US3005857A - Process for the production of unsaturated hydrocarbons from liquid hydrocarbons - Google Patents

Process for the production of unsaturated hydrocarbons from liquid hydrocarbons Download PDF

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Publication number
US3005857A
US3005857A US843099A US84309959A US3005857A US 3005857 A US3005857 A US 3005857A US 843099 A US843099 A US 843099A US 84309959 A US84309959 A US 84309959A US 3005857 A US3005857 A US 3005857A
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United States
Prior art keywords
hydrocarbons
cracking
liquid
wall
temperature
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US843099A
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English (en)
Inventor
Steinhofer Adolph
Buschmann Karl
Unterstenhoefer Leo
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BASF SE
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BASF SE
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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
    • Y10S585/00—Chemistry of hydrocarbon compounds
    • Y10S585/909—Heat considerations
    • Y10S585/911—Heat considerations introducing, maintaining, or removing heat by atypical procedure

Definitions

  • This process has the disadvantage that part of the substance to be cracked is cracked at the hot wall of the reaction chamber so that carbon black-and coke are formed which may give rise to disturbances in the reaction chamber and also in the apparatus attached thereto behind the same.
  • This disadvantage is especially evident in the cracking of high boiling hydrocarbons, as for example heavy residue oils, because these are very .difficult to atomize and tend to a high degree to form carbon black and coke.
  • One object of theinvention is to provide a process for the production of unsaturated hydrocarbons, especially ethylene, propylene and acetylene, by thermal cracking in hot gases, by which the formation of carbonaceous deposits, e.g., carbon black and coke, is avoided.
  • Another object of'the invention is to provide a method of thermally cracking liquid hydrocarbons by means of hot gases, in which no heat-carrying solids are used.
  • a further object of the invention is to provide a process of the said kind, in which the liquid hydrocarbons are vaporized inside the reaction chamber rather than prior to their introduction into the same.
  • a temperature distribution of this kind is achieved by allowing gases or vapors, especially steam, acting as a propellant, of a temperature which does not cause appreciable cracking, i.e., about 200 to 400 C., advantageously 250 to 350 C., to flow with a high speed of 50 to 300 meters per second, especially 100 to 200 meters per second, tangentially into a cylindrical reaction chamber through which hot gases flow axially as a heat carrier.
  • the substance to be cracked is introduced through one or more tubes near to the wall with a free outlet to the chamber Wall, advantageously tangentially or radially, so that it is spread out by the tangential stream of propellant gas to form a rotating band like a film along the wall of the chamber.
  • the liquid hydrocarbons are thereby vaporized by heat radiation from the core of the chamber and brought by gradual thorough mixing with the hot gases to the temperature necessary for cracking.
  • the average temperature of the reaction mixture on its path through the reaction chamber increases Patented Oct. 24, 1961 continually from the beginning of the reaction chamber to its end.
  • the process is carried out at temperatures between 600 and 1400 C. When using high temperatures, as for example about 900 to 1400" C., and very short residence periods, mainly acetylene is obtained, and at lower temperatures (600 to 900 C.) and longer residence periods, mainly olefines are produced.
  • Initial materials which may be used in the process according to our invention are hydrocarbons which are liquid under normal conditions.
  • Suitable hydrocarbons include gasolenes, petroleum and petroleum fractions as well as residues from petroleum distillation, such as gasolene having a boiling range fromto 220 C., middle oil fractions boiling between and 350 C., as well as higher-boiling hydrocarbons such as bunker-C oil.
  • gases include inert gases such as nitrogen or carbon dioxide, combustible gases such as hydrogen and/or carbon monoxide, and also mixtures thereof.
  • the amount of gas used may be, for example, from 10 to 80% by volume with reference to steam.
  • the steam may be usedfin amount of from 0.2 to 1 kg, preferably 0.3 to 0.5 kg, per kilogram of hydrocarbon introduced.
  • the heat required for the cracking is introduced directly into the reaction zone by means of hot gases.
  • Gases which may serve as heat carriers include inert gases, such as nitrogen or carbon dioxide, and vapors, e.g. steam. It is preferable, however, to produce a hot gas in a combustion chamber arranged before the reaction chamber by burning a fuel, e.g., natural gas, gasolenes, or fuel oil, and to introduce the hot gas directly into the reaction chamber.
  • a fuel e.g., natural gas, gasolenes, or fuel oil
  • the hot gas should be heated to a temperature of between 800 and 1500 C., preferably between 1000 and 1400 C.
  • combustion gas produced in a burner 1 is led through an intermediate member 2, which may have various shapes depending on the liquid hydrocarbon being used and the desired cracked products, into a reaction chamber 3 in axial direction.
  • the intermediate member 2 may, as shown in FIGURE 1, be offset from the reaction chamber 3, or as shown in FIG- URE 2, may pass into the same directly without forming corners.
  • an attachment 4 having a tangential rectangular opening into the reaction chamber, the propellant gas flows at a temperature up to about 300 C., and the liquid hydrocarbon freely flowing through a pipe 5 is thereby spread out to a film-like band on the wall of the chamber.
  • the propellant gas for example steam or another vapor or gas, with which oxygen may also be mixed in order to achieve the desired temperature, advantageously to 200 C., by combustion of part of the combustible fraction, rotates along the wall of the chamber at high speed.
  • the combustion gas flows in axial direction.
  • the cracking of the vapors of the hydrocarbon thereby takes place to form unsaturated hydrocarbons.
  • the propellant gas which cools the wall of the chamber mixes during its path to the end of the chamber with the cracked gases until the intended cracking temperature is achieved through the entire cross-section of the chamber.
  • FIGURES l to 3 give difierent possibilities for the construction of the reactors.
  • the intermediate member 2 is oflset with respect to the reaction chamber 3.
  • the latter is subdivided into two chambers of which the first is connected to the second by a conical section and the second widens conically toward its end.
  • intermediate member 2 may also be prolonged by a hollow jet member of refractory material to enhance the heat radiation to the film-like band of liquid hydrocarbon and a part may project into the reaction chamber.
  • the gaseous unsaturated hydrocarbons produced are cooled to such a temperature that after-reactions can no. longer occur. This is effected for example by spraying in Water or by injecting other volatile cooling agents. Since it is preferable to carry out the process under a pressure of 2 or more, e.g. 2 to 50, especially '15 to 30 excess atmospheres, the cooling may also be achieved by partial or complete decompression of the gases.
  • Example for the production of heat for cracking 18 kilograms per hour of heavy residue oil are burned in a previous burner with the addition of 22.5 kilograms per hour of steam. 17 cubic meters of oxygen per hour being necessary for the purpose.
  • the gas passes into the reaction chamber at a temperature of about 1200 to 1300 C.
  • 31 kilograms per hour of bunker-C oil are introduced into the reaction chamber at the same time.
  • 13.5 kilograms per hour of steam, serving as a propellant, are used for spreading out the oil.
  • the cracking temperature decays from 780 C. to about 550 C.
  • the composition of the cracked gas obtained is as follows:
  • propylene and acetylene by thermal cracking of hydrocarbons which are liquid under normal conditions in hot gases at temperatures of from 600 to 1400 C., which comprises introducing a liquid hydrocarbon onto the inner wall of a cylindrical reaction zone, spreading out said liquid hydrocarbon to be cracked to a film-like rotating band on said inner wall of said cylindrical chamber by means of steam introduced tangentially with respect to said inner wall and having a temperature below that which efliects appreciable cracking and at a speed of to 30-0 meters per second, and vaporizing and cracking the liquid hydrocarbons by means of a hot gas which is made to enter the cylindrical zone at a temperature of from 800 to1500" C. and which fiows through said cylindrical zone in axial direction.
  • a process for the production of unsaturated hydrocarbons selected from the group consisting of ethylene, propylene and acetylene by thermal cracking of hydrocarbons which are liquid under normal conditions in hot gas at temperatures of from 600 to 1400" C. and pressures of 2 to 50 excess atmospheres which comprises introducing a liquid hydrocarbon onto the inner wall of a cylindrical reaction zone spreading out said liquid hydrocarbon to be cracked to a film-like rotating band on said inner wall of said cylindrical Zone by means of steam introduced tangentially with respect to said inner wall at a temperature of 200 to 400 C. and at a speed of from to 200 meters per second, and vaporizing and cracking the liquid hydrocarbons by means of hot gases at 800 to 1500 C. produced in a burner arranged in front of said cylindrical zone and flowing through said cylindrical zone in axial direction.

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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)
US843099A 1958-09-30 1959-09-29 Process for the production of unsaturated hydrocarbons from liquid hydrocarbons Expired - Lifetime US3005857A (en)

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DE3005857X 1958-09-30

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FR (1) FR1236499A (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3116344A (en) * 1960-08-19 1963-12-31 Shell Oil Co Vortex tube reactor and process for converting hydrocarbons therein
US3240836A (en) * 1960-06-21 1966-03-15 Hoechst Ag Process for cracking hydrocarbons
US3397251A (en) * 1964-09-30 1968-08-13 Glinka Carl Method of producing ethylene and acetylene
US3959401A (en) * 1973-05-14 1976-05-25 Union Carbide Corporation Process for cracking
US4458096A (en) * 1983-05-26 1984-07-03 Air Products And Chemicals, Inc. Process for the production of ethylene and propylene
US4613426A (en) * 1983-06-30 1986-09-23 Mitsubishi Jukoygo Kabushiki Kaisha Thermal cracking process for producing petrochemical products from hydrocarbons
US4832822A (en) * 1983-05-20 1989-05-23 Rhone-Poulenc Chimie De Base Steam cracking of hydrocarbons

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4142963A (en) * 1977-06-07 1979-03-06 Union Carbide Corporation Penetration enhanced fluid mixing method for thermal hydrocarbon cracking

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2372591A (en) * 1943-04-03 1945-03-27 Harald E Lonngren Method and means of cracking petroleum oils
US2413407A (en) * 1941-12-18 1946-12-31 Bonard Claude Method of cracking hydrocarbons in the presence of a diluent gas
US2750434A (en) * 1953-06-11 1956-06-12 Phillips Petroleum Co Conversion of hydrocarbons
US2750420A (en) * 1953-04-29 1956-06-12 Phillips Petroleum Co Conversion of hydrocarbons

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2413407A (en) * 1941-12-18 1946-12-31 Bonard Claude Method of cracking hydrocarbons in the presence of a diluent gas
US2372591A (en) * 1943-04-03 1945-03-27 Harald E Lonngren Method and means of cracking petroleum oils
US2750420A (en) * 1953-04-29 1956-06-12 Phillips Petroleum Co Conversion of hydrocarbons
US2750434A (en) * 1953-06-11 1956-06-12 Phillips Petroleum Co Conversion of hydrocarbons

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3240836A (en) * 1960-06-21 1966-03-15 Hoechst Ag Process for cracking hydrocarbons
US3116344A (en) * 1960-08-19 1963-12-31 Shell Oil Co Vortex tube reactor and process for converting hydrocarbons therein
US3397251A (en) * 1964-09-30 1968-08-13 Glinka Carl Method of producing ethylene and acetylene
US3959401A (en) * 1973-05-14 1976-05-25 Union Carbide Corporation Process for cracking
US4832822A (en) * 1983-05-20 1989-05-23 Rhone-Poulenc Chimie De Base Steam cracking of hydrocarbons
US4458096A (en) * 1983-05-26 1984-07-03 Air Products And Chemicals, Inc. Process for the production of ethylene and propylene
US4613426A (en) * 1983-06-30 1986-09-23 Mitsubishi Jukoygo Kabushiki Kaisha Thermal cracking process for producing petrochemical products from hydrocarbons

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FR1236499A (fr) 1960-07-15

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