US3617493A - Process for steam cracking crude oil - Google Patents

Process for steam cracking crude oil Download PDF

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Publication number
US3617493A
US3617493A US2258A US3617493DA US3617493A US 3617493 A US3617493 A US 3617493A US 2258 A US2258 A US 2258A US 3617493D A US3617493D A US 3617493DA US 3617493 A US3617493 A US 3617493A
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steam
cracking
fraction
zone
feed
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Guy B Wirth
Charles E Jahnig
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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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
    • C10G51/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only
    • C10G51/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural parallel stages only

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  • ABSTRACT An improved process for steam cracking a crude oil feed to produce products useful as chemical raw materials or fuels characterized by the steps wherein the crude oil feed is first passed through the convection section of a steam cracking furnace to vaporize the materials in the feed boiling below about 450 F., i.e.. a naphtha fraction. The vaporized portion of the crude oil feed is then separated from the liquid portion of the feed by passing the liquid and vapor fractions into a separation zone, i.e., a flash drum separator wherein the vaporized portion of the feed passes overhead and is then fed, with steam, into the steam cracking furnace and subjected to short residence time, high-temperature cracking conditions.
  • a separation zone i.e., a flash drum separator
  • This invention relates to an improved process for the steam cracking of crude oil and heavy unsaturated hydrocarbon feedstocks. More specifically, this invention relates to a twostage process for steam cracking a crude oil feed wherein about 50 volume percent of the feed has a boiling point above 900 F. In the two-stage process of this invention, the feed is first passed to the convection section of a steam cracking furnace to flash off those volatile materials which vaporize below about 450 F.
  • This vaporize portion of the feed which corresponds approximately to a naphtha fraction, along with the remaining liquid portion of the crude feed is introduced into a separation zone, i.e. flash drum separator.
  • the vaporized portion of the feed passes overhead from the separation zone and then being admixed with steam, is introduced back into convection and then the radiant section of the steam cracking furnace.
  • the conditions under which the first cracking furnace are operated are those conditions, i.e. residence time and cracking temperature, which are optimum for the cracking of a naphtha fraction to form valuable chemical raw materials.
  • liquid portion of the feed is withdrawn from the first separation zone and passed through the convection section of a second steam cracking furnace and then introduced into a second separation zone.
  • Stripping steam is introduced either into the liquid stream withdrawn from the first separation zone or into the bottom portion of the second separation zone, i.e. flash drum separator, to flash off i.e. overhead, materials boiling above about 450 F. and below about l,l F., i.e. a gas oil fraction.
  • This vapor mixture after leaving the second separation zone, is cooled about 50-200 F. in order to liquefy a portion of said vapor mixture. Through this process, entrained droplets of liquid hydrocarbon are washed from the vapor mixture.
  • the cracking conditions employed in the second steam cracking furnace are those which are optimum for the cracking of a gas oil fraction. in this manner, both the naphtha fraction and the gas oil fraction are each cracked under their own specific optimum cracking conditions while eliminating the need for a crude still to separately form a naphtha fraction and a gas oil fraction.
  • the cracking conditions i.e. temperature, steam rate, pressure, etc.
  • severities can be selected to optimize the product yields and minimize coking or operability problems for each feed stream.
  • stripping steam in the second flash drum separator serves not only to reduce the hydrocarbon partial pressure in the flash drum and thus allow more hydrocarbon to vaporize, but also provides the diluent steam, i.e. carrying and cracking medium, for the vaporized hydrocarbon fraction passing overhead from the second separation zone into the second steam cracking furnace.
  • the products formed in the cracking process may then be separated using well-known separation techniques.
  • the crude oil is fractionated in a crude still into a light fraction, i.e. naphtha, a middle fraction, i.e. gas oil and a heavy residuum fraction, i.e. topped crude.
  • a light fraction i.e. naphtha
  • a middle fraction i.e. gas oil and a heavy residuum fraction
  • topped crude Either the naphtha or the gas oil fraction can be subsequently subjected to thermal-cracking, i.e. steam cracking or catalytic refining treatment processes to obtain lower boiling products, i.e. ethylene, propylene, butadiene and the like.
  • the topped crude is generally subjected to a further distillation at reduced pressure in a vacuum still to recover a light fraction, i.e. vacuum gas oil and a heavy fraction, i.e. vacuum residuum.
  • the vacuum gas oil may then be steam cracked or catalytically treated, as above, and the
  • the type of crude oil which is employed as the hydrocarbon feed significantly afi'ects the percentage of the naphtha and gas oil fractions obtained and thus the amount of the crude which can be ultimately subjected to thermal cracking processes.
  • a process is described wherein a crude oil feed, having a high gasoline content is heated with steam in the convection section of a cracking oven; passed into a separation zone where nonvolatilized components are separated off, and thereafter the volatilized components are thermally cracked.
  • a major deficiency associated with such a process is that lower temperatures must be used in the cracking zone to prevent fouling.
  • the crude oil feed is passed into the convection section of a steam cracking furnace wherein the temperatures are in the range of from about 450 to 700 F. in order to vaporize the materials in the feed boiling below about 450 F.
  • the vaporized portion of the crude feed which is in the range of from about 20 to 50 wt. percent based on feed, is then introduced along with the liquid portion of the feed, i.e. that portion of the feed which was not flashed in the convection section of the furnace, into a separation zone, i.e.
  • the separation zone is operated at a pressure of from about 30 to about I00 p.s.i.g. or greater such that the vaporized portion of the feed passes overhead and is then admixed with about 0.1 to 2.0, and more preferably 0.4 to 0.7 pounds of steam per pound of hydrocarbon before being introduced into the cracking zone in the steam cracking furnace.
  • the feed to the first cracking zone comprises about 10 to 67 wt. percent steam in order to lower the hydrocarbon partial pressure and thus increase yields to low molecular weight hydrocarbons.
  • This vaporized portion of the feed which approximates a naphtha fraction, along with the above-described amount of steam, is cracked in the radiant section of a steam cracking furnace under those conditions which are optimum for the cracking of a naphtha fraction.
  • the vaporized feed in the cracking zone is cracked at a temperate at the outlet of the furnace coil between about 1,500 to about 1,700 F., with a residence time in the radiant section, i.e. cracking section of the steam cracking furnace of about 0.1 to 0.5 seconds with a steam dilution of about 0.4 to about 0.7 pounds of steam per pound of hydrocarbon feed.
  • the liquid portion of the crude feed which forms a liquid phase in the bottom portion of the first flash drum separator is withdrawn therefrom and passed through the convection section of a second cracking furnace wherein the feed is heated to a temperature of from about 600 to about 900 F. Since low boiling materials have been removed in the first flash zone, it is now possible to operate this second convection zone at a higher liquid/vapor ratio, which improves heat transfer and reduces the fouling tendency.
  • the materials which are vaporized by being passed through the convection section of the second cracking furnace are those materials in the crude feed which vaporize below about 850 to 1,l F., more preferably about 950 F. These vaporized materials comprise about 35 to 90 wt.
  • the amount of stripping steam which is employed is in the range of from about 0.1 to 2.0, and more preferably from about 0.2 to about 0.7 pounds/steam per pound of hydrocarbon feed such that the feed to thesecond cracking zone comprises about 17 to 38 wt. percent steam.
  • the gas oil fraction along with steam thus passes overhead from the second separation zone and is passed into the second cracking zone in the radiant section of the second steamcracking furnace.
  • the conditions in the second cracking zone are those optimum conditions for steam cracking a gas oil fraction. Accordingly, the contact time of vaporized portion in the second cracking zone, i.e. radiant section of second steam cracking furnace is in the range of from about 0.1 to L0 seconds, preferably 0.3 to 0.6 seconds.
  • the temperature at the coil outlet of the cracking zone i.e. the radiant section of the furnace is within the range of l,350-1,700E- F.
  • Pressures within the tubes may range from 1 to 200 p.s.i.g. at the coil outlet.
  • the liquid portion remaining in the bottom of the second flash drum, i.e. heavy residua of the crude feed oil, may be stripped with steam and withdrawn and employed as a fuel.
  • the present invention eliminates much of the heat exchange apparatus which was heretofore required, while utilizing the convection sections of the cracking furnace to vaporize those fractions, i.e. naphtha and gas oil fractions which may be conventionally steam cracked to produce high yields of valuable chemical raw materials.
  • a signiflcant advantage of the instant process is the steam cracking of crude oils and hydrocarbon feeds wherein about 50 volume percent or higher of the materials in said feed have a boiling point above 900 F.
  • the use of the two-stage process of this invention allows, the naphtha fraction and the gas oil fraction each be cracked under their optimum cracking conditions in order to increase overall yields of unsaturated cracked hydrocarbon products, especially C -C diolefins such as butadiene, isoprene and cyclopentadiene and the like without significant loss of ethylene, etc.
  • special equipment such as a heat exchanger on the furnace effluent (to make steam) can then be used on the naphtha cracker, whereas it is not considered operable with gas oil feeds.
  • a crude oil feed is fed by way of line K through the convection section of a cracking furnace 2 in order to flash off i.e. vaporize that portion of the feed which boils below about 450 F.
  • feeds include, but are not limited to, hydrocarbon feedstocks wherein about 5 to about 50 volume percent of the materials in such a feedstock have a boiling point above 900 F.
  • a significant advantage of the instant invention is that feedstocks wherein as high as about 50 volume percent of the materials in such feedstock have a boiling point above 900 F may be successfully employed in the process of this invention.
  • the vaporized portion of the crude feed along with the nonvaporized portion are passed by way of line 3 into the upper portion of a flash drum separator 4.
  • the flash drum separator 4 is operated under a pressure in the range of from about 30 to about p.s.i.g. in order to effect a phase separation between the gas phase containing approximately the naphtha fraction and the liquid phase containing that portion of the feed which comprises above about 30 wt. percent based on total feed.
  • the vaporized portion of the feed thus passes overhead by way of line 5, is admixed with steam via line 6 and reintroduced back into the convection section of the cracking furnace via line 7.
  • the conditions under which the cracking furnace is operated are those which are optimum for the cracking of a naphtha fraction, as described above. These cracking conditions increase the cracking selectivity to C C dioleflns such as butadiene and isoprene over that which would be obtained by cracking the naphtha and gas oil fractions together at other than optimum conditions for the naphtha fraction.
  • the unvaporized, liquid portion of the feed which settles to the bottom of the first flash drum separator 8 is withdrawn therefrom and passed by way of line 9 through the convection section of a second cracking furnace 10.
  • the temperature of the liquid which is withdrawn from the flash drum separator is in the range of about 450 to about 700 F. After passing through the convection section of the second cracking furnace, the temperature of the feed has been raised to about 600 to about 900 F.
  • the portion of the feed which has been vaporized by passing through the second convection zone 10 along with the remaining liquid portion of the feed is passed by way of line 11 into a second flash drum separator 12.
  • the second flash drum separator is operated at a pressure in the range from about 30 to about I00 p.s.i.g.
  • Steam is introduced into the second flash drum separator 12 by way of line 13 or into line 9 in order to reduce the partial pressure of the hydrocarbon in the flash drum in order to increase the vaporization of the hydrocarbon and to provide diluent steam for the subsequent steam cracking of the vaporized products recovered from the second flash drum separator.
  • the vaporized products which are produced by passing the feed through the convection section of the second cracking zone and by steam stripping, are passed overhead from the flash drum by way of line 14 into the convection section of the second cracking furnace and thence through the radiant section from which the cracked products are recovered.
  • the vapor leaving the separator is cooled about 20200 F. to
  • the condensed portion is used to scrub or wash the vapor stream to remove droplets or mist particles that are carried by the vapor stream. Removal of the droplets are necessary to prevent fouling of the steam cracker coil by heavy fractions contained in said droplets.
  • the residue from the second flash drum separator, which is in liquid phase, is withdrawn from the flash drum separator 12 by way of line 14.
  • a process for cracking a hydrocarbon feedstock which comprises:
  • step (d) passing the vaporized and unvaporized fractions formed in step (d) into a second separation zone;
  • a process for cracking a hydrocarbon feedstock which comprises:
  • step (d) withdrawing the unvaporized fraction of the feedstock from the first separation zone and passing said unvaporized fraction, with steam, into the convection section of a second steam cracking furnace, to vaporize those materials boiling below l,l00 F e. passing the vaporized and unvaporized fractions formed in step (d) into a second separation zone;
  • a process for cracking a crude hydrocarbon feedstock which comprises:
  • step (d) passing the vaporized and unvaporized fractions formed in step (d) into a second separation zone;

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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)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US2258A 1970-01-12 1970-01-12 Process for steam cracking crude oil Expired - Lifetime US3617493A (en)

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US225870A 1970-01-12 1970-01-12
NL7108129A NL7108129A (de) 1970-01-12 1971-06-14

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CA (1) CA952461A (de)
DE (1) DE2100910A1 (de)
FR (1) FR2076054B1 (de)
GB (1) GB1332916A (de)
NL (1) NL7108129A (de)

Cited By (76)

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US4908121A (en) * 1986-05-12 1990-03-13 The M. W. Kellogg Company Flexible feed pyrolysis process
WO1990006351A1 (en) * 1988-12-02 1990-06-14 Lummus Crest Inc. Inhibition of coke formation during vaporization of heavy hydrocarbons
US6632351B1 (en) 2000-03-08 2003-10-14 Shell Oil Company Thermal cracking of crude oil and crude oil fractions containing pitch in an ethylene furnace
US20040004028A1 (en) * 2002-07-03 2004-01-08 Stell Richard C. Converting mist flow to annular flow in thermal cracking application
US20040004022A1 (en) * 2002-07-03 2004-01-08 Stell Richard C. Process for steam cracking heavy hydrocarbon feedstocks
US20040004027A1 (en) * 2002-07-03 2004-01-08 Spicer David B. Process for cracking hydrocarbon feed with water substitution
US20040039240A1 (en) * 2002-08-26 2004-02-26 Powers Donald H. Olefin production utilizing whole crude oil
US20050010075A1 (en) * 2003-07-10 2005-01-13 Powers Donald H. Olefin production utilizing whole crude oil and mild controlled cavitation assisted cracking
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US20050261536A1 (en) * 2004-05-21 2005-11-24 Stell Richard C Apparatus and process for controlling temperature of heated feed directed to a flash drum whose overhead provides feed for cracking
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Cited By (185)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1986002376A1 (en) * 1984-10-09 1986-04-24 Stone & Webster Engineering Corp. Integrated heavy oil pyrolysis process
US4615795A (en) * 1984-10-09 1986-10-07 Stone & Webster Engineering Corporation Integrated heavy oil pyrolysis process
JPH0684500B2 (ja) * 1984-10-09 1994-10-26 スト−ン・アンドヴェブスタ−・エンジニアリング・コ−ポレ−シヨン 統合された重油熱分解処理
US4908121A (en) * 1986-05-12 1990-03-13 The M. W. Kellogg Company Flexible feed pyrolysis process
WO1990006351A1 (en) * 1988-12-02 1990-06-14 Lummus Crest Inc. Inhibition of coke formation during vaporization of heavy hydrocarbons
US6632351B1 (en) 2000-03-08 2003-10-14 Shell Oil Company Thermal cracking of crude oil and crude oil fractions containing pitch in an ethylene furnace
US7578929B2 (en) 2002-07-03 2009-08-25 Exxonmoil Chemical Patents Inc. Process for steam cracking heavy hydrocarbon feedstocks
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FR2076054B1 (de) 1975-01-17
FR2076054A1 (de) 1971-10-15
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CA952461A (en) 1974-08-06
DE2100910A1 (de) 1971-07-22
NL7108129A (de) 1972-12-18

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