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US3018309A - Pyrolytic conversion of paraffins - Google Patents

Pyrolytic conversion of paraffins Download PDF

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Publication number
US3018309A
US3018309A US841380A US84138059A US3018309A US 3018309 A US3018309 A US 3018309A US 841380 A US841380 A US 841380A US 84138059 A US84138059 A US 84138059A US 3018309 A US3018309 A US 3018309A
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United States
Prior art keywords
feed
hydrocarbon
reaction zone
steam
zone
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Expired - Lifetime
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US841380A
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English (en)
Inventor
Joseph C Krejci
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Phillips Petroleum Co
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Phillips Petroleum Co
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Priority to US841380A priority Critical patent/US3018309A/en
Priority to DE19601443014 priority patent/DE1443014A1/de
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Publication of US3018309A publication Critical patent/US3018309A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G9/00Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/34Thermal 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
    • C10G9/36Thermal 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
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20C2-C4 olefins
    • 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
    • Y10S585/919Apparatus considerations
    • Y10S585/921Apparatus considerations using recited apparatus structure
    • Y10S585/924Reactor shape or disposition
    • Y10S585/925Dimension or proportion
    • 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
    • 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
    • Y10S585/955Specified mixing procedure

Definitions

  • the invention is an improvement in the process of my U.S. Patent 2,750,434, issued June 12, 1956.
  • the process disclosed and claimed therein comprises pyrolyzing hydrocarbon feed stocks at temperatures in the range of about 1300 to 3500 F. by introducing a preheated hydrocarbon feed axially into a first cylindrical reaction zone of greater diameter than its length contiguous to and coaxial with a secondY cylindrical reaction zone of lesser diameter than the first zone and of greater length than diameter; injecting tangentially into the first reaction zone a combustible mixture of gaseous fuel and oxidant, such as O2 or air; and burning the mixture to form hot combustion gases for heating the feed; passing the feed, initially surrounded by a helically moving annular blanket of said combustion gases, into the second reaction zone, whereby the feed is heated by the combustion gases to a temperature in the range of 1300 to 3500 F.
  • an object of the invention to provide an improved process for pyrolytically converting hydrocarbon feed stocks containing parans to less saturated hydrocarbons with increased yield of unsaturates and higher concentrations thereof in the reaction efuent. Another object is to provide a pyrolytic process for converting hydrocarbon feed stocks to less saturated products with less formation of coke in the reaction system and particularly in the reactor and in the quench chamber adjacent the eluent end of the reaction system. Another object is to reduce coking in a precracking furnace and increase the unsaturates produced therein. Other objects of the invention will become apparent upon consideration of the aompanying disclosure.
  • the invention comprises incorporating in the feed to the precracking furnace an amount of steam in the range of about 10 to 125 volume percent of the hydrocarbon feed and preheating the mixture to a temperature in the range of 1000 to 1600 F. so as to crack and upgrade a substantial proportion of the hydrocarbon feed, and passing the precracked feed into a reactor of the character described and under the reaction conditions set forth in the aforesaid patent.
  • FIGURE l is a transverse sectional view taken on the line 1-1 of FIGURE 2
  • FIGURE 2 is a cross-sectional view of the furnace taken on the line 2-2 of FIGURE 1.
  • an elongated reaction zone l. is lined with highly refractory material 12, such as corun dum, silica, mullite, zirconia, or sillimanite brick, or other similar suitable materials resistant to high temperatures developed in the reactor.
  • highly refractory material 12 such as corun dum, silica, mullite, zirconia, or sillimanite brick, or other similar suitable materials resistant to high temperatures developed in the reactor.
  • a combustion zone 14 Upstream from and contiguous to reaction zone 10 is a combustion zone 14, axial with zone 10, also lined with refractory material 12.
  • Lining 12 is surrounded by a layer of insulating material 16 and the whole is sheathed in a steel shell 18.
  • Combustion chamber ⁇ 14 should have a relatively large diameter in comparison to "its length while the reverse is true of reaction chamber 10.
  • a feed inlet tube 20 is arranged axially so that hydrocarbon feed introduced therethru passes axially thru both chambers 14 and 10.
  • a coaxial larger conduit 22 for introducing oxygen or air to the axial feed when this is desired.
  • the arrangement of conduits 20 and 22 defines an annular space thru which oxygen or air may be passed into tube 20 thru holes therein (not shown) so that the fuel and air mixture may be passed axially into chamber 14.
  • a cooling jacket 24 surrounds the inner end of injection tube 20 and is connected with an inlet water line 25 and an outlet water line 26. Water is circulated thru the jacket from line 25 along the length of the jacket and back to outlet line 26. This cooling of tube 20 lengthens its life.
  • FIGURE 2 shows combustion chamber 14 coaxial with reaction chamber 10 and provided with tangential ports or tunnels 28 spaced 180"V apart.
  • the outer end of tho tunnel 30 is of smaller diameter than the inner portion.
  • a feed inlet pipe 32 is surrounded by a water jacket 34 of the same or similar construction to jacket 24 provided with inlet and outlet lines 36 and 37, respectively.
  • the inlet assembly is positioned so as to inject the feed thru tunnels 30 and 28 into combustion zone 14 where it is burned.
  • Each tangential inlet conduit 32 is connected with an oxygen or air supply line 40 and a fuel gas supply line 42. Most of the tangentially introduced fuel gas is burned in tunnels 28 and chamber 14.
  • Air line 44 and steam line 45 connect with line 46 leading into preheater 48 containing heating coils 50.
  • Line 47 connects the outlet end of heating coil 50 with line 40 leading into feed injection conduit 32.
  • these gases may bypass preheater 48 thru line 52.
  • a cooling assembly 56 at the eluent end of reaction chamber 10, contiguous and coaxial therewith, comprises a water jacket 58, water-spray 60, water inlet conduit 62 extending thru vthe jacket, a cooling water inlet 64, and a cooling water outlet 66 from jacket space 68.
  • Etlluent hot gases from the reactor are quenched in cooling assembly 56 to below reaction temperature and the quenched gases are passed via conduit 70 to conventional separation means 72 where acetylene is removed thru line 74, ethylene thru line 76, other olens thru line 78, aromatics thru line 86, byproduct paraiins thru line 82, heavy residual materials thru line 84, and water thru line 86.
  • the axial feed comprising steam and parancontaim ing hydrocarbon materail introduced thru lines 88 and 89, respectively, are introduced to pre-cracking furnace 90 thru line 91 where the hydrocarbon feed is subjected ice to cracking in tube coil 92.
  • the partially cracked hot eluent is passed thru line 93 into feed injection tube 20 for injection axially thru combustion chamber 14 into reaction chamber 10.
  • this gas may be introduced thru line 94 to preheater 95 and thence into line 96, or it may bypass heater 95 and pass thru line 97 into line 96.
  • Operation in accordance with the invention comprises injecting a mixture of natural gas (or other fuel gas) and air or oxygen wherein the amount of oxygen is in the range of 50 to 140 percent and, preferably, 90 to l20 percent of theoretical for complete combustion, is preferably preheated and charged to the tangential burners through burner tubes 32 to provide tunnel temperatures up to 3500' F. and sufficient to heat the axial feed to the desired temperature. It is preferred not to heat the air or oxygen in admixture with the fuel gas because of the explosion hazard.
  • the oxygen supply may be heated in admixture with steam, ⁇ in the event steam is utilized in the tangential feed.
  • the axial feed comprising hydrocarbon and steam is preheated in heater or tube cracker 90 to convert paraflins to unsaturates before introducing the hot effluent from line 93 into injection tube 20.
  • the steam admixed with the feed should be in the range of to 125 volume percent of the hydrocarbon. lt is preferred to maintain the steam in the axial feed in the range of 25 to 100 volume percent of the hydrocarbon.
  • This feed is heated preferably to a temperature in the range of 800 to 1600 F. so as to crack and upgrade a substantial proportion of the hydrocarbon in the feed.
  • axial hydrocarbon feed may contain unsaturates, it is preferred to utilize aliphatic paratlins because of their relative cheapness.
  • lt is recognized that unsaturates convert more readily to ethylene and acetylene, but the cost of these hydrocarbons is substantially greater than the cost of corresponding parains.
  • Suitable parains include methane, ethane, propane, butane, pentane, hexane and other available hydrocarbon stocks containing substantial amounts of these parains such as naphtha, kerosene, and gas oils.
  • the parafiins may be introduced singly in high concentration or in admixture with each other or with unsaturates.
  • the axial feed In passing through reaction zone l0, the axial feed is heated to the desired range to produce the desired acetylene and/or ethylene and the effluent is quenched in quenching means 56 by the water injected through spray and by water circulating through jacket 58.
  • the effluent from chamber 10 is quenched to a temperature below reaction temperature which is generally below 800 F.
  • the quenched effluent is then passed through line into conventional product separation means 72 from which the various constituents are separated in known manner and recovered as desired.
  • reaction time is very short in order to avoid overcracking and decomposition to carbon and hydrogen and is usually in the range of 0.5 to 0.001 second and even less.
  • the reaction time depends upon the feed, the temperature in the reaction zone, and the product desired. Reaction time may be calculated in accordance with the equations set forth in my U.S. Patent 2,750,- 434, referred to supra.
  • the volume ratio of steam to O2 is in the range of 1:1 to 8:1 and it is preferred to preheat the steam -03 mixture to the range of 800 to 1600 F.
  • the axial feed was preheated and cracked by being passed through a tube furnace prior to introduction to the reactor.
  • run l no steam was included in the axial feed.
  • run 2 the effect of mixing 25 volume percent steam with the butane may be seen.
  • concentration of the acetylene in the effluent was about 8 hours in each instance.
  • run 3 the volume of steam was doubled but there was no significant improvement in results. However, this run was of only 8 hours duration and it is possible that over longer periods of operation, higher steam concentration may result in further reduction in coking in the quencher.
  • run 4 steam was included in the tangential feed and this feed was preheated to 1015 F.
  • the acetylene concentration was slightly higher than without air preheat and the yield was slightly lower.
  • the composition of the propane feed utilized in the runs predominantly unsatuated hyqmcarbons; .the emuem is as fouowsfrom said second reaction zone is quenched in a quench zone to a temperature below reaction temperature; and Run 5: Percent said unsaturated hydrocarbons are recovered; the im- CaHs 67-8 10 provement comprising including at least 50 volume per- CaHs 0-3 cent of aliphatic paran hydrocarbon in said feed; heatiCiHio 18-7 ing said feed in the preheating step toa temperature in nCiHio 13-2 tha rango of about 10oo to i600' F.
  • reaction conditions invention effects improved yields of ethylene and acetylene Pl'OdtlCmg mallmum Ylelds 0f acetylen, including a illfrom relatively cheap'parans and also decreases the 00 pramI0fat1a5t1900 F-,alemallllallled and afylelle carbon deposition in the reactor and in the quench cham- 1S ICCUVeId from the UIlSalll'ttS- ber at the gluem end of the Nador, 9.
  • reaction conditions 1 claim; producing maximum yields of ethylene, including a tem l.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US841380A 1959-09-21 1959-09-21 Pyrolytic conversion of paraffins Expired - Lifetime US3018309A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US841380A US3018309A (en) 1959-09-21 1959-09-21 Pyrolytic conversion of paraffins
DE19601443014 DE1443014A1 (de) 1959-09-21 1960-09-21 Pyrolytische Umwandlung von Kohlenwasserstoffen

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3081257A (en) * 1960-06-06 1963-03-12 Phillips Petroleum Co Production of aromatic feedstock for carbon black reactors
US3170863A (en) * 1960-09-30 1965-02-23 Monsanto Co Hydrocarbon conversion process
US3213015A (en) * 1963-02-25 1965-10-19 Phillips Petroleum Co Cracking of hydrocarbons with steam or carbon dioxide
US3347949A (en) * 1965-06-15 1967-10-17 Phillips Petroleum Co Heat recovery in thermal conversion process
US4288408A (en) * 1978-07-07 1981-09-08 L. A. Daly Company Apparatus for the diacritic cracking of hydrocarbon feeds for the selective production of ethylene and synthesis gas
US4929797A (en) * 1987-11-14 1990-05-29 Mitsubishi Kasei Corporation Method for producing hydrocarbons having two carbon atoms
US4982039A (en) * 1987-09-03 1991-01-01 University Of Southern California Conversion of halogenated toxic substances
US5942652A (en) * 1994-09-30 1999-08-24 Institut Français Du Petrole Ethane pyrolysis
WO2001090277A1 (en) * 2000-05-25 2001-11-29 Shell Internationale Research Maatschappij B.V. Apparatus and process for vaporizing a heavy hydrocarbon feedstock with steam

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US2790838A (en) * 1952-01-16 1957-04-30 Eastman Kodak Co Process for pyrolysis of hydrocarbons

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2790838A (en) * 1952-01-16 1957-04-30 Eastman Kodak Co Process for pyrolysis of hydrocarbons
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 (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3081257A (en) * 1960-06-06 1963-03-12 Phillips Petroleum Co Production of aromatic feedstock for carbon black reactors
US3170863A (en) * 1960-09-30 1965-02-23 Monsanto Co Hydrocarbon conversion process
US3213015A (en) * 1963-02-25 1965-10-19 Phillips Petroleum Co Cracking of hydrocarbons with steam or carbon dioxide
US3347949A (en) * 1965-06-15 1967-10-17 Phillips Petroleum Co Heat recovery in thermal conversion process
US4288408A (en) * 1978-07-07 1981-09-08 L. A. Daly Company Apparatus for the diacritic cracking of hydrocarbon feeds for the selective production of ethylene and synthesis gas
US4982039A (en) * 1987-09-03 1991-01-01 University Of Southern California Conversion of halogenated toxic substances
US4929797A (en) * 1987-11-14 1990-05-29 Mitsubishi Kasei Corporation Method for producing hydrocarbons having two carbon atoms
US5942652A (en) * 1994-09-30 1999-08-24 Institut Français Du Petrole Ethane pyrolysis
WO2001090277A1 (en) * 2000-05-25 2001-11-29 Shell Internationale Research Maatschappij B.V. Apparatus and process for vaporizing a heavy hydrocarbon feedstock with steam
US20020028977A1 (en) * 2000-05-25 2002-03-07 Krishnamoorthy Chandrasekharan Apparatus and process for vaporizing a heavy hydrocarbon feedstock with steam
AU2001274069B2 (en) * 2000-05-25 2004-05-06 Shell Internationale Research Maatschappij B.V. Apparatus and process for vaporizing a heavy hydrocarbon feedstock with steam
US6797238B2 (en) 2000-05-25 2004-09-28 Shell Oil Company Apparatus and process for vaporizing a heavy hydrocarbon feedstock with steam
US20050014986A1 (en) * 2000-05-25 2005-01-20 Krishnamoorthy Chandrasekharan Apparatus and process for vaporizing a heavy hydrocarbon feedstock with steam
RU2260031C2 (ru) * 2000-05-25 2005-09-10 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Аппарат и способ испарения тяжелого углеводородного перерабатываемого сырья водяным паром
US7374663B2 (en) 2000-05-25 2008-05-20 Shell Oil Company Process for vaporizing a heavy hydrocarbon feedstock with steam

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Publication number Publication date
DE1443014A1 (de) 1969-01-30

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