US3392211A - Production of ethylene by thermal cracking of hydrocarbons - Google Patents

Production of ethylene by thermal cracking of hydrocarbons Download PDF

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Publication number
US3392211A
US3392211A US437352A US43735265A US3392211A US 3392211 A US3392211 A US 3392211A US 437352 A US437352 A US 437352A US 43735265 A US43735265 A US 43735265A US 3392211 A US3392211 A US 3392211A
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US
United States
Prior art keywords
hydrocarbons
cooling tubes
cracked gas
ethylene
cooling
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US437352A
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English (en)
Inventor
Buschmann Karl
Markert Ferdinand
Meyer Hermann
Vollhardt Frohmut
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.)
BASF SE
Schmidtsche Heissdampf GmbH
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BASF SE
Schmidtsche Heissdampf GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE, Schmidtsche Heissdampf GmbH filed Critical BASF SE
Application granted granted Critical
Publication of US3392211A publication Critical patent/US3392211A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • C10G9/002—Cooling of cracked gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D51/00—Auxiliary pretreatment of gases or vapours to be cleaned
    • B01D51/10—Conditioning the gas to be cleaned
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/04—Thermal processes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F9/00—Casings; Header boxes; Auxiliary supports for elements; Auxiliary members within casings
    • F28F9/02—Header boxes; End plates
    • F28F9/026—Header boxes; End plates with static flow control means, e.g. with means for uniformly distributing heat exchange media into conduits
    • F28F9/0263—Header boxes; End plates with static flow control means, e.g. with means for uniformly distributing heat exchange media into conduits by varying the geometry or cross-section of header box
    • 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
    • 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
    • Y10S585/919—Apparatus considerations
    • Y10S585/921—Apparatus considerations using recited apparatus structure

Definitions

  • the hot cracked gas is indirectly cooled by passing the gas through a quench boiler at a mass velocity of at least 50 kg./sq.m./sec., the wall temperatures of the cooling tubes of the quench boiler being kept above 310 C., by maintaining a steam pressure of at least 100 atmospheres on the side of the boiling Water.
  • the process has the advantage that deposits of coke and other cracked products are controlled while still making use of the preferred indirect cooling.
  • This invention relates to a process for the production of ethylene by thermal cracking of hydrocarbons.
  • a special object of the invention is to avoid the deposition of coke and other cracked products as well as high polymers in the cooling tubes of the quench boiler by passing the hot cracked gas through the cooling tubes at a high and specific mass velocity.
  • olefins particularly ethylene
  • olefins may be produced by cracking gaseous or completely vaporizable liquid hydrocarbons by various prior art methods, for example thermally in metal tubes which are externally heated, in admixture with steam at temperatures of more than 750 C.
  • cracked gases are obtained having a high content of olefinic hydrocarbons, especially ethylene.
  • the byproducts of these processes include propylene, higher olefins and diolefins as well as other cracked products.
  • the highly reactive gas mixture must be cooled rapidly. This cooling is effected in practice either by directly spraying in coolants, for example liquid hydrocarbons, into the gas mixture, or by indirect cooling in a quench boiler.
  • Indirect cooling is generally preferred in order to obtain high-pressure steam.
  • a disadvantage of indirect cooling of the cracked gas is that deposits of coke and other cracked products form on the heat-exchanging surfaces and these impair heat transfer and thus lessen the effect of the cooling. Operation thus has to be interrupted at more or less short intervals of time and the quench boiler cleared mechanically of the coke deposits.
  • hydrocarbons examples include ethane, propane and butane, if desired, in admixture with olefins, for example to 20% of propylene.
  • olefins for example to 20% of propylene.
  • liquid hydrocarbons boiling between 35 and 200 C., for example full range naphtha or light naphtha boiling between 35 and 100 C. are used.
  • gaseous and/or vaporous hydrocarbons are mixed with steam and thermally cracked at temperatures of from 750 to 900 C., preferably more than 800 C., and the hot cracked gas thus formed is cooled in the manner described above in a quench boiler to temperatures of less than 450 C., preferably to temperatures of 340 to 400 C.
  • the temperature during passage through the cooling tubes should not be lower than the dewpoint of the component of the cracked gas having the highest boiling point. It has been found that wall temperatures of the cooling tubes of at least 310 C. or more, e.g., 310 to 330 C., are necessary for this purpose. This wall temperature is achieved under the said conditions when the coolant, for example water, is kept at a minimum pressure of atmospheres, preferably at a pressure of to atmospheres.
  • the use of the process according to this invention is of particular importance for high-severity cracking in which cracking temperatures of 810 to 850 C. and residence times of less than 0.3 second, related to the volume of cracked gas at the heater outlet, are desirable. Further cooling of the cracked gas after it leaves the quench boiler may be carried out in conventional manner by direct cooling, for example by spraying in high boiling point hydrocarbons, or in another quench boiler. Undisturbed operation of the cracking plant is ensured by the process according to this invention and a. particularly advantageous recovery of the heat liberated during the cracking is possible because the heat is recovered in the form of high-pressure steam.
  • Deposition of coke and other cracked products also takes place in the connections between the cracking furnace and the cooling tubes.
  • the risk of coke formation in these connections i.e., in the inlet cone of the quench boiler, prior to distribution of the hot cracked gas to the individual cooling tubes can be lessened by designing the inlet cone in the manner of a diffuser, turbulence due to sharp deflections of the stream of gas as encountered in conventional equipment thus being prevented.
  • the residence time of the cracked gas in the quench boiler is shortened owing to the incorporation of the connecting member. It is advantageous for the inlet cone to be designed so that the space velocity therein is more than 20 kg. of cracked gas/cu.rn./sec., preferably from 20 to 45 kg./cu.m./sec.
  • Example 3700 kg./h. of light naphtha having a boiling range of 35 to C. is premixed with 1850 kg./h. of steam and the mixture heated to 600 C. and thermally cracked at 820 C. in a tube heated externally with gas flames.
  • the residence time of the hot reaction mixture from the beginning of the cracking reaction to the entry of the cracked gas into the cooling tubes of the quench boiler is 0.3 second.
  • Distribution of the hot cracked gas to the cooling tubes of the quench boiler illustrated in the drawing takes place in a connecting member 1 resembling a diffuser which is the inlet cone of the quench boiler.
  • the space velocity in this connecting member is 38 kg./cu. m./sec. 5550 kg./h. of cracked gas flows through the cooling tubes 2 at a mass velocity of 51 kg./sq.m./sec.
  • a process for the production of ethylene by thermal cracking of hydrocarbons at temperatures of from 750 to 900 C. and by indirect cooling of the hot cracked gas in a quench boiler, wherein the hot cracked gas is passed through the cooling tubes of the quench boiler at a mass velocity of at least 50 kg./sq.m./second, the wall temperature of said cooling tubes being maintained at a temperature not lower than the dewpoint of the component of the cracked gas having the highest boiling point.
  • a process for the production of ethylene by thermal cracking of hydrocarbons at temperatures of from 750 to 900 C. and by indirect cooling of the hot cracked gas in a quench boiler wherein the hot cracked gas is passed through the cooling tubes of the quench boiler at a mass velocity of from to kg./sq.m./second and the wall temperature of the cooling tubes is kept at from 310 to 330 C. by maintaining a steam pressure of to atmospheres on the side of the boiling water.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Thermal Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Geometry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US437352A 1964-03-07 1965-03-05 Production of ethylene by thermal cracking of hydrocarbons Expired - Lifetime US3392211A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEB75780A DE1217944B (de) 1964-03-07 1964-03-07 Verfahren zur Erzeugung von Olefinen, insbesondere AEthylen, durch thermische Spaltung von Kohlenwasserstoffen

Publications (1)

Publication Number Publication Date
US3392211A true US3392211A (en) 1968-07-09

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Family Applications (1)

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US437352A Expired - Lifetime US3392211A (en) 1964-03-07 1965-03-05 Production of ethylene by thermal cracking of hydrocarbons

Country Status (6)

Country Link
US (1) US3392211A (xx)
BE (1) BE660726A (xx)
DE (1) DE1217944B (xx)
FR (1) FR1432867A (xx)
GB (1) GB1032690A (xx)
NL (2) NL6502860A (xx)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3412482A1 (de) * 1984-04-03 1985-10-10 Linde Ag, 6200 Wiesbaden Verfahren und reaktor zur katalytischen dehydratisierung von methanol und/oder dimethylaether
US4614229A (en) * 1983-06-20 1986-09-30 Exxon Research & Engineering Co. Method and apparatus for efficient recovery of heat from hot gases that tend to foul heat exchanger tubes
US4617109A (en) * 1985-12-23 1986-10-14 The M. W. Kellogg Company Combustion air preheating
US5254781A (en) * 1991-12-31 1993-10-19 Amoco Corporation Olefins process which combines hydrocarbon cracking with coupling methane
US5427655A (en) * 1990-11-29 1995-06-27 Stone & Webster Engineering Corp. High capacity rapid quench boiler
US5981818A (en) * 1995-03-21 1999-11-09 Stone & Webster Engineering Corp. Integrated cracking and olefins derivative process utilizing dilute olefins
US20030192683A1 (en) * 2002-04-16 2003-10-16 Menon Raghunath Gopal Flow distributor for an alkylation reactor or heat exchanger
WO2014003880A1 (en) * 2012-06-29 2014-01-03 Praxair Technology, Inc. Compressed gas cooling apparatus
WO2024025988A1 (en) 2022-07-28 2024-02-01 Chevron Phillips Chemical Company, Lp Flexible benzene production via selective-higher-olefin oligomerization of ethylene
EP4410928A3 (en) * 2021-09-24 2024-10-23 Muroran Institute of Technology Olefin production method

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5523807B2 (xx) * 1972-07-04 1980-06-25
DE3010000A1 (de) * 1980-03-15 1981-09-24 Basf Ag, 6700 Ludwigshafen Verfahren zur thermischen entkokung von spaltgaskuehlern
RU2061018C1 (ru) * 1995-12-05 1996-05-27 Акционерное общество закрытого типа "Ареопаг ЭКС", Лтд. Способ получения низших олефинов
US8709233B2 (en) 2006-08-31 2014-04-29 Exxonmobil Chemical Patents Inc. Disposition of steam cracked tar
US7560020B2 (en) 2006-10-30 2009-07-14 Exxonmobil Chemical Patents Inc. Deasphalting tar using stripping tower
US7744743B2 (en) * 2006-10-30 2010-06-29 Exxonmobil Chemical Patents Inc. Process for upgrading tar

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1998571A (en) * 1930-07-24 1935-04-23 Gasoline Prod Co Inc Process for converting petroleum oils
US3060116A (en) * 1959-11-06 1962-10-23 Socony Mobil Oil Co Inc Combination reforming and cracking process

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1108362B (de) * 1960-01-26 1961-06-08 Schmidt Sche Heissdampf Verfahren und Vorrichtung zur Kuehlung von Spaltgasen

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1998571A (en) * 1930-07-24 1935-04-23 Gasoline Prod Co Inc Process for converting petroleum oils
US3060116A (en) * 1959-11-06 1962-10-23 Socony Mobil Oil Co Inc Combination reforming and cracking process

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4614229A (en) * 1983-06-20 1986-09-30 Exxon Research & Engineering Co. Method and apparatus for efficient recovery of heat from hot gases that tend to foul heat exchanger tubes
DE3412482A1 (de) * 1984-04-03 1985-10-10 Linde Ag, 6200 Wiesbaden Verfahren und reaktor zur katalytischen dehydratisierung von methanol und/oder dimethylaether
US4617109A (en) * 1985-12-23 1986-10-14 The M. W. Kellogg Company Combustion air preheating
US5427655A (en) * 1990-11-29 1995-06-27 Stone & Webster Engineering Corp. High capacity rapid quench boiler
US5254781A (en) * 1991-12-31 1993-10-19 Amoco Corporation Olefins process which combines hydrocarbon cracking with coupling methane
US5981818A (en) * 1995-03-21 1999-11-09 Stone & Webster Engineering Corp. Integrated cracking and olefins derivative process utilizing dilute olefins
US20030192683A1 (en) * 2002-04-16 2003-10-16 Menon Raghunath Gopal Flow distributor for an alkylation reactor or heat exchanger
US6863121B2 (en) * 2002-04-16 2005-03-08 Shell Oil Company Flow distributor for an alkylation reactor or heat exchanger
WO2014003880A1 (en) * 2012-06-29 2014-01-03 Praxair Technology, Inc. Compressed gas cooling apparatus
EP4410928A3 (en) * 2021-09-24 2024-10-23 Muroran Institute of Technology Olefin production method
WO2024025988A1 (en) 2022-07-28 2024-02-01 Chevron Phillips Chemical Company, Lp Flexible benzene production via selective-higher-olefin oligomerization of ethylene

Also Published As

Publication number Publication date
FR1432867A (fr) 1966-03-25
NL6502860A (xx) 1965-09-08
NL128466C (xx)
BE660726A (xx) 1965-09-06
DE1217944B (de) 1966-06-02
GB1032690A (en) 1966-06-15

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