US2549518A - Combined selective adsorptioncatalytic cracking process - Google Patents

Combined selective adsorptioncatalytic cracking process Download PDF

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Publication number
US2549518A
US2549518A US69911A US6991149A US2549518A US 2549518 A US2549518 A US 2549518A US 69911 A US69911 A US 69911A US 6991149 A US6991149 A US 6991149A US 2549518 A US2549518 A US 2549518A
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United States
Prior art keywords
catalyst
zone
cracking
boiling
oil
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US69911A
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English (en)
Inventor
Stephen F Perry
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Standard Oil Development Co
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Standard Oil Development Co
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Priority to NL75508D priority Critical patent/NL75508C/xx
Application filed by Standard Oil Development Co filed Critical Standard Oil Development Co
Priority to US69911A priority patent/US2549518A/en
Priority to GB29173/49A priority patent/GB659566A/en
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Publication of US2549518A publication Critical patent/US2549518A/en
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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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • 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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/06—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with moving sorbents or sorbents dispersed in the oil

Definitions

  • the present invention is concerned with a improved process for the refining of petroleum hydrocarbon fractions.
  • the invention is more particularly concerned with the processing of a hydrocarbon fractionv utilizing an adsorption stage and catalytic cracking stage in combination one. with-the other.
  • a petroleum fraction is catalytically cracked using a solid catalyst. The catalyst is removed from the cracking zone and regenerated in a regeneration zone.
  • a portion of the catalyst from the regeneration zone is then passed throughV an adsorption Azone wherein the regenerated catalyst contacts Aa petroleum fraction to remove therefrom the relatively more aromatic type constituents.
  • This portion of the catalyst containing the adsorption constituents having a relatively high carbon to hydrogen ratio is then passed to the catalytic y cracking zone.
  • a preferred embodiment of the present process is to contact a hydrocarbon fraction boiling in the lubricating oil or kerosene boiling ranges with a catalyst; to remove the catalyst and to utilize the same to crack a hydrocarbon Vfraction boiling in the gas oil boiling range.
  • kerosene boiling range and in the lubricating oil boiling range are usually cracking the gas oil fraction by either a thermal or a fluid "or fixed bed catalytic cracking operation. Temperatures and pressures, as well as feed rates may be varied depending upon the particular stock being cracked. Cracking temperatures are generally in the range from about 750-1000 F., while the pressures are in the range from atmospheric to 1000 pounds. Preferred cracking temperatures are in the range from about 850"2 F.9'75 F. If ⁇ a fluid operation is utilized any suitable cracking .are undesirable with respect to the fractions boil- 'ingin the kerosene range. pIt is, thus, desirable to remove these aromatic fractions from certain Y products such as kerosene, and lubricating oils.
  • Vmeans of feed line l Vmeans of feed line l.
  • a feed oil which'for the purpose of illustration is taken to be a crude oil, is introduced into distillation zone l0 by Temperature and pressure conditions are adjusted in distillation zone I0 lto segregate; normally gaseous hydrocarbons,
  • zone l l0 may comprise any suitable number and arl lfraction is introduced into catalytic cracking zone 20 by means of line 4. Regenerated or fresh catalyst is introduced into the top of catalytic cracking zone 2li by means of line 1, and the spent cata- :lyst Withdrawn from the bottom of zone 20 by means of line 8.
  • the cracking catalyst comprises silica and alumina. Temperature and pressure conditions in zone 20 as well as oil and catalyst feed rates are maintained within a range to secure the desired cracking of the gas oil fraction and tov produce lower boiling constituents.
  • a product stream is withdrawn overhead from zone 2U by means of line 9 and introduced into distillation zone B. Uncondensed gases are removed overhead from zone 3B While a cracked gasoline 'is withdrawn by means of line i I. Heavier higher boiling constituents are removed from zone v3f) by means of line I2. It is to be understood that suitable cooling, condensing and heat exchange equipment is utilized.
  • the spent catalyst is withdrawn from zone 20 by means of line 8 as hereinbefore described and introduced into regeneration Zone 40.
  • the catalyst is regenerated in zone I0 preferably by burning the catalyst with air which is introduced into zone 40 by means of line I3. Steam is also utilized and is introduced by means of line I4. A portion of the regenerated catalyst is withdrawn from the bottom of zone 40 by meansV of line 'I and returned to Zone 20.
  • a portion of this catalyst is segregated by means of line I5, passed through a heat exchanger Zone, introduced to cyclone separator I8 and then passed to contacting zone 50.
  • the lubricating oil fraction withdrawn from Zone I by means of line 5 is preferably mixed with a diluent comprising liquied propane, butane or a light naphtha which is segregated in zone 30 and introduced into line 5 by means of line I'I.
  • the lubricating oil is introduced into contacting zones 50 and 60 alternately. In zone 50 and in zone 60 the lubricating oil fraction contacts the regenerated adsorbent under conditions to remove the more aromatic type constituents, the sulfur compounds, resins and gumforming materials selectively.
  • the quality Vof the lubricating oil fraction is materially imheater I9 and introduced into distillation Zone 10.
  • zone 'I0 Temperature and pressure conditions are adjusted in zone 'I0 to remove overhead by means of line 2i the diluent which may be handled as desired but is preferably condensed and recycled to contacting Zones and 60.
  • the high viscosity lubricating oil fraction is withdrawn from zone 'I0 by means of line 22 and may be further treated as desired.
  • the adsorbent is withdrawn from filter 80 by rleans of line 23 and is introduced into cracking zone 20 by means of line 1. If desired, this stream may be subjected to a mild steaming or purging operation prior to introducing the adsorbent into the reactor. This steaming or purging operation is conducted under conditions such that the loosely held diluent is removed and the adsorbed aromatic fraction is retained.
  • the more aromatic type constituents which are retained on the spent adsorbent has very poor lubricant qualities but is an excellent feed stock for a cracking operation.
  • the resulting gasoline has a relatively high anti-knock value.
  • the aromatic kerosene fraction is retained by the adsorbent and recycled to the cracking step.
  • the present invention comprises a combination operation wherein aromatic constituents are removed from a feed oil andv returned to a cracking Zone under conditions so that both the quality of the heavier fraction and the quality In accordance with the 4 of the gasoline fraction is materially improved.
  • the invention is specifically adapted to the production of high quality kerosenes, lubricating oil and gasolines.
  • the invention is generally concerned with the catalytic cracking of hydrocarbon constituents boiling in the gas oil boiling range in the presence of adsorbed aromatic type constituents removed from a petroleum fraction boiling either above or below the gas oil boiling range. It is preferred that the aromatic constituents present be secured from a heavier boiling fraction, as for example, 'a fraction boiling in the range from about 675 F. to 900 F. A satisfactory operation is also attained when the aromatic constituents present in the catalytic cracking zone are segregated from kerosene fractions boiling in the general range from about 375 F. to 550 F. In general it is preferred that the gas oil fraction boil in the range from about 400 F. to 700 F.
  • the preferred catalyst comprises a silica-alumina catalyst particularly, a catalyst which comprises about -90% S102 and from 10-20% A1203.
  • a particularly desirable catalyst comprises SiO2 and 15% A1203.
  • the amount of catalyst segregated from the regeneration zone and passed to the adsorption zone may vary considerably. However, in general it is preferred that fromV about 20-50% of the catalyst withdrawn from the regeneration zone is passed through the adsorption zone.
  • the quantity of catalyst used in the adsorption zone when contacting a petroleum oil boiling in the lubricating oil boiling' range should vary in the r-ange from about' 2-6 parts by weight of catalyst per 1 part by Weight of oil.
  • the volume of diluent used should be from 2-10 parts of diluent per part of oil.
  • the Vtemperature employed in the adsorption zone may be in the range from about 80 to 300 F., although it is preferred that the temperature be in the general range from to 150 F.
  • the time of Contact should be in the range from about 5 to 30 minutes, preferably from about 15 to 20 minutes.
  • the amount of catalyst used should be in the range from 0.5 to l part by weight of catalyst per 1 part by weight of oil.
  • the amount of diluent used under these conditions should be in the range of from 1 to 3 parts of diluent per p-art of oil.
  • the temperatures used are similar to those used. when contacting lubricating oils.
  • Improved process forv the production of a high quality lubricating oilY and a high quality cracked gasoline from a petroleum feed oil which comprises segregating saidfpetroleum feed oil into a petroleum fraction boiling in the gas oil boiling range and into a petroleum fraction boiling in the lubricating oil boiling range, catalytically cracking said fraction boiling in the gas oil boiling range in a cracking zone with a cracking catalyst under conditions to produce a cracked gasoline, separating the cracking catalyst and regenerating the same, segregating a portion of said regenerated cracking catalyst and contacting said petroleum fraction boiling. in the lubricating oil boiling range withY said catalyst under conditions to adsorb thereon the more aromatic type constituents, thereafter separating said catalyst from the oil and recycling said cracking. catalyst containing said adsorbed constituents to said cracking zone.
  • Improved process for the production of a lhigh quality lubricating oil and a high quality cracked gasoline from a petroleum feed oil which comprises segregating said petroleum feed oil into a petroleum fraction boiling in the gas oil boiling range and into a petroleum fraction boiling in the lubricating oil boiling range, catalytically cracking said fraction boiling in the gas oil boiling range in a cracking zone with a cracking catalyst under conditions to produce a cracked gasoline, separating the cracking catalyst and regenerating the same, segregating a portion of said regenerated cracking catalyst, adding a diluent to said petroleum fraction boiling in the lubricating oil boiling range, and contacting said petroleum fraction with said segregated portion of regenerated catalyst under conditions to adsorb thereon the more aromatic type constituents, separating said catalyst from the oil and recycling said catalyst to said cracking 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)
  • Dispersion Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US69911A 1949-01-08 1949-01-08 Combined selective adsorptioncatalytic cracking process Expired - Lifetime US2549518A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
NL75508D NL75508C (en, 2012) 1949-01-08
US69911A US2549518A (en) 1949-01-08 1949-01-08 Combined selective adsorptioncatalytic cracking process
GB29173/49A GB659566A (en) 1949-01-08 1949-11-15 Improvements in or relating to the catalytic cracking of hydrocarbons

Applications Claiming Priority (1)

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US69911A US2549518A (en) 1949-01-08 1949-01-08 Combined selective adsorptioncatalytic cracking process

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US2549518A true US2549518A (en) 1951-04-17

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GB (1) GB659566A (en, 2012)
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2663676A (en) * 1951-03-16 1953-12-22 Standard Oil Dev Co Catalyst recovery
US2666732A (en) * 1949-02-12 1954-01-19 Standard Oil Co Method of treating hydrocarbons with a double-function catalyst
US2666733A (en) * 1950-04-27 1954-01-19 Standard Oil Co Method of treating hydrocarbons
US2692223A (en) * 1949-09-21 1954-10-19 Standard Oil Co Combination solvent refining and catalytic cracking process
US2920031A (en) * 1955-05-11 1960-01-05 Sun Oil Co Producing stable cracked gasoline by contacting a cracked gasoline fraction with a regenerated cracking catalyst
US2943040A (en) * 1956-06-01 1960-06-28 Socony Mobil Oil Co Inc Hydrocarbon conversion process
US4619758A (en) * 1982-07-09 1986-10-28 Texaco, Inc. Fluid catalytic cracking method
US4748289A (en) * 1985-11-14 1988-05-31 Hydratron Systems, Inc. Method and apparatus for catalytic processing of light hydrocarbons and catalysts for use therein

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2091892A (en) * 1935-02-21 1937-08-31 Standard Oil Dev Co Treating oils in the presence of clay
US2303047A (en) * 1940-08-22 1942-11-24 Standard Oil Dev Co Catalytic treatment of hydrocarbons
US2357136A (en) * 1941-02-28 1944-08-29 Kellogg M W Co Method of catalytically converting hydrocarbon oils
US2380760A (en) * 1944-04-27 1945-07-31 Universal Oil Prod Co Catalytic conversion of hydrocarbon oil
US2382755A (en) * 1941-05-24 1945-08-14 Standard Oil Dev Co Catalytic conversion of hydrocarbon oils
US2430784A (en) * 1944-12-13 1947-11-11 Kellogg M W Co Conversion of hydrocarbons
US2441572A (en) * 1944-07-18 1948-05-18 Sun Oil Co Cyclic process for separating aromatic hydrocarbons from a mixture of hydrocarbons
US2450724A (en) * 1946-12-28 1948-10-05 Universal Oil Prod Co Conversion of sulfur containing hydrocarbons
US2461958A (en) * 1944-12-14 1949-02-15 Standard Oil Dev Co Treating hydrocarbon fluids

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2091892A (en) * 1935-02-21 1937-08-31 Standard Oil Dev Co Treating oils in the presence of clay
US2303047A (en) * 1940-08-22 1942-11-24 Standard Oil Dev Co Catalytic treatment of hydrocarbons
US2357136A (en) * 1941-02-28 1944-08-29 Kellogg M W Co Method of catalytically converting hydrocarbon oils
US2382755A (en) * 1941-05-24 1945-08-14 Standard Oil Dev Co Catalytic conversion of hydrocarbon oils
US2380760A (en) * 1944-04-27 1945-07-31 Universal Oil Prod Co Catalytic conversion of hydrocarbon oil
US2441572A (en) * 1944-07-18 1948-05-18 Sun Oil Co Cyclic process for separating aromatic hydrocarbons from a mixture of hydrocarbons
US2430784A (en) * 1944-12-13 1947-11-11 Kellogg M W Co Conversion of hydrocarbons
US2461958A (en) * 1944-12-14 1949-02-15 Standard Oil Dev Co Treating hydrocarbon fluids
US2450724A (en) * 1946-12-28 1948-10-05 Universal Oil Prod Co Conversion of sulfur containing hydrocarbons

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2666732A (en) * 1949-02-12 1954-01-19 Standard Oil Co Method of treating hydrocarbons with a double-function catalyst
US2692223A (en) * 1949-09-21 1954-10-19 Standard Oil Co Combination solvent refining and catalytic cracking process
US2666733A (en) * 1950-04-27 1954-01-19 Standard Oil Co Method of treating hydrocarbons
US2663676A (en) * 1951-03-16 1953-12-22 Standard Oil Dev Co Catalyst recovery
US2920031A (en) * 1955-05-11 1960-01-05 Sun Oil Co Producing stable cracked gasoline by contacting a cracked gasoline fraction with a regenerated cracking catalyst
US2943040A (en) * 1956-06-01 1960-06-28 Socony Mobil Oil Co Inc Hydrocarbon conversion process
US4619758A (en) * 1982-07-09 1986-10-28 Texaco, Inc. Fluid catalytic cracking method
US4748289A (en) * 1985-11-14 1988-05-31 Hydratron Systems, Inc. Method and apparatus for catalytic processing of light hydrocarbons and catalysts for use therein

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Publication number Publication date
NL75508C (en, 2012) 1954-03-15
GB659566A (en) 1951-10-24

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