US2908625A - Olefin production process - Google Patents

Olefin production process Download PDF

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Publication number
US2908625A
US2908625A US482031A US48203155A US2908625A US 2908625 A US2908625 A US 2908625A US 482031 A US482031 A US 482031A US 48203155 A US48203155 A US 48203155A US 2908625 A US2908625 A US 2908625A
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United States
Prior art keywords
zone
vapors
charge
cracking
withdrawing
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Expired - Lifetime
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US482031A
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English (en)
Inventor
Mekler Valentine
August H Schutte
Karl J Korpi
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CB&I Technology Inc
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Lummus Co
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Priority to US482031A priority Critical patent/US2908625A/en
Priority to GB955/56A priority patent/GB830968A/en
Priority to DEL23851A priority patent/DE1116212B/de
Priority to FR1200022D priority patent/FR1200022A/fr
Application granted granted Critical
Publication of US2908625A publication Critical patent/US2908625A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
    • 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

Definitions

  • This invention relates to improvements in apparatus for the production of gaseous olefins vfrom heavy residual hydrocarbons such as asphalt, tars and heavy reduced crudes.
  • V,tirst reaction to produce maximum yields of valuable formation and the production of undesirable quantities of finely divided carbon and oil soot, resulting in low oleiin yields and in operational difficulties.
  • these operations have also been hampered by the necessity of providing for burning oif of the carbon deposit after a very short on-stream period, the heat evolved usually being in excess of the process heat requirements.
  • the coking zone vapors are cracked in regen erative furnaces which are used in pairs to give cony tinuous ilow, each furnace utilizing stationary refractory masses for heat storage and operating with cyclic reheating.
  • This method has several advantages. It obviates .the necessity for circulating highly preheated heat very economical ultimate cost. ⁇
  • the principal object of the present invention is to integrate a coking system, a regenerative furnace system and a recovery and purification ⁇ system whereby low cost residual oil is converted into useable coke and a maximum yield of gaseous oleiins under readily controlled conditions and at a minimum cost of end products.
  • a still further object of our invention is to integrate a coking system with regenerative furnaces and fractionation apparatus whereby optimum temperatures and pressures may be employed in all parts of the system with maximum heat recovery, whereby the products from each section of the system may be most effectively utilized for 'the production of maximum yields of ethylene and/or acetylene.
  • the integrated unit more particularly shown may be more effectively understood if it is considered to include several sections as follows: l
  • VThe first major section is the coker or decoking section, wherein the residual carbon and the heavy ends are removed Vfrom charging stock. ⁇ As will be understood hereinafter, the selected removal of certain constituents of the heavy residue of such charging stock is particularly helpful for subsequent processing of lighter hydrocarbons thusproduced.
  • the second major section includes regenerative crack- ,ing furnaces of which several examples are known, but
  • a third section may be considered to be the gas cleanup section and this includes the removal of aromatics in one step and the treatment for the removal of acidic gaseous constituents particularly H28 and CO2.
  • a fourth section maybe used in which acetylene is converted to ethylene by suitable catalytic methods, particularly where high yields of ethylene are required with a minimum of acetylene contamination.
  • V The nal stage of the apparatus includes fractionation equipment which also may be of well known type in whichV the specific olens are recovered as desired.
  • Coker section Thelowest cost oleiin product is economically made from the lowest cost raw material and whereasit has been common practice to produce olenes from normally out, it can also be cracked to a significantly high yield ofeolens.
  • the coker section lthus includes as a primary step, any of the well known coke production units Whether of the continuous gravity type shown by the Schutte Patent 2,561,334 or of the fluid type or of the more generally used delayed coker type. For purposes of explanation, the latter type is 'illustrated but it will be understood that this is only one of the types that may be used.
  • coke drums 17 and 17a are used in parallel with switch valve 18 directing the material first into one drum and then into the other while the first is being cleaned out. Coke is removed through lines 19 or 19a and the overhead is removed at 20 or 20a.
  • the coker overhead which is removed at about 800 to 900 F., is introduced through line 21 into the lower part of flash tower 13 and thereby aids in driving off the light ends from the fuel oil removed at the bottom.
  • this fuel oil if there is any excess Vover coking requirements, may be used as heater fuel through line 14b.
  • the overhead in line 22 from the flash tower 13 then becomes the charge to the regenerative furnace 23.
  • the overhead contains in the order of 5060% of a gas oil fraction having a boiling range of S50-850 F.; a gasoline fraction of around 10-15 of a boiling range of C to 350 F. and approximately 5 to 15% of normally gaseous material.
  • the coke already removed accounts for about 20-30%-all being based on original charge.
  • Regenerative furnace system i' center is lled with refractory tiles of special design.
  • the ends of the furnace are provided with plenum boxes and battles for the proper distribution of feed to the furnace.
  • furnaces are operated in pairs on a regenerative cycle, heat being removed from the refractory tiles by the pyrolysis of the gas feed and restored by the combustion of fuel gas with preheated air.
  • a complete cycle for each furnace consists of a pyrolysis step and a heating step in the forward direction followed by a pyrolysis step and a heating step in the reverse direction. Each step usually occurs for approximately one minute. The time of these steps may, however, be varied according to needs.
  • a description of the complete cycle follows. Y
  • Air is introduced at the front of the furnace and preheated by the refractory tile before the air reaches the combustion zone.
  • Fuel gas is admitted to the combustion zone and hot combustion gas passes through the refractory tiles and out the back of the furnace.
  • step (c) The pyrolysis step is repeated with the steam-gas mixture owing in the opposite direction Vto lthat described in step (a), i.e. back to front.
  • step (d) The heating part of the cycle is repeated and the air and combustion gases flow through the heater in the opposite direction to that described in step (b), i.e. back to front.
  • the regenerative furnaces are generally operated at about one-half atmosphere absolute pressure, in both the heating and cracking cycles, when acetylene is the preferred product, we prefer to operate at one to two atmospheres absolute pressure when ethylene is the preferred product.
  • the charge ,(hydrocarbon plus steam) rate is increased, in such operation, so that the time of residence of the feed is the same as it would be if the furnace were at one-half atmosphere absolute pressure.
  • the following table better illustrates furnace operating conditions where the major oleinic product desired is either ethylene or acetylene.
  • ethylene is the preferred major product
  • an increase in feed rate also increases the production capacity of a given furnace. For instance, if the pressure is one atmosphere, the production capacity would be about double that at one-half atmosphere. However, if the pressure on the furnace is too high polymerization and loss of the olens to higher molecular weight products can occur in the cooler parts of the checker work. Hence, the preferred choice of pressure is about one to two atmospheres.
  • Gas for combustion purposes within the pair of furnaces is provided from off-gas sources throughout the system and enters in line 24.
  • the crackedhydrocarbons are automatically quenched to about 900 F. by the refractory mass in the heat side of the furnace as described 4in the afore-mentioned article.
  • the cracked effluent from furnace 23 which includes either'a major portion of ethylene or acetylene depending upon furnace operating conditions and which has been partially quenched to halt further reaction is passed through line 30 to a quench and tar separator 31.
  • a quench and tar separator 31 Preferably water is used as the 'quench material being introduced through line 32. Tar, steam and other contaminants are removedthrough line 33.
  • a portion of the absorber bottoms in line 41 may be forwarded to ash tower as a reflux with the remainder being diverted through line 51 to a rerun tower 52.
  • Overheads from the tower 52 pass through line 53 to condenser 54 and accumulator 55.
  • Distillate from the accumulator may be passed in part to the rerun tower as reflux in line 56 and in part to line 57 as product C5s and aromatics while gases from the accumulator 55 may pass in line 58 to join the absorber overhead gases in line 42.
  • Bottoms from the rerun tower may pass in line 59 through cooler 60 to unite with bottoms in line 41 from absorber 38.
  • the absorber overhead gases in line 42 which have been compressed at 43 are passed through line 61 to an acidic acid removal section indicated generally at 62.
  • acid gases including H28 and CO2 may be removed in any well known manner.
  • an acetylene conversion system indicated generally at 64.
  • the major product desired at the finalv output is ethylene.
  • the acetylenes in the gases in line 63 may be hydrogenated to olefns in any well known manner.
  • vImpurities of the acetylenes conversion may be removed at 65.
  • the gaseous olefns pass .from the acetylene conversion system through line 66 and are compressed at 67 prior to entering fractionation system 68.
  • the compressed gases including a major percentage of ethylene in ⁇ our preferred embodiment are fractionated in a known manner which may include two or more stages of fractionation (notshown).
  • aromatics would be generally removed as tower bottoms with tower overheads including thane, ethylene, propane, Vpropylene and C4 hydrocarbons removed to recovery apparatus for separation into product gas streams 69, 70, 71 and 72 which may include off gas or recycle, ethylene, propylene and a C4 cut.
  • the reaction temperature of the furnaces may be increased to the optimum temperature range of 1800 to 2200".
  • the process -for thermally treating a heavy hydrocarbon charge to simultaneously produce coke ⁇ and predominant yields of gaseous unsaturated hydrocarbons having less than four carbon atoms to the molecule which comprises preheating said hydrocarbon charge to a temperature below its cracking temperature and in the order of about 700 to 800 F.; introducing said preheated charge into a Hash zone wherein ilight ends are ashed from said preheated charge; withdrawing as a bottom stream ⁇ from said flash zone normally liquid hydrocarbons having a Iboiling range of heavy fuel oil; heating said bottoms to about 900 ⁇ to 950 F.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US482031A 1955-01-17 1955-01-17 Olefin production process Expired - Lifetime US2908625A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US482031A US2908625A (en) 1955-01-17 1955-01-17 Olefin production process
GB955/56A GB830968A (en) 1955-01-17 1956-01-11 Process for the production of coke and gaseous unsaturated hydrocarbons
DEL23851A DE1116212B (de) 1955-01-17 1956-01-16 Thermisch regeneratives Spaltverfahren und Vorrichtung zur Herstellung von gasfoermigen Olefinen und/oder Acetylen aus schweren Kohlenwasserstoffen
FR1200022D FR1200022A (fr) 1955-01-17 1956-01-17 Procédé de craquage combiné d'huiles lourdes et dispositifs pour sa mise en oeuvre

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US482031A US2908625A (en) 1955-01-17 1955-01-17 Olefin production process

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US2908625A true US2908625A (en) 1959-10-13

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US (1) US2908625A (de)
DE (1) DE1116212B (de)
FR (1) FR1200022A (de)
GB (1) GB830968A (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3470084A (en) * 1967-11-20 1969-09-30 Universal Oil Prod Co Method of separation of gaseous hydrocarbons from gasoline
US4832718A (en) * 1982-05-03 1989-05-23 Advanced Extraction Technologies, Inc. Processing nitrogen-rich, hydrogen-rich, and olefin-rich gases with physical solvents
US20140296597A1 (en) * 2011-01-19 2014-10-02 Exxon Mobile Chemical Patents Inc. Method and Apparatus for Converting Hydrocarbons Into Olefins
US20150166430A1 (en) * 2011-01-19 2015-06-18 Exxonmobil Chemical Patents Inc. Method and Apparatus for Converting Hydrocarbons Into Olefins Using Hydroprocessing and Thermal Pyrolysis

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1490862A (en) * 1923-03-05 1924-04-15 Vergil T Smith Process for distilling and cracking oils
US1907029A (en) * 1930-03-03 1933-05-02 C P T Dev Company Method of cracxing petroleum vapors
US2245819A (en) * 1937-07-14 1941-06-17 Solvay Process Co Process for the manufacture of ethylene
US2310317A (en) * 1938-05-27 1943-02-09 Standard Oil Co Combination coking and catalytic cracking process
US2552277A (en) * 1945-12-08 1951-05-08 Eastman Kodak Co Furnace
US2580002A (en) * 1949-12-24 1951-12-25 Standard Oil Dev Co Process for the production of ethylene
US2656307A (en) * 1949-12-15 1953-10-20 Phillips Petroleum Co Conversion of hydrocarbon materials
US2731508A (en) * 1951-06-08 1956-01-17 Exxon Research Engineering Co Conversion of hydrocarbons for the production of unsaturates and gasoline with the use of inert solids

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2174196A (en) * 1937-12-06 1939-09-26 Solvay Process Co Process for the manufacture of ethylene

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1490862A (en) * 1923-03-05 1924-04-15 Vergil T Smith Process for distilling and cracking oils
US1907029A (en) * 1930-03-03 1933-05-02 C P T Dev Company Method of cracxing petroleum vapors
US2245819A (en) * 1937-07-14 1941-06-17 Solvay Process Co Process for the manufacture of ethylene
US2310317A (en) * 1938-05-27 1943-02-09 Standard Oil Co Combination coking and catalytic cracking process
US2552277A (en) * 1945-12-08 1951-05-08 Eastman Kodak Co Furnace
US2656307A (en) * 1949-12-15 1953-10-20 Phillips Petroleum Co Conversion of hydrocarbon materials
US2580002A (en) * 1949-12-24 1951-12-25 Standard Oil Dev Co Process for the production of ethylene
US2731508A (en) * 1951-06-08 1956-01-17 Exxon Research Engineering Co Conversion of hydrocarbons for the production of unsaturates and gasoline with the use of inert solids

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3470084A (en) * 1967-11-20 1969-09-30 Universal Oil Prod Co Method of separation of gaseous hydrocarbons from gasoline
US4832718A (en) * 1982-05-03 1989-05-23 Advanced Extraction Technologies, Inc. Processing nitrogen-rich, hydrogen-rich, and olefin-rich gases with physical solvents
US20140296597A1 (en) * 2011-01-19 2014-10-02 Exxon Mobile Chemical Patents Inc. Method and Apparatus for Converting Hydrocarbons Into Olefins
US20150166430A1 (en) * 2011-01-19 2015-06-18 Exxonmobil Chemical Patents Inc. Method and Apparatus for Converting Hydrocarbons Into Olefins Using Hydroprocessing and Thermal Pyrolysis
US9708231B2 (en) * 2011-01-19 2017-07-18 Exxonmobil Chemical Patents Inc. Method and apparatus for converting hydrocarbons into olefins using hydroprocessing and thermal pyrolysis
US9708232B2 (en) * 2011-01-19 2017-07-18 Exxonmobil Chemical Patents Inc. Method and apparatus for converting hydrocarbons into olefins

Also Published As

Publication number Publication date
DE1116212B (de) 1961-11-02
GB830968A (en) 1960-03-23
FR1200022A (fr) 1959-12-17

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