US3718708A - Method and apparatus for thermal cracking and quenching - Google Patents

Method and apparatus for thermal cracking and quenching Download PDF

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Publication number
US3718708A
US3718708A US00055403A US3718708DA US3718708A US 3718708 A US3718708 A US 3718708A US 00055403 A US00055403 A US 00055403A US 3718708D A US3718708D A US 3718708DA US 3718708 A US3718708 A US 3718708A
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United States
Prior art keywords
quenching
reaction
heating
tower
molten metals
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Expired - Lifetime
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US00055403A
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English (en)
Inventor
S Suzuki
T Ozawa
M Uyeda
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Mitsui Engineering and Shipbuilding Co Ltd
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Mitsui Engineering and Shipbuilding Co Ltd
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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
    • 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
    • Y10S585/949—Miscellaneous considerations
    • Y10S585/95—Prevention or removal of corrosion or solid deposits

Definitions

  • the object of this invention is to provide a novel apparatus which may be simplified by means of molten metals used as heat carrier and which can exhaust all the cracked coke formed during the reaction out of the reaction zone with the stream of gaseous and vaporous reaction products.
  • Another object of this invention is to prevent deposition of cracked coke in the transfer line between the reaction zone and the quenching zone and deposition of cracked coke on the tube walls of quenching tube bundles by filling up and fluidizing solid grains or oils of high boiling point in the area from the surface of molten metals to the upper part of quenching tube bundles, as well as to prevent deposition by wetting the said tube walls with entraining molten metals.
  • a heating and reaction tower is filled with molten metals, in which dilution agent spouting nozzles for force circulating the molten metals, heating tube bundles and raw material spouting nozzles are submerged.
  • a quenching tower which ice is provided with quenching tube bundles and filled up with fluidized solid grains or oils of high boiling point from the surface of the molten metals to the upper part of the quenching tube bundles.
  • Spouting of dilution agents or raw oils forces the molten metals to circulate and agitate, and the molten metals are heated by the heating tube bundles up to a predetermined temperature, come in contact with the raw oils spouted into the upper or lower portion of the heating tube bundles, and contribute to the thermal cracking reaction.
  • the floating solid grains or oils of high boiling point on the surface of the molten metals are kept in fluidization by means of reaction products and diluent coming out of the heating and reaction tower to prevent deposition of cracked coke in a transfer line and quenching tube bundles in a quenching tower.
  • a heating and reaction tower 2 is filled with single metallic elements of low melting point such as lead, tin, zinc, bismuth, and cadmium or alloys mainly consisting of these elements in a molten state.
  • Liquid or vaporous hydrocarbons are, preferably after pre-heating, charged to a middle part of the heating and reaction tower 2, that is an upper part of heating tube bundles 3 positioned in the heating and reaction tower, through a feedstock supplying nozzle 1 alone or together with diluents such as Water vapour.
  • the hydrocarbons supplied through the feedstock supplying nozzle 1 come in contact with molten metals heated at 700l C. in the heating tube bundles 3 to contribute to thermal cracking reaction for the residence time of shorter than 0.5 second, and then convert to reaction products mainly consisting of gaseous olefines, particularly ethylene, propylene or other olefines and aromatics.
  • Metallic elements of low melting point or alloys mainly consisting of these elements in a molten phase, that is molten metals are accelerated and forced to ascend by the action of spouting hydrocarbons from the feedstock supplying nozzle 1, by the spontaneous circulating action of convection current due to heating in the heating tube bundles 3, by the action of ejecting and spouting diluents, from a high velocity spouting nozzle 4 for dilution agents such as water vapour positioned in the lower part of the heating tube bundles 3, or by the action of ejecting and spouting diluents from a diluents spouting nozzle 5 for regulating the molten metals.
  • the molten metals After contributing to the reaction, the molten metals overflow over an overflowing weir 6 and flow downward along the inner wall of the heating and reaction tower 2. Molten metals, thus, are conve-ctively circulated, and depending of this action the heat of reaction necessary for endothermic cracking reaction can be transferred. In other words. the molten metals serve as heat carrier.
  • the molten metals whose temperature falls to 600-1000" C. due to the reaction, th ough an opening 7 provided at the lower part of the overflow weir 6. and heated up to 700- C. in contact with the heating tube bundles 3.
  • the heating tube bundles 3 are heated by flowing high-temperature fluids such as high-temperature flue gas in the tubes or directly by burning fuels by burners, for instance, a tunnel burner system.
  • the diluent high velocity spouting nozzle 4 is positioned in the lower part of the heating tube bundles 3 for accelerating the molten metals to flow upward and make a uniform ascending current.
  • the circulating rate of the molten metals can be controlled by adjusting the spouting rate of the diluents from the said nozzle. To the said nozzle, not only diluents, but also raw materials can be supplied.
  • the diluent spouting nozzle 5 for flow regulation is positioned at the opening 7 in the lower part of the overflow weir 6 for more severely flow adjustment, and the circulating rate can be varied by adjusting the spouting rate from the said nozzle.
  • the cracked coke formed during the thermal cracking reaction has the specific gravity smaller than that of molten metals, so that it is readily separated from the molten metals and exhausted together with reaction products from the heating and reaction tower 2, without circulating together with the molten metals.
  • the reaction products accompanied with diluents, cracked coke and entrained molten metals enter a quenching tower 9 through a transfer line 8 directly joined with the upper part of the heating and reaction tower 2.
  • quenching tube bundles 10 are provided for quenching the reaction products. Solid grains such as sand are contained in an area from the surface of the molten metals to the upper part of the quenching tube bundles 10 and are kept in a fluidization state by reaction products and diluents.
  • the transfer line 8 is formed in a smaller way in cross section and separates the heating and reaction tower 2 from the quenching tower 9.
  • a uniformly distributing structure 11 built up with fireproof materials to reduce the cross section at area, and by the structure the reaction products and diluents coming from the heating and reaction tower 2 are uniformly distributed to keep the solid grains in a uniform fluidization state in the quenching tower 9.
  • the cross section of the transfer line 8 is reduced in order to raise the flow rate of the reaction products and diluents not to allow the solid grains to fall down frequently from the upper part and absorb heat of the molten metals.
  • the average temperature of the solid grain layer which is kept in fluidized motion in the quenching tower 9 provided with the quenching tube bundles 10 is kept. at 200-- 600 C.
  • the temperature of the reaction products and diluents such as water vapour ascending from the heating and reaction tower 2 is 600-1000 C., and they are quenched to 200600 C. in contact with the solid grain layer and the quenching tube bundles 10.
  • the coke formed in quenching is apt to deposit on the walls of the quenching tube bundles 10', but it is immediately stripped off and removed by frictional collision of the solid grains.
  • the entrained molten metals coming from the heating and reaction owner 2 also promote the action of the stripping off and removing of deposits on the tube walls. More particularly, the molten metals collide against the tube walls of the quenching tube bundles 10 and wet them to prevent the coke from depositing directly on the tube walls.
  • the cracked coke adhering on the surface of solid grains, the cracked coke stripped off from tube walls and other places, and the cracked coke formed in reaction in the heating and reaction tower 2 are pulverized by friction and collision in the solid grain layer, exhausted through an exhaust tube 12, together with the reaction products and diluents, and treated by a well-known method.
  • a transfer line 8 and a quenching tower 9 can be directly connected to a reaction tower 2 which is not provided with a diluent spouting nozzle for flow regulation 5, an overflow weir 6 and an opening 7, a so-called reaction tower of a forced agitating type.
  • raw materials of hydrocarbons are preferably supplied from a diluent high velocity spouting nozzle 4.
  • the quenching tower 9 can be filled with oils having high boiling point, instead of solid grains.
  • oils having high boiling point cracked coke is not exhausted through an exhaust tube 12 but contained in the oils having high boiling point. Accordingly, it should be noted that Conradson carbon in the oils must not exceed 40% by weight.
  • Solid grains or oils of high boiling point and molten metals are made up intermittently from a make-up nozzle 13. On starting up the operation solid grains or oils of high boiling point and solid metals are supplied from a supply nozzle 14. In shutting down the operation, solid grains or oils of high boiling point are discharged from a discharge nozzle 15 and molten metals are exhausted from an exhaust nozzle 16. The entrained molten metals gather together in the lower part of a quenching tower 9 during the operation and flow down along the inner wall of a transfer line 8.
  • the solid grains or oils of high boiling point are discharged from a discharge nozzle 17 by a well-known method to keep the surface of the layer in the quenching tower 9 at predetermined level.
  • fluid molten metals are used as heat carrier in this invention, there is no need to employ such a regenerator for heat carrier grains as used in a conventional heat carrier grain circulation system.
  • Heating of the molten metal heat carrier and thermal cracking of the hydrocarbons can be performed successively by circulating molten metal heat carrier or agitating it in a tower.
  • the apparatus is very simplified, the investment cost is low, the site area is reduced and the operation becomes very easy.
  • cracked coke formed in thermal cracking reaction accompanies reaction products to be exhausted from the heating and reaction tower, the reaction system is never inhibited by coke.
  • the quenching tower filled with fluid solid grains or oils of high boiling point from the surface of molten metals to the upper part of the quenching tube bundles is installed just above the heating and reaction tower, the problem of coke deposition in the transfer line between the heating and reaction tower and the quenching tower is resolved by continuous removal of cracked coke due to collision of solid grains or flow of oils of high boiling point, and also the deposition of coke is prevented by molten metals wetting the inner wall of the transfer line. Cracked coke which is going to deposit on the walls of quenching tube bundles in quenching is similarly continuously removed by collision of solid grains or flow of oils of high boiling point, and cracked coke hardly deposits on the walls as entraining solid metals also collide against the walls and wet them. Thus, there can be treated hydrocarbons having high boiling point and those containing much Conradson carbon.

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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)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
US00055403A 1969-07-18 1970-07-16 Method and apparatus for thermal cracking and quenching Expired - Lifetime US3718708A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP44056987A JPS4820523B1 (enrdf_load_stackoverflow) 1969-07-18 1969-07-18

Publications (1)

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US3718708A true US3718708A (en) 1973-02-27

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US00055403A Expired - Lifetime US3718708A (en) 1969-07-18 1970-07-16 Method and apparatus for thermal cracking and quenching

Country Status (6)

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US (1) US3718708A (enrdf_load_stackoverflow)
JP (1) JPS4820523B1 (enrdf_load_stackoverflow)
DE (1) DE2035630C3 (enrdf_load_stackoverflow)
FR (1) FR2051862B1 (enrdf_load_stackoverflow)
GB (1) GB1279514A (enrdf_load_stackoverflow)
NL (1) NL7010563A (enrdf_load_stackoverflow)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4012457A (en) * 1975-10-06 1977-03-15 Shell Development Company Thermal cracking method for the production of ethylene and propylene in a molten metal bath
US4345990A (en) * 1979-04-12 1982-08-24 Boliden Aktiebolag Method for recovering oil and/or gas from carbonaceous materials
US4351275A (en) * 1979-10-05 1982-09-28 Stone & Webster Engineering Corp. Solids quench boiler and process
US4356151A (en) * 1979-10-05 1982-10-26 Stone & Webster Engineering Corp. Solids quench boiler
US4426359A (en) 1980-07-03 1984-01-17 Stone & Webster Engineering Corp. Solids quench boiler
US4437979A (en) 1980-07-03 1984-03-20 Stone & Webster Engineering Corp. Solids quench boiler and process
US4702818A (en) * 1983-11-28 1987-10-27 Mitsubishi Jukogyo Kabushiki Kaisha Process for recovering heat of a tar-containing high-temperature gas
DE3490292C2 (de) * 1984-06-29 1989-07-20 Sankyo Yuki Kk Verfahren und Vorrichtung zur Kohleverfl}ssigung
US5073249A (en) * 1989-11-21 1991-12-17 Mobil Oil Corporation Heavy oil catalytic cracking process and apparatus
US5110448A (en) * 1991-03-12 1992-05-05 Adams Stephen P Coking process
US5762659A (en) * 1990-03-08 1998-06-09 Katona; Paul G. Waste processing
US20100155216A1 (en) * 2008-12-23 2010-06-24 Benham Roger A Device and method for thermal decomposition of organic materials
US10676355B2 (en) 2014-10-23 2020-06-09 Ipco Germany Gmbh Device for cooling a fluid

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4012457A (en) * 1975-10-06 1977-03-15 Shell Development Company Thermal cracking method for the production of ethylene and propylene in a molten metal bath
US4345990A (en) * 1979-04-12 1982-08-24 Boliden Aktiebolag Method for recovering oil and/or gas from carbonaceous materials
US4351275A (en) * 1979-10-05 1982-09-28 Stone & Webster Engineering Corp. Solids quench boiler and process
US4356151A (en) * 1979-10-05 1982-10-26 Stone & Webster Engineering Corp. Solids quench boiler
US4426359A (en) 1980-07-03 1984-01-17 Stone & Webster Engineering Corp. Solids quench boiler
US4437979A (en) 1980-07-03 1984-03-20 Stone & Webster Engineering Corp. Solids quench boiler and process
US4702818A (en) * 1983-11-28 1987-10-27 Mitsubishi Jukogyo Kabushiki Kaisha Process for recovering heat of a tar-containing high-temperature gas
DE3490292C2 (de) * 1984-06-29 1989-07-20 Sankyo Yuki Kk Verfahren und Vorrichtung zur Kohleverfl}ssigung
US5073249A (en) * 1989-11-21 1991-12-17 Mobil Oil Corporation Heavy oil catalytic cracking process and apparatus
US5762659A (en) * 1990-03-08 1998-06-09 Katona; Paul G. Waste processing
US5110448A (en) * 1991-03-12 1992-05-05 Adams Stephen P Coking process
US20100155216A1 (en) * 2008-12-23 2010-06-24 Benham Roger A Device and method for thermal decomposition of organic materials
US8506765B2 (en) * 2008-12-23 2013-08-13 Roger A. Benham Device and method for thermal decomposition of organic materials
US10676355B2 (en) 2014-10-23 2020-06-09 Ipco Germany Gmbh Device for cooling a fluid

Also Published As

Publication number Publication date
FR2051862A1 (enrdf_load_stackoverflow) 1971-04-09
DE2035630B2 (de) 1974-05-30
JPS4820523B1 (enrdf_load_stackoverflow) 1973-06-21
FR2051862B1 (enrdf_load_stackoverflow) 1973-07-13
DE2035630C3 (de) 1975-02-13
GB1279514A (en) 1972-06-28
DE2035630A1 (de) 1971-02-18
NL7010563A (enrdf_load_stackoverflow) 1971-01-20

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