US3761394A - Catalytic cracking of naphtha - Google Patents

Catalytic cracking of naphtha Download PDF

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Publication number
US3761394A
US3761394A US00889714A US3761394DA US3761394A US 3761394 A US3761394 A US 3761394A US 00889714 A US00889714 A US 00889714A US 3761394D A US3761394D A US 3761394DA US 3761394 A US3761394 A US 3761394A
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US
United States
Prior art keywords
naphtha
zeolite
catalyst
cracking
catalytic cracking
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Expired - Lifetime
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US00889714A
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English (en)
Inventor
D Reynolds
D Youngblood
L Parker
J Colvert
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Texaco Inc
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Texaco Inc
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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G11/00Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04Oxides
    • C10G11/05Crystalline alumino-silicates, e.g. molecular sieves

Definitions

  • This invention relates to the catalytic cracking of hydrocarbons.
  • this invention relates to the fluid catalytic cracking of naphtha having a low octane rating and boiling in the range of 100 to 450 F.
  • Gasolines are blended from naphtha stocks whose octane ratings are often increased through catalytic reforming. Both virgin and cracked stocks may be upgraded by reforming operations. Catalytic reformers are usually operated to provide the desired octane improvement with the least conversion of gasoline to butanes and lighter materials.
  • the gasoline blending pool is maintained by a variety of operations--isobutane and butenes are charged to alkylation units and light olefins are polymerized to pro vide high octane blending components while the catalytic cracking of gas oil augments the supply of naphtha as well as providing additional feed for the alkylation and polymerization units.
  • hydrocracking provides additional quantities of gasoline blending naphthas
  • the heavy naphtha from hydrocracking often has a relatively low octane number which may be increased by catalytic reforming.
  • Naphtha is a more difiicult stock to crack than gas oil and up to the present time limited success has been obtained in cracking naphtha catalytically.
  • Traditional cracking catalyst such as silica-alumina, exhibited relatively poor selectivity and activity when employed to crack naphtha resulting in the formation of relatively large amounts of gas and coke and producing small amounts of desirable olefins and aromatics.
  • US. 3,284,341 discloses a process for the catalytic cracking of naphtha with a silica-alumina catalyst to produce substantial quantities of olefins and aromatics by maintaining the space velocity above about 4.5, the pressure between 0 and 20 p.s.i.g. and the reaction temperature between 1000 and 1200 F.
  • our invention is directed to the catalytic cracking of hydrocarbons boiling in the gasoline range to increase the octane rating of the naphtha and to yield substantial quantities of lighter materials to serve as feed for petrochemical, polymer and alkylate manufacture.
  • Zeolitic cracking catalysts containing type X or type Y aluminosilicates have been found to oifer particular utility in the catalytic cracking of such feed streams.
  • Our invention contemplates a process for the fluid catalytic cracking of naphtha which comprises:
  • hydrocarbons boiling in the range of 100 to 450 F. comprisethe feedstock for this process.
  • Many refinery streams having low economic value may be upgraded by employing the process of our invention.
  • Useful feedstocks are usually highly paraffinic and include such light hydrocarbon fractions as low octane naphthas, Udex raffinate, low octane naphthas from thermal cracking or hydrocracking operations and straight run naphthas.
  • the term low octane naphtha refers to these useful feedstocks.
  • the catalyst employed in the instant invention is a cracking catalyst of the zeolitic type as exemplified by those catalysts wherein the aluminosilicate is dispersed in a siliceous matrix.
  • the catalysts which may be usefully employed in the process of our invention are those zeolitic cracking catalysts comprising aluminosilicates of type X or type Y, including both the naturally occuring and synthetic varieties. Because of their extremely high activity these zeolitic materials are composited with a material possessing a substantially lower level of catalytic activity, a siliceous matrix which may be of the synthetic, semisynthetic or natural type.
  • the composite crystalline zeolitic catalyst comprises about 1 to 50 wt. percent zeolite, about to 50 wt. percent alumina and the remainder silica.
  • the crystalline aluminosilicate portion of the catalyst composition is a natural or synthetic, type X or type Y, alkali metal, crystalline aluminosilicate which has been treated to replace all or at least a substantial portion of the original alkali metal ions with other ions such as hydrogen and/or a metal or combination of metals such as barium, calcium, magnesium, manganese or rare earth metals, for example, cerium, lanthanum, neodymium, praseodymium, sarnarium and yttrium.
  • the crystalline zeolites contemplated above may be represented by the formula where M represents hydrogen or a metal, 11 its valance, x has a value ranging from 2 to and y ranges from 0 to 10, in dehydrated zeolites, y will be substantially 0.
  • the crystalline zeolites are either natural or synthetic zeolite X or zeolite Y.
  • in is selected from the group consisting of hydrogen, calcium, magnesium and the rare earth metals.
  • the operating conditions contemplated herein to catalytically crack naphtha include: a reactor temperature of 700 to 1600 F., preferably 8501200 F., a reactor contact time between 0.5 seconds and minutes, preferably 1 second to 10 minutes and a catalyst to oil ratio between 0.5 and 30, preferably between 2 and 15.
  • a reactor temperature of 700 to 1600 F., preferably 8501200 F. a reactor contact time between 0.5 seconds and minutes, preferably 1 second to 10 minutes and a catalyst to oil ratio between 0.5 and 30, preferably between 2 and 15.
  • a contact time in the riser of 0.5 to 30 seconds, preferably 5 to seconds and a contact time in the reactor bed of 0 to 15 minutes, preferably 0 to 10 minutes and regenerator temperature of 1000 to 1500 F., particularly 11001350 F.
  • any of the catalytic cracking equipment currently employed in the petroleum industry may be utilized to practice our invention including a fixed bed catalyst reactor, a moving bed unit or a fluid catalytic cracking unit of varying types including those employing riser cracking. If a fixed bed reactor is employed, it will be periodically removed from operation for regeneration of the catalyst. In moving bed or fluid catalyst systems the catalyst is continually regenerated.
  • the naphtha feed is introduced into the catalyst reactor under the operating conditions described above to effect the desired conversion of the feedstock.
  • the efiluent is introduced into conventional recovery equipment which will include distillation equipment for the purpose of separating the vaporous effluent into products including naphtha and hydrocarbons lighter than naphtha whose high content of olefins and isobutane make them particularly useful as alkylate feedstocks and whose general characteristics make them particularly useful as petrochemical and polymer gasoline feeds.
  • the silica-alumina catalyst was employed in Runs 1 and 6 while a mixture of hydrogen mordenite and silica alumina was employed in Runs 4 and 8.
  • Zeolite No. 1 was Aerocat Triple S-4. This fluid catalytic cracking catalyst contains approximately 3 wt. percent of type Y zeolite composited in a silica-alumina matrix and containing rare earth metal cations;
  • Zeolite No. 2 was Davison XZ-25-This zeolitic cracking catalyst contains approximately 11 wt. percent of type X zeolite composited in a silica-alumina matrix and contains cations of rare earth metals;
  • Zeolite No. 3 was a high zeolite content catalyst containing approximately 40 wt. percent of type X zeolite composited in a silica-alumina matrix and containing rare earth metal cations. Zeolite No. 1 was employed in Runs 2 and 7; Zeolite No. 2 in Runs 3 and 9 and Zeolite No. 3 in Run 5.
  • Runs 1 to 3 were conducted at a temperature of 1025 F. and a space velocity of 3.6. Run 1 demonstrates the prior art and Runs 2 and 3 the process of our invention.
  • Run 4 'Runs 4 and 5 were conducted at a temperature of 880 F. and a space velocity of 7.2.
  • Run 4 demonstrates the prior art and Run 5 the process of this invention.
  • Runs 6 and 7 were conducted at approximately 895 F. and a space 'velocity of 3.6.
  • Run 6 exemplifies the prior art;
  • Run 7, the process of this invention.
  • Runs 8 and 9 were conducted at approximately 910 F. and a space velocity of 3.6.
  • Run 8 demonstrates the prior art and Run 9, the process of this invention.
  • Each of the catalysts was subjected to an activation step by heating at 1480" F. for 17 hours before a test run was made.
  • said aluminosilicate selected from the group consisting of zeolite X and zeolite Y and comprising cations selected from the group consisting of hydrogen, barium, calcium, magnesium, manganese, rare earth metals and mixtures thereof and (b) recovering products boiling below the initial boiling point of the low octane naphtha and a naphtha having an increased octane rating.
  • cracking conditions comprise a temperature of 700-1600 F., a catalyst-to-oil ratio between 0.5 and and a content time of 0.5 second to 15 minutes.
  • a process according to claim 1 wherein the cracking conditions comprise a temperature of 850-1200 F., a
  • a process for catalytic cracking of naphtha which comprises:
  • catalyst-to-oil ratio between 2 and 15 and a contact time of 1 second to 10 minutes.

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
US00889714A 1969-12-31 1969-12-31 Catalytic cracking of naphtha Expired - Lifetime US3761394A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US88971469A 1969-12-31 1969-12-31

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US3761394A true US3761394A (en) 1973-09-25

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US00889714A Expired - Lifetime US3761394A (en) 1969-12-31 1969-12-31 Catalytic cracking of naphtha

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US (1) US3761394A (pt)
AU (1) AU2379070A (pt)
BE (1) BE761080A (pt)
BR (1) BR7025026D0 (pt)
CA (1) CA945098A (pt)
ES (1) ES386941A1 (pt)
FR (1) FR2072151B1 (pt)
NL (1) NL7018911A (pt)
ZA (1) ZA708586B (pt)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3928175A (en) * 1973-05-24 1975-12-23 Mobil Oil Corp Upgrading crude oil by combination processing
US3928172A (en) * 1973-07-02 1975-12-23 Mobil Oil Corp Catalytic cracking of FCC gasoline and virgin naphtha
US4066531A (en) * 1975-09-26 1978-01-03 Mobil Oil Corporation Processing heavy reformate feedstock
US4376038A (en) * 1979-11-14 1983-03-08 Ashland Oil, Inc. Use of naphtha as riser diluent in carbo-metallic oil conversion

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1386552A (fr) * 1962-12-28 1965-01-22 Socony Mobil Oil Co Reformage catalytique
US4933280A (en) * 1984-12-11 1990-06-12 California Biotechnology Inc. Recombinant DNA sequence encoding Alveolar Surfactant Protein

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3928175A (en) * 1973-05-24 1975-12-23 Mobil Oil Corp Upgrading crude oil by combination processing
US3928172A (en) * 1973-07-02 1975-12-23 Mobil Oil Corp Catalytic cracking of FCC gasoline and virgin naphtha
US4066531A (en) * 1975-09-26 1978-01-03 Mobil Oil Corporation Processing heavy reformate feedstock
US4376038A (en) * 1979-11-14 1983-03-08 Ashland Oil, Inc. Use of naphtha as riser diluent in carbo-metallic oil conversion

Also Published As

Publication number Publication date
FR2072151A1 (pt) 1971-09-24
DE2064195A1 (de) 1971-07-15
ES386941A1 (es) 1973-04-16
BE761080A (fr) 1971-06-30
NL7018911A (pt) 1971-07-02
ZA708586B (en) 1972-04-26
FR2072151B1 (pt) 1973-12-07
CA945098A (en) 1974-04-09
DE2064195B2 (de) 1973-04-05
AU2379070A (en) 1972-06-29
BR7025026D0 (pt) 1973-03-13

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