US3563709A - Apparatus for pyrolyzing hydrocarbons - Google Patents

Apparatus for pyrolyzing hydrocarbons Download PDF

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Publication number
US3563709A
US3563709A US760240A US3563709DA US3563709A US 3563709 A US3563709 A US 3563709A US 760240 A US760240 A US 760240A US 3563709D A US3563709D A US 3563709DA US 3563709 A US3563709 A US 3563709A
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United States
Prior art keywords
chamber
temperature
pyrolysis
raw material
oxygen
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
US760240A
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English (en)
Inventor
Miloslav Staud
Anatolij Lazarev
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CHEPOS Z CHEMICKEHO A POTRAVIN
CHEPOS ZAVODY CHEMICKEHO A POTRAVINARSKEHO STROJIRENSTVI
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CHEPOS Z CHEMICKEHO A POTRAVIN
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    • 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
    • C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
    • C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • 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
    • Y10S48/00—Gas: heating and illuminating
    • Y10S48/05—Diffusion membrane for gas reaction or separation
    • 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
    • Y10S585/00—Chemistry of hydrocarbon compounds
    • Y10S585/909—Heat considerations
    • Y10S585/91—Exploiting or conserving heat of quenching, reaction, or regeneration
    • 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
    • Y10S585/00—Chemistry of hydrocarbon compounds
    • Y10S585/919—Apparatus considerations
    • Y10S585/921—Apparatus considerations using recited apparatus structure
    • 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
    • Y10S585/00—Chemistry of hydrocarbon compounds
    • Y10S585/919—Apparatus considerations
    • Y10S585/921—Apparatus considerations using recited apparatus structure
    • Y10S585/922—Reactor fluid manipulating device
    • Y10S585/923—At reactor inlet

Definitions

  • This invention relates to the pyrolysis of hydrocarbons to unsaturated aliphatic hydrocarbons having fewer carbon atoms, and particularly to a pyrolyzing method and to apparatus for performing the method.
  • a primary object of the invention is the provision of a continuous pyrolysis method for a hydrocarbon raw material in which the temperature can be controlled at will along the stream of reactants, more particularly, the raw material is heated almost instantaneously to the pyrolysis temperature, and the thermal energy consumed by the endothermic reaction is replenished as needed to provide constant or even rising temperature through the reaction zone.
  • Another object is the provision of reliable and practical apparatus for performing the method.
  • An additional amount of oxygen bearing gas is introduced inward of the conduit through the porous wall at a rate suflicient to supply the thermal energy consumed by the endothermic pyrolysis reaction, whereby the temperature is at least substantially maintained, but may be increased by oxidation of a portion of the reaction products. The remainder of the products is then withdrawn from the conduit.
  • the apparatus employed includes the burner required for burning the fuel, a reaction chamber having a wall of permeable material, and a source of hydrocarbon raw material.
  • a mixing device is interposed between the burner and the reaction chamber and is connected to the raw material source for receiving the combustion gas and the raw material, mixing the same, and discharging the mixture so produced into the reaction chamber.
  • a pressure chamber is in contact with a face of the aforementioned wall outside the reaction chamber and means are provided for feeding an oxygen bearing gas to the pressure chamber.
  • the reaction chamber has an outlet for discharge of a reaction mixture formed therein, and a cooling device is provided for cooling the discharged reaction mixture.
  • FIG. 1 shows a pyrolysis apparatus of the invention in side elevation, and partly in section
  • FIG. 2 shows a modified element for use in the apparatus of FIG. 1.
  • the otherwise closed top wall of the combustion chamber 1 is separately supplied with fuel and oxygen through supply lines 8, 9, and the length of the flame and the tem-.
  • perature of the combustion gas can be controlled in a known manner by a steam inlet 10 on the lower portion of the combustion chamber near the mixer 2.
  • the apparatus is further equipped with control valves in the several supply lines for proper adjustment of process variables, and with indicating or recording instruments for measuring flow rates of materials entering the illustrated apparatus and for indicating temperatures wherever of interest.
  • the combustion chamber 1, the mixer 2 and the cooling chamber 6 are lined with refractory material in a conventional manner.
  • the wall 4 is made of sintered spherical particles of phosphorbronze having a nominal composition of 92% copper and 8% tin, and a solidus temperature of 880 C.
  • Other materials which have been used'successfully include a similar bronze wall prepared by sintering short length of wire, walls of sintered nickel and stainless steel, and sintered ceramic materials such as alumina, zi'rconia, mullite, or cermets consisting mainly of'alumina or chromium oxide and Cr, Mo, Co, Was the metallic constituent. It is preferred to prepare the porous wall 4 by sintering, but other methods of construction may be resorted to.
  • Any gas containing elementary oxygen may be employed for combustion if commercially pure oxygen is not available or if the resulting dilution of the product is acceptable. Atmospheric air or air enriched with oxygen 'may thus be employed.
  • the temperature of the combustion gas can reach as steam through the inlet 10.
  • the hot gas is mixed in the throat of the Venturi mixer 2 with the hydrocarbon raw material that isto be pyrolyz ed and which is initially in the liquid state.
  • the temperature of the hydrocarbons is raised almost instan taneous ly to the desired pyrolysis temperature by suitable control of the feed rates.
  • the reaction temperature is 750 C. for the preparation of propylene and ethylene as the predominant pyrolysis products, and somewhat higher if it is desired to prepare mainly ethylene aiid acetylene, the necessary conditions of pyrolysis being well known among those skilled in the art and not different in the method of this invention from the usual operating conditions.
  • the period during which the raw material isheated through the temperature range below the pyrolysis temperature is extremely short, and the percentage of undesired products known to be generated at the lower temperatures by polymerization, dehydrogenation, or cracking is minimal. It is further reduced if the temperature in the reaction chamber is controlled to rise in the direction'of fluid flow.
  • Thermal energy is supplied to the stream of material in the chamber 5 by partial combustion of the pyrolysis products with secondary oxygen supplied through the porous wall 4 from the pressure chamber 15. Hydrogen, methane, and carbon monoxide in the mixture are preferentially oxidized to maintain the initial pyrolysis temperature, or to raise the temperature of the gaseous stream for further pyrolysis of compounds of relatively low much as 3000 C. and may be adjusted by introducing molecular weight formed in the initial stage of pyrolysis.
  • the reaction mixture is quickly cooled in the chamber 6, typically to about 500 C., by a fluid coolant introduced through the pipe 13.
  • a fluid coolant may be employed as coolant, and it may be liquid or gaseous. Water in the liquid form or as steam may be employed, but liquid or gaseous hydrocarbons have also been employed.
  • An excess of liquid coolant, if any, is withdrawn through the bottom flange 14 whereas the gaseous pyrolysis products together with combustion products and volatile coolant are withdrawn from the illustrated apparatus through the outlet 7 for recovery of thermal energy and fractionation in a conventional manner.
  • EXAMPLE 1 A laboratory reactor of the type shown in FIG. 1 was used for pyrolysis of a gasoline fraction boiling between 80 and 180 C.
  • the porous wall 40f the reactor had an internal diameter of 40 mm., and other dimensions of the combustion chamber 1, the Venturi mixer 2, and the vessel 3 may be read from the drawing which is substantially to scale with respect to elements 1, 2, 3, 4.
  • the combustion chamber was supplied with 0.415 cubic meter of a fuel gas consisting of 42% hydrogen, 38% carbon monoxide, and 20% methane, and having a net heating value of 4.792 cal. per m It will be understood that all percentage ,values are by volume unless stated otherwise, and that absolute values of gas volume relate to measurements reduced to standard conditions of temperature and pressure.
  • Oxygen was supplied to the combustion chamber 1 at a rate of 0.440 m. and to the pressure chamber 15 at a rate of 0.140 m. per kg. of hydrocarbon stock.
  • the dwell time of the reaction mixture in the tube 4 was 0.01 to 0.001 second, and the temperature in the tube had an average value of approximately 1,000 to 1,100 C., and increased by about 200 C. in the direction of gas flow.
  • the pressure in the tube 4 was approximately 7 p.s.i.g., and the pressure differential across the wall 4 was approximately 20 mm. Hg.
  • the effiuent gas contained, on a dry basis, 20.7% ethylene, 3.9% acetylene, 4.5% propylene, and 28.9% hydrogen, the remainder being carbon monoxide, carbon dioxide, methane, and smaller amounts of ethane, propane and butane.
  • the material recovered by condensation per kilogram of raw gasoline feed consisted of 0.418 kg. ethylene, 0.074 acetylene, and 0.139 propylene.
  • Example 2 The reactor of Example 1 was supplied with the same gasoline fraction at a rate of 5 kg. per hour.
  • the combustion chamber was supplied, per kilogram of hydrocarbon stock, with 0.480 m. fuel gas and 0.510 ml oxygen while 0.162 m. oxygen were fed to the pressure chamber 15.
  • the temperature in the tube 4 varied from 1,500 C. near the Venturi mixer 2 to 1,700 C. near the cooling chamber 6.
  • the dwell time in the pyrolysis zone was approximately 0.001 to 0.0001 second and the pressure about 7 p.s.i.g.
  • the pressure differential across the porous Wall was 25 mg. Hg.
  • combustion means for burning said fuel to a combustion gas
  • reaction chamber having a wall of permeable material
  • mixing means interposed between said combustion means and said reaction chamber for receiving said combustion gas and said raw material, for mixing the received combustion gas with said raw material, and for discharging the mixture so produced into said reaction chamber;
  • said wall of permeable material forming said reaction chamber extending longitudinally, and being cylindrically shaped, a vessel constituting said pressure chamber, said vessel surrounding, and being coextensive and eccentric with, said reaction chamber.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
US760240A 1966-10-14 1968-09-17 Apparatus for pyrolyzing hydrocarbons Expired - Lifetime US3563709A (en)

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Application Number Priority Date Filing Date Title
CS653566 1966-10-14

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US61144A Expired - Lifetime US3692862A (en) 1966-10-14 1970-08-05 Method for pyrolyzing hydrocarbons

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DE (1) DE1643811A1 (cs)
FR (1) FR1555656A (cs)
GB (1) GB1178449A (cs)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4038036A (en) * 1974-09-16 1977-07-26 The Ralph M. Parsons Company Apparatus for the production of sulfur from mixtures of hydrogen sulfide and fixed nitrogen compounds
WO1982002548A1 (en) * 1981-01-27 1982-08-05 Maxwell P Sweeney Partial oxidation system
FR2528443A1 (fr) * 1982-06-14 1983-12-16 Neste Oy Procede de craquage thermique d'huiles d'hydrocarbures
US4724272A (en) * 1984-04-17 1988-02-09 Rockwell International Corporation Method of controlling pyrolysis temperature
US4760210A (en) * 1981-01-27 1988-07-26 Sweeney Maxwell P Partial oxidation system
US4832822A (en) * 1983-05-20 1989-05-23 Rhone-Poulenc Chimie De Base Steam cracking of hydrocarbons
US4983783A (en) * 1989-07-25 1991-01-08 Illinois Institute Of Technology Reduction in carbon oxides in oxidative pyrolysis of halogenated methanes
EP2888216A4 (en) * 2012-08-21 2016-03-30 Uop Llc METHODAL CONVERSION DEVICE AND METHOD USING AN OVERHEAD RATE REACTOR
EP2888210A4 (en) * 2012-08-21 2016-04-20 Uop Llc METHODAL CONVERSION DEVICE AND METHOD USING AN ULTRASOUND FLOW REACTOR
EP2888211A4 (en) * 2012-08-21 2016-06-22 Uop Llc METHODAL CONVERSION DEVICE AND METHOD USING AN OVERHEAD RATE REACTOR
US10029957B2 (en) * 2012-08-21 2018-07-24 Uop Llc Methane conversion apparatus and process using a supersonic flow reactor
US10160697B2 (en) * 2012-08-21 2018-12-25 Uop Llc Methane conversion apparatus and process using a supersonic flow reactor
US10214464B2 (en) * 2012-08-21 2019-02-26 Uop Llc Steady state high temperature reactor
US11143399B2 (en) * 2018-05-09 2021-10-12 Paloma Co., Ltd Premixing device and combustion device

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4044068A (en) * 1975-10-14 1977-08-23 Allied Chemical Corporation Process and apparatus for autothermic cracking of ethane to ethylene
US4321131A (en) * 1981-04-15 1982-03-23 Union Carbide Corporation Process for heat carrier generation
US4536603A (en) * 1983-12-22 1985-08-20 Rockwell International Corporation Production of acetylene from coal by contact with a combustion gas
US5104417A (en) * 1990-07-13 1992-04-14 E. I. Du Pont De Nemours And Company Substitute coal from acetylene production by-products
GB9117216D0 (en) * 1991-08-09 1991-09-25 British Petroleum Co Plc Process for the production of mono-olefins
US5344862A (en) * 1991-10-25 1994-09-06 Kimberly-Clark Corporation Thermoplastic compositions and nonwoven webs prepared therefrom
WO1997002223A2 (en) * 1995-06-30 1997-01-23 Vitaly Lissianski Method for producing ethylene and other chemicals
GB0229497D0 (en) * 2002-12-18 2003-01-22 Bp Chem Int Ltd Process for the production of olefins
US8450552B2 (en) * 2009-05-18 2013-05-28 Exxonmobil Chemical Patents Inc. Pyrolysis reactor materials and methods
CN101920187B (zh) * 2010-09-17 2012-10-24 王仲华 一种裂解反应制备低碳烯烃的设备及方法
KR20160147482A (ko) * 2015-06-15 2016-12-23 삼성전자주식회사 가스 혼합부를 갖는 반도체 소자 제조 설비

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1808168A (en) * 1923-07-31 1931-06-02 Standard Oil Dev Co Dehydrogenating hydrocarbons
US2174288A (en) * 1935-06-07 1939-09-26 Ig Farbenindustrie Ag Production of olefins from gaseous or vaporous saturated hydrocarbons
US2387731A (en) * 1943-07-06 1945-10-30 Phillips Petroleum Co Manufacture of diolefins
US2790838A (en) * 1952-01-16 1957-04-30 Eastman Kodak Co Process for pyrolysis of hydrocarbons
US3161695A (en) * 1960-05-13 1964-12-15 Du Pont Process for making acetylene
US3361839A (en) * 1964-10-28 1968-01-02 Universal Oil Prod Co Dehydrogenation process
US3375288A (en) * 1964-10-28 1968-03-26 Universal Oil Prod Co Dehydrogenation of hydrocarbons at high conversion levels

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4038036A (en) * 1974-09-16 1977-07-26 The Ralph M. Parsons Company Apparatus for the production of sulfur from mixtures of hydrogen sulfide and fixed nitrogen compounds
WO1982002548A1 (en) * 1981-01-27 1982-08-05 Maxwell P Sweeney Partial oxidation system
US4760210A (en) * 1981-01-27 1988-07-26 Sweeney Maxwell P Partial oxidation system
FR2528443A1 (fr) * 1982-06-14 1983-12-16 Neste Oy Procede de craquage thermique d'huiles d'hydrocarbures
WO1984000036A1 (en) * 1982-06-14 1984-01-05 Neste Oy Procedure for thermal cracking of hydrocarbon oils
US4832822A (en) * 1983-05-20 1989-05-23 Rhone-Poulenc Chimie De Base Steam cracking of hydrocarbons
US4724272A (en) * 1984-04-17 1988-02-09 Rockwell International Corporation Method of controlling pyrolysis temperature
US4983783A (en) * 1989-07-25 1991-01-08 Illinois Institute Of Technology Reduction in carbon oxides in oxidative pyrolysis of halogenated methanes
WO1991001285A1 (en) * 1989-07-25 1991-02-07 The Dow Chemical Company Oxidative pyrolysis of halogenated methanes
EP2888210A4 (en) * 2012-08-21 2016-04-20 Uop Llc METHODAL CONVERSION DEVICE AND METHOD USING AN ULTRASOUND FLOW REACTOR
EP2888216A4 (en) * 2012-08-21 2016-03-30 Uop Llc METHODAL CONVERSION DEVICE AND METHOD USING AN OVERHEAD RATE REACTOR
EP2888211A4 (en) * 2012-08-21 2016-06-22 Uop Llc METHODAL CONVERSION DEVICE AND METHOD USING AN OVERHEAD RATE REACTOR
US9656229B2 (en) 2012-08-21 2017-05-23 Uop Llc Methane conversion apparatus and process using a supersonic flow reactor
US9707530B2 (en) 2012-08-21 2017-07-18 Uop Llc Methane conversion apparatus and process using a supersonic flow reactor
US10029957B2 (en) * 2012-08-21 2018-07-24 Uop Llc Methane conversion apparatus and process using a supersonic flow reactor
US10160697B2 (en) * 2012-08-21 2018-12-25 Uop Llc Methane conversion apparatus and process using a supersonic flow reactor
US10166524B2 (en) * 2012-08-21 2019-01-01 Uop Llc Methane conversion apparatus and process using a supersonic flow reactor
US10195574B2 (en) * 2012-08-21 2019-02-05 Uop Llc Methane conversion apparatus and process using a supersonic flow reactor
US10214464B2 (en) * 2012-08-21 2019-02-26 Uop Llc Steady state high temperature reactor
US11143399B2 (en) * 2018-05-09 2021-10-12 Paloma Co., Ltd Premixing device and combustion device

Also Published As

Publication number Publication date
GB1178449A (en) 1970-01-21
DE1643811A1 (de) 1971-03-11
FR1555656A (cs) 1969-01-31
US3692862A (en) 1972-09-19

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