling thereof. Once the steel has become embrittled it is susceptible to high rates of corrosion and catalytic site formation which in turn leads to the deposition of carbon in the form of coke thereon.
  • the present invention relates to the thermal decomposi- -tion of an organic compound in contact with a heatresistant alloy steel wherein the alloy steel is comprised of at least 1% by weight silicon and the alloy steel is pretreated prior to the thermal decomposition by contact with steam at a temperature and for a period of time effective to form a protective film comprised of silicon oxidation compounds thereon.
  • a further object of the present invention is the provision of an improved process for the thermal decomposi- DESCRIPTION OF THE PREFERRED EMBODIMENTS It has been found by the applicants that the surfaces of heat-resistant alloy steel containing silicon in an amount of at least 1% by weight can be pretreated' by contact with steam at elevated temperatures, and that when such surfaces are subsequently placed inservice for'the thermal decomposition of organic compounds, such as cracking or: disproportionation, the' rate of J carburization and corrosion of such surfaces as well as the deposition of coke thereon are reduced.
  • the present invention is based upon the discovery that contact of alloy steel surfaces containing silicon in an amount of at least about 1% by weight with an oxidizing agent such as steam brings about the formation of a protective film comprised of silicon oxidation compounds. Specifically, when contacted with steam, silicon contained in the alloy steel is oxidized and hydrated to form a protective film of hydrated silicon dioxide (SiO -nH O).
  • Silicates of other elements contained in the'alloy steel are also formed which contribute to the protective film, such as manganese silicate (MnSiO Heat resistant iron-chromium-nickel alloys containing at least about 1% silicon by weight are preferred for use in the present inventionflHowever, other chromium or chromium-nickel type alloys may be utilized so long as silicon is'present' therein in an amount of at least about the silicon containing alloy can be used as a lining in another alloy which will provide the ductility and toughness required, the silicon liner can consist essentially of silicon only.
  • MnSiO Heat resistant iron-chromium-nickel alloys containing at least about 1% silicon by weight are preferred for use in the present inventionflHowever, other chromium or chromium-nickel type alloys may be utilized so long as silicon is'present' therein in an amount of at least about the silicon containing alloy can be used as a lining in another alloy which will provide the ductility and toughness required,
  • duration of the treatment is subject to variation, although lengthy periods are not advantageous. Thus, exposure of the alloy surface to steam contact for at least one minute is required. An exposure for an hour or more is-preferred.
  • a protective film of silicon oxidation compounds may be formed during the thermal decomposition of an organic compound by combining small amounts of steam with the organic compound being processed.
  • the thermal decomposition is carried out the surfaces of the silicon containing alloy steel will be contacted by the steam and the protective film of silicon oxidation compounds formed thereon.
  • Large quantities of steam are not required for this purpose, and it has been found that traces of steam combined with the organic compound are suflicient to'inhibit carburization.
  • steam is added to the organic compound in an amount of from about 0.01 pound steam per pound of organic compound to about 1.0 pound of steam per pound of organic compound.
  • the alloy steel pretreatment described above may be advantageously combined with theaddition of small amounts of steam to the organic compound being thermally decomposed to reduce the carburization, corrosion, and deposition of coke on the alloy steel. That is, after the protective film of silicon oxidation compounds has.
  • the film may be maintained during the carrying out of the decomposition reaction by the addition of small amounts of steam to the organic compound.
  • the present invention is advantageously used for thermal, as opposed to catalytic processes.
  • exemplary of such processes are thermal disproportionation and cracking, e.g., cracking of hydrocarbons such as ethane, propane, etc. to produce olefins or acetylenes.
  • alloy steel is meant those steels which have become prevalent for furnaces recently because of the increased demand for metals capable of withstanding high temperatures and pressures.
  • Such alloys generally, but not by way of limitation, include major portions of iron, chromium, and nickel, and can include minor amounts of such elements as aluminum, manganese, phosphorus, sulfur, molybdenum, tantalum, titanium, and zirconium in addition to silicon which, as hereinbefore described, must be present in an'amount of at least about 1% by weight.
  • EXAMPLE 3 Five identical new cracking furnaces were erected, the tubes being formed of the HK alloy described as sample Number 3 in Table I above. The tubes of one furnace were pretreated with steam at about 1750 F. for about fifteen hours, while the other furnaces were not subjected to any treatment. All five furnaces were then placed on duty cracking ethane to produce ethylene. During the initial approximately five months of operation of these furnaces, the pretreated furnace was on stream about 82.3% of the time, while the average of the other four was about 74.7%.
  • EXAMPLE 4 A cracking furnace having tubes being formed of the HK alloy described as sample Numbers 1 and 2 in Table I above was pretreated with steam at about 1750 F. for about 15 hours prior to placing in ethane cracking service. After approximately five months of operation these tubes were examined for carburization depth. In the HK alloy having 1.0% silicon the carburization depth was one-eighth of an inch and the HK alloy having 1.5% silicon showed no noticeable signs of carburization.
  • said heat resisting alloy steel being comprised of at least 1% by weight silicon
  • pretreating said alloy prior to said thermal cracking by contacting it with steam at a temperature and for a period of time effective to form a protective film thereon of hydrated silicon dioxide.
  • said heat-resistant alloy steel containing at least 1% by weight silicon
  • pretreating said alloy prior to said thermal cracking by contacting it with steam at a temperature and for -a period of time effective to form a protective film thereon comprised of hydrated silicon dioxide; and combining at least about 0.01 pound of steam per pound of hydrocarbon with said hydrocarbon so that during the thermal cracking thereof said alloy is contacted with said steam thereby maintaining said protective film of hydrated silicon dioxide thereon.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Chemical Vapour Deposition (AREA)
US65665A 1970-08-20 1970-08-20 Thermal decomposition of organic compounds Expired - Lifetime US3704333A (en)

Applications Claiming Priority (1)

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US6566570A 1970-08-20 1970-08-20

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US3704333A true US3704333A (en) 1972-11-28

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US (1) US3704333A (cs)
BE (1) BE771594A (cs)
CA (1) CA958037A (cs)
DE (1) DE2141919A1 (cs)
FR (1) FR2103387B1 (cs)
GB (1) GB1332569A (cs)
NL (1) NL7106789A (cs)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4379745A (en) * 1980-11-21 1983-04-12 Exxon Research And Engineering Co. Carburization resistance of austenitic stainless steel tubes
US4410418A (en) * 1982-03-30 1983-10-18 Phillips Petroleum Company Method for reducing carbon formation in a thermal cracking process
US4424083A (en) 1980-11-21 1984-01-03 Exxon Research And Engineering Co. Carburization resistance of austenitic stainless steel tubes
US4454021A (en) * 1981-12-17 1984-06-12 Showa Denko Kabushiki Kaisha Method for thermal cracking of hydrocarbons in an apparatus of an alloy having alkali or alkaline earth metals in the alloy to minimize coke deposition
US4500364A (en) * 1982-04-23 1985-02-19 Exxon Research & Engineering Co. Method of forming a protective aluminum-silicon coating composition for metal substrates
US5399257A (en) * 1991-12-23 1995-03-21 Uop Coke inhibiting process using glass bead treating
US5520751A (en) * 1993-09-24 1996-05-28 Exxon Research And Engineering Company Oxidation of low chromium steels
US6071563A (en) * 1995-04-24 2000-06-06 Corning Incorporated Method of protecting metal
US6228253B1 (en) 1997-06-05 2001-05-08 Zalman Gandman Method for removing and suppressing coke formation during pyrolysis
US6358618B1 (en) 1999-09-22 2002-03-19 Corning Incorporated Protective coating on metal

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1483144A (en) * 1975-04-07 1977-08-17 British Petroleum Co Protective films
JPS5684789A (en) * 1979-12-13 1981-07-10 Toyo Eng Corp High-temperature treatment of hydrocarbon-containing material
GB2233672A (en) * 1989-06-30 1991-01-16 Shell Int Research High temperature treatment of stainless steals used in high temperature reactors
US5208069A (en) * 1991-10-28 1993-05-04 Istituto Guido Donegani S.P.A. Method for passivating the inner surface by deposition of a ceramic coating of an apparatus subject to coking, apparatus prepared thereby, and method of utilizing apparatus prepared thereby
DE19604844C2 (de) * 1996-02-10 1998-02-26 Forschungszentrum Juelich Gmbh Verklebung von nichtoxidischen keramischen, keramometallischen oder metallischen Körpern sowie verfahrensgemäß hergestellte Körper

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4379745A (en) * 1980-11-21 1983-04-12 Exxon Research And Engineering Co. Carburization resistance of austenitic stainless steel tubes
US4424083A (en) 1980-11-21 1984-01-03 Exxon Research And Engineering Co. Carburization resistance of austenitic stainless steel tubes
US4454021A (en) * 1981-12-17 1984-06-12 Showa Denko Kabushiki Kaisha Method for thermal cracking of hydrocarbons in an apparatus of an alloy having alkali or alkaline earth metals in the alloy to minimize coke deposition
US4410418A (en) * 1982-03-30 1983-10-18 Phillips Petroleum Company Method for reducing carbon formation in a thermal cracking process
US4500364A (en) * 1982-04-23 1985-02-19 Exxon Research & Engineering Co. Method of forming a protective aluminum-silicon coating composition for metal substrates
US5399257A (en) * 1991-12-23 1995-03-21 Uop Coke inhibiting process using glass bead treating
US5520751A (en) * 1993-09-24 1996-05-28 Exxon Research And Engineering Company Oxidation of low chromium steels
US6071563A (en) * 1995-04-24 2000-06-06 Corning Incorporated Method of protecting metal
US6228253B1 (en) 1997-06-05 2001-05-08 Zalman Gandman Method for removing and suppressing coke formation during pyrolysis
US6358618B1 (en) 1999-09-22 2002-03-19 Corning Incorporated Protective coating on metal

Also Published As

Publication number Publication date
FR2103387B1 (cs) 1975-01-17
FR2103387A1 (cs) 1972-04-14
CA958037A (en) 1974-11-19
BE771594A (fr) 1972-02-21
NL7106789A (cs) 1972-02-22
GB1332569A (en) 1973-10-03
DE2141919A1 (de) 1972-02-24

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Date Code Title Description
AS Assignment

Owner name: VISTA CHEMICAL COMPANY, 15990 NORTH BARKERS LANDIN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST. SUBJECT TO TERMS OF AGREEMENT DATED JUNE 26,1984;ASSIGNOR:CONOCO INC.;REEL/FRAME:004349/0285

Effective date: 19840720