US3907920A - Two-stage hydropyrolysis-cracking process for producing ethylene - Google Patents

Two-stage hydropyrolysis-cracking process for producing ethylene Download PDF

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US3907920A
US3907920A US454482A US45448274A US3907920A US 3907920 A US3907920 A US 3907920A US 454482 A US454482 A US 454482A US 45448274 A US45448274 A US 45448274A US 3907920 A US3907920 A US 3907920A
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stream
stage
range
hydropyrolysis
zone
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US454482A
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English (en)
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Charles M Starks
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ConocoPhillips Co
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Continental Oil Co
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Priority to US454482A priority Critical patent/US3907920A/en
Priority to ZA00750795A priority patent/ZA75795B/xx
Priority to BE157879A priority patent/BE830876A/fr
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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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Definitions

  • TWO-STAGE HYDROPYROLYSIS-CRACKING PROCESS FOR PRODUCING ETHYLENE This invention relates to an integrated process for producing ethylene. More particularly, theinvention relates to an integrated two-stage hydropyrolysis cracking process for producing ethylene from higher hydrocarbons.
  • a novel integrated two-stage hydropyrolysis-cracking process whereby higher hydrocarbons, including whole crude oil and hydrogenated coal liquids, are pyrolyzed to produce ethylene.
  • the integrated process provides not only for production of ethylene but also methane which can be used in synthetic natural gas. Hydrogen and all other higher organics may be recycled back into the process for eventual conversion to ethylene and methane although it'is possible to make further separations on the heavy organic stream to recover aromatics which include benzene, toluene, and xylenes. In the event aromatics are not separated from the heavy organic stream prior to recycle, it is desirable to hydrogenate the stream to convert unsaturates to saturates.
  • hydrocarbon oils suitable for use in the process of this invention may be defined as those'having a density of less than about 0.99, preferably less than about 0.95, and a Conradson carbon content of less than about weight percent, preferably less than about 2 weight percent.
  • non-distillate and distillate hydrocarbon oils are suitable such as respectively described in US. Pat. No. Re. 27599 and U.S. Pat. No. 3,363,024.
  • crude petroleum or other oils having similar density and volatility characteristics may be used as well as oils derived from coal such as hydrogenated coal oil.
  • Distillate oils boiling in the range of C to 360C may be used.
  • coal tar distillates containing unsubstituted or hydroxy-substituted hydrocarbons can be used. Gases consisting primarily of butane and propane are satisfactory feedstocks. All of the above are intended to be included within the expression hydrocarbon oils.
  • hydrocarbon oils as described above are introduced to a first-stage hydropyrolysis zone along with hydrogen.
  • the hydrocarbon oils are pyrolytically crackedin the presence of hydrogen to lower hydrocarbons.
  • a suitable reactor for conducting the hydropyrolysis is described in US. Pat. No. 3,363,024, supra.
  • Another suitable device is a conventional tubular furnace used in the usual cracking operations.
  • the hydropyrolysis is conducted with a mol ratio of hydrogen to hydrocarbonoils of at leastl/l, preferably at least 3/1.
  • Another factor to be considered in determining the amount of hydrogen to employ in a particular operation is that increased hydrogen favors ethane production over ethylene. This factor has significance in connection with the second-stage cracking in that ethane is dehydrogenated to ethylene in that stage.
  • a further consideration is with the amount of excess hydrogen that must be processed and recycled through the integrated process. All factors considered, it is preferable to operate with hydrogen to hydrocarbon oil mol ratios in the range of about 3/1 to 30/1.
  • the hydrogen for the hydropyrolysis stage is provided by recycling the hydrogen separated in the subsequent separation stage to be described more fully hereinafter, and additionally from any suitable outside source.
  • the hydrogen and hydrocarbon oil feed may be separately introduced to the hydropyrolysis stage or they may be combined and introduced as a mixture.
  • the hydrocarbon may be introduced through an atomizing nozzle using hydrogen as the atomizing gas.
  • the hydrocarbon oil is preheated to a temperature approaching the operating temperature of the hydropyrolysis zone; e.g., 300C to as high as 550C.
  • the hydropyrolysis is carried out at temperatures in the range of 600C to 900C, preferably 700C to 850C. Higher temperatures favor ethylene over ethane. Pressures of at least 5 atmospheres gauge are employed, usually in the range of 5 to atmospheres gauge and preferably in the range of 15 to 30 atmospheres gauge. Lower pressures favor ethylene to ethane. Residence times in the range of 0.1 second to 60 seconds, preferably 0.5 to 20 seconds, are employed. Shorter residence times favor ethylene over ethane.
  • Carbon deposition arising from side reactions in the hydropyrolysis zone can be inhibited by providing a small concentration of sulfur compounds in the hydrocarbon oil feed if not already present; e.g., 10 ppm. This is well known in the art and is generally referred to as passification. Usually the addition of sulfur compounds is done on a continuous basis.
  • the effluent from the first-stage hydropyrolysis zone is then introduced to the second-stage cracking zone.
  • the effluent is subjected to low pressure cracking. Temperatures in the range of 750 to 900C, preferably 800850C, are employed. Pressures usually not above about 2 atmospheres gauge, and preferably not above 1 atmosphere gauge, are used.
  • the residence time may be in the range of about 0.01 second to 10 seconds with 0.1 second to 1 second being preferred.
  • the second-stage zone not only serves to crack higher hydrocarbons in the effluent from the first stage hydropyrolysis zone but also serves to dehydrogenate ethane which is produced both in the first and second stages as well as that recycled.
  • the effluent product mixture from the second stage cracking zone is then processed for recovery of methane and ethylene in the separation zone.
  • Conventional techniques for separating hydrogen, methane, ethylene, ethane and higher hydrocarbons may be employed.
  • a convenient separation and recovery system involves rapidly cooling or quenching the product mixture immediately on exiting from the second-stage cracking zone and then processing the cooled mixture through a series of low-temperature fractional distillation columns as are known in the art.
  • Hydrogen is first separated and recycled to the firststage hydropyrolysis zone as earlier discussed.
  • Methane is then separated and recovered and may be conveniently utilized as a synthetic natural gas component.
  • Ethylene is next to be separated and may be sent to storage or transport as an item of commerce.
  • Ethane is next separated and recycled to the second-stage cracking zone as earlier described.
  • the remaining higher hydrocarbons are then hydrogenated in a conventional manner to remove any unsaturation and recycled to the first-stage hydropyrolysis zone to again be processed and converted to lower hydrocarbons and eventually to ethylene and methane.
  • a further separation step may be performed prior to hydrogenation and recycle. Such separation may be accomplished in any known manner to separate essentially all aromatics or only those components desired. If essentially all aromatics are separated, the remaining higher hydrocarbon stream may be recycled as is to the first-stage hydropyrolysis zone without hydrogenation. It is preferred, however, to hydrogenate the higher hydrocarbon stream prior to recycle even though the aromatics or some of the aromatics have been removed.
  • EXAMPLE 1 A mixture of 2.3 liquid vol/min kerosene (boiling point range of 190C to 270C and a specific gravity of 0.82), 2.65 liquid vol/min water and 161 gas vol/min hydrogen (mol ratio of H to hydrocarbon is about 18.0) are introduced to the first-stage hydropyrolysis zone of a type described in US. Pat. No. 3,363,024. Recycle hydrogen and recycle higher hydrocarbon inlets are also provided. The hydropyrolysis is conducted at temperatures ranging from 750-800C, a pressure of 20.4 atmospheres gauge and a residence time of conducted into a series of fractional distillation columns. Hydrogen is separated and recycled to the firststage hydropyrolysis zone. Methane is separated and sent to storage. Ethylene is separated and sent to storage. Ethane is separated and recycled to the secondstage cracking zone. The remaining higher hydrocarbon stream is hydrogenated and recycled to the firststage hydropyrolysis zone.
  • EXAMPLE 2 A light naphtha (BP 150C) at a rate of 0.034 rnl/min and hydrogen at a rate of cc/min (mol ratio of hydrogen to hydrocarbon to about 16.2) were introduced to a hydropyrolysis zone formed by a %-inch stainless steel tubular, reactor one foot in length of which a volume of about 16 cc in the central area constituted the hot zone.
  • the hydropyrolysis was carried out at a temperature of 750C (hot point), a pressure of 6.8 atmospheres gauge and an average residence time of 2.5 sec.
  • the effiuent from the hydropyrolysis zone was analyzed by GLC as 12.4 weight percent H 36.3 weight percent methane, 1.1 weight percent ethylene, 41.4 weight percent ethane, and 9.0 weight percent higher hydrocarbons.
  • the effluent from the hydropyrolysis is then introduced to second-stage cracking operated under atmospheric pressure and 800850C.
  • Calculations based on thermodynamic equilibrium at 850C indicate a product containing a hydrocarbon distribution as follows: 41 weight percent methane, 23.4 weight percent ethylene, 26.6 Weight percent ethane, 4.9 weight percent benzene, and 4.1 weight percent higher hydrocarbons.
  • the methane, ethylene, and benzene are recovered, the hydrogen and higher hydrocarbons are recycled to the hydropyrolysis zone and the ethane is recycled to the second-stage cracking zone.
  • a process for producing ethylene from higher hydrocarbons comprising a. introducing a hydrocarbon oil and hydrogen to a first-stage hydropyrolysis zone, the mol ratio of hydrogen to hydrocarbon oil being at least l/l;v
  • hydrocarbon oil has a density of less than about 0.99 and a Conradson carbon content of less than about weight percent.
  • a process according to claim 1 wherein the conditions of hydropyrolysis are temperatures in the range of about 700C to 850C, pressures in the range of about 5 to 100 atmospheres gauge and residence times in the range of 0.5 to 20 seconds.
  • a process according to claim 3 wherein the second-stage cracking zone conditions are temperatures in the range of about 800C to 850C, pressures not in excess of about 1 atmosphere gauge and residence times in the range of 0.1 to 1 second.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (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)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US454482A 1974-03-25 1974-03-25 Two-stage hydropyrolysis-cracking process for producing ethylene Expired - Lifetime US3907920A (en)

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Application Number Priority Date Filing Date Title
US454482A US3907920A (en) 1974-03-25 1974-03-25 Two-stage hydropyrolysis-cracking process for producing ethylene
ZA00750795A ZA75795B (en) 1974-03-25 1975-02-07 Two stage hydropyrolysis-cracking process for producing ethylene
BE157879A BE830876A (fr) 1974-03-25 1975-07-01 Procede d'hydropyrolyse et de craquage en deux stades pour produire de l'ethylene

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2306181A1 (fr) * 1975-04-03 1976-10-29 Continental Oil Co Procede de production d'ethylene
US4061562A (en) * 1976-07-12 1977-12-06 Gulf Research & Development Company Thermal cracking of hydrodesulfurized residual petroleum oils
US4127393A (en) * 1975-01-13 1978-11-28 British Gas Corporation Method and apparatus for vaporizing hydrocarbon based liquids
US4179474A (en) * 1977-12-22 1979-12-18 Gulf Research And Development Company Process for conversion of naphtha to ethylene
US4209305A (en) * 1975-12-08 1980-06-24 British Gas Corporation Process for making substitute natural gas
US4244808A (en) * 1978-09-21 1981-01-13 Linde Aktiengesellschaft Method of processing a high-boiling fraction obtained in the cracking of hydrocarbons
US4297204A (en) * 1978-02-17 1981-10-27 Linde Aktiengesellschaft Thermal cracking with post hydrogenation and recycle of heavy fractions
US4405442A (en) * 1981-11-24 1983-09-20 Institut Francais Du Petrole Process for converting heavy oils or petroleum residues to gaseous and distillable hydrocarbons
US6190533B1 (en) * 1996-08-15 2001-02-20 Exxon Chemical Patents Inc. Integrated hydrotreating steam cracking process for the production of olefins
RU2249611C1 (ru) * 2003-12-15 2005-04-10 Открытое акционерное общество "Нижнекамскнефтехим" Способ гидропиролиза углеводородного сырья
RU2548002C1 (ru) * 2014-03-06 2015-04-10 Игорь Анатольевич Мнушкин Способ получения этилена из углеводородного сырья
WO2019111079A1 (fr) 2017-12-04 2019-06-13 Sabic Global Technologies B.V. Procédés et systèmes pour produire des oléfines légères à partir de naphta
FR3076295A1 (fr) * 2018-01-04 2019-07-05 IFP Energies Nouvelles Procede d'hydrotraitement de distillats sous vide comprenant un recyclage de la fraction non convertie
US10899979B2 (en) 2017-08-15 2021-01-26 Sabic Global Technologies, B.V. Light olefin production via an integrated steam cracking and hydrocracking process

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2089616A (en) * 1932-12-14 1937-08-10 Ernest A Ocon Process for the hydrogenation and cracking of hydrocarbon oils
US2245819A (en) * 1937-07-14 1941-06-17 Solvay Process Co Process for the manufacture of ethylene
US3373220A (en) * 1964-08-03 1968-03-12 Phillips Petroleum Co Ethylene production
US3511771A (en) * 1967-07-24 1970-05-12 Exxon Research Engineering Co Integrated hydrofining,hydrodesulfurization and steam cracking process
US3839484A (en) * 1970-07-17 1974-10-01 Marathon Oil Co Pyrolyzing hydrocracked naphthas to produce unsaturated hydrocarbons
US3842138A (en) * 1971-12-21 1974-10-15 Pierrefitte Auby Sa Method of cracking hydrocarbons under hydrogen pressure for the production of olefins

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2089616A (en) * 1932-12-14 1937-08-10 Ernest A Ocon Process for the hydrogenation and cracking of hydrocarbon oils
US2245819A (en) * 1937-07-14 1941-06-17 Solvay Process Co Process for the manufacture of ethylene
US3373220A (en) * 1964-08-03 1968-03-12 Phillips Petroleum Co Ethylene production
US3511771A (en) * 1967-07-24 1970-05-12 Exxon Research Engineering Co Integrated hydrofining,hydrodesulfurization and steam cracking process
US3839484A (en) * 1970-07-17 1974-10-01 Marathon Oil Co Pyrolyzing hydrocracked naphthas to produce unsaturated hydrocarbons
US3842138A (en) * 1971-12-21 1974-10-15 Pierrefitte Auby Sa Method of cracking hydrocarbons under hydrogen pressure for the production of olefins

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4127393A (en) * 1975-01-13 1978-11-28 British Gas Corporation Method and apparatus for vaporizing hydrocarbon based liquids
FR2306181A1 (fr) * 1975-04-03 1976-10-29 Continental Oil Co Procede de production d'ethylene
US4209305A (en) * 1975-12-08 1980-06-24 British Gas Corporation Process for making substitute natural gas
US4061562A (en) * 1976-07-12 1977-12-06 Gulf Research & Development Company Thermal cracking of hydrodesulfurized residual petroleum oils
US4179474A (en) * 1977-12-22 1979-12-18 Gulf Research And Development Company Process for conversion of naphtha to ethylene
US4297204A (en) * 1978-02-17 1981-10-27 Linde Aktiengesellschaft Thermal cracking with post hydrogenation and recycle of heavy fractions
US4244808A (en) * 1978-09-21 1981-01-13 Linde Aktiengesellschaft Method of processing a high-boiling fraction obtained in the cracking of hydrocarbons
US4405442A (en) * 1981-11-24 1983-09-20 Institut Francais Du Petrole Process for converting heavy oils or petroleum residues to gaseous and distillable hydrocarbons
US6190533B1 (en) * 1996-08-15 2001-02-20 Exxon Chemical Patents Inc. Integrated hydrotreating steam cracking process for the production of olefins
RU2249611C1 (ru) * 2003-12-15 2005-04-10 Открытое акционерное общество "Нижнекамскнефтехим" Способ гидропиролиза углеводородного сырья
RU2548002C1 (ru) * 2014-03-06 2015-04-10 Игорь Анатольевич Мнушкин Способ получения этилена из углеводородного сырья
US10899979B2 (en) 2017-08-15 2021-01-26 Sabic Global Technologies, B.V. Light olefin production via an integrated steam cracking and hydrocracking process
WO2019111079A1 (fr) 2017-12-04 2019-06-13 Sabic Global Technologies B.V. Procédés et systèmes pour produire des oléfines légères à partir de naphta
FR3076295A1 (fr) * 2018-01-04 2019-07-05 IFP Energies Nouvelles Procede d'hydrotraitement de distillats sous vide comprenant un recyclage de la fraction non convertie

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BE830876A (fr) 1976-01-02
ZA75795B (en) 1976-01-28

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