US2260279A - Catalytic conversion of hydrocarbons - Google Patents

Catalytic conversion of hydrocarbons Download PDF

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Publication number
US2260279A
US2260279A US247132A US24713238A US2260279A US 2260279 A US2260279 A US 2260279A US 247132 A US247132 A US 247132A US 24713238 A US24713238 A US 24713238A US 2260279 A US2260279 A US 2260279A
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United States
Prior art keywords
hydrocarbons
line
chain
hydrogen
complex
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Expired - Lifetime
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US247132A
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English (en)
Inventor
Ouville Edmond L D
Bernard L Evering
Alex G Oblad
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Standard Oil Co
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Standard Oil Co
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Priority to NL63052D priority Critical patent/NL63052C/xx
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Priority to US247132A priority patent/US2260279A/en
Priority to FR861563D priority patent/FR861563A/fr
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Publication of US2260279A publication Critical patent/US2260279A/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
    • C10G61/00—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen
    • C10G61/02—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen plural serial stages only
    • C10G61/06—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen plural serial stages only the refining step being a sorption process
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2767—Changing the number of side-chains
    • C07C5/277—Catalytic processes
    • C07C5/2778—Catalytic processes with inorganic acids; with salts or anhydrides of acids
    • C07C5/2786—Acids of halogen; Salts thereof
    • C07C5/2789—Metal halides; Complexes thereof with organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C9/00—Aliphatic saturated hydrocarbons

Definitions

  • This invention relates to the preparation of saturated branched-chain hydrocarbons from hydrocarbon mixtures containing aliphatic hydrocarbons, naphthenes and aromatic hydrocar bons.
  • the 'invention relates to the preparation of 'motor fuel products containing large quantities of branchedchain saturated hydrocarbons and to the preparation of high solvency naphthas.
  • Saturated branched-chain hydrocarbons are very useful as motor fuels because of their nondetonating properties and high heating values. Furthermore, the saturated branched-chain hyconversion of the aromatic-free residue to prodrocarbons have lower boilingpoints than the corresponding Astraight-chain parafns so that motor fuels containing substantial quantities of 'the former have better starting characteristics than motor fuels containing large quantities of the straight-chain paramns. In addition,
  • ybranched-chainparaffin hydrocarbons are very useful as raw materials in the preparation of many chemical products.
  • One object of the present invention is' to process an admixture of parafns together with naphthenes and/or aromatics by a series of steps whereby two main products are formed, namely 'a product containing predominantly aromatic hydrocarbons and a product containing predominantly saturated branched-chain hydrocarbons f to be used in motor fuels having high octane numbers.
  • Another object of our invention is to secure improved yields of branched-chain par.-
  • Figure 1 is a general flow diagram of one arrangement for carrying out the invention
  • Figure 2 is a schematic flow diagram of a modified method of carrying out the invention
  • Figure 3 is a -schematic flow diagram of another modication according to our invention wherein aromatic hydrocarbons4 are removed from the isomerization feed stock by ⁇ alkylation followed by fractional distillation.
  • the feed stocks employed generally comprise mixtures containing at least normal paraflins, aromatics and naphthenes, it is advantageous to convert naphthenes to aromaticsby catalytic aromatization in the presence of hydrogen prior to the removal of aromatics from the isomerization feed stock.
  • Aromatization means the catalytic conversion of naphthenes, such as cyclohexane and its derivatives, to the corresponding aromatic hydrocarbons
  • “isomerization means f the catalytic conversion of normal paramns to saturated branched-chain hydrocarbons
  • space velocity means the volume of cold liquid, per volume of gross space occupied by the catalyst, passed through the catalyst per hour.
  • naphthenes and aromatic hydrocarbons is passed through a line l0, a heater Il and a line I2 to black, palladium,
  • aromatizer I3 Hydrogen from aline I4 is passed through the heater II, and lines I5 and I 6 to the aromatizer I3.
  • the aromatizer I3 is packed with a suitable aromatization catalyst, for example 90 AlaOa; 10 CrzOa (a mixture of 90 parts aluminum oxide by weight and parts chromic oxide by weight), platinum on magnesium chromite, nickel on magnesium chromite, platinum nickel or reduced copper suitably supported, or other suitable catalysts. .By maintaining the catalyst in the aromatizerV I3 at a temperature ranging from about 500 F.
  • the products in the aromatizer I3 are removed therefrom through a line I ⁇ 1 to a gas separator I8 wherein hydrogen is head through a line I9. to be either-recycled t0 the aromatizer I3 throughv a line 20 or utilized in a subsequent isomerization stage as hereinafter described.
  • the gas-free stock from the gas separator I8 is removed therefrom through a line 2I,and introduced into an extractor 22 wherein the aromatic hydrocarbons undergo substantially complete removal by countercurrent contact with a suitable selective solvent from a solvent storage tank -23 introduced into the upper portion of the extractor 22 through a line 24.
  • a suitable selective solvent we may use liquefied SO2, an aluminum chloride-complex, to which further reference will be made hereinafter, other solvents such as furfural, nitrobenzene, nitromethane, or other solvents selected with respect to the distillation characteristics of the feed stock employed and the boiling point of the solvent.
  • the temperature employed in the extraction stage will depend upon the solvent used, but in general this temperature will be between about 40 F. and 120 F.
  • the extract from the extractor 22 is removed therefrom through a line 25 and introduced into a separator 26. wherein the aromatic hydrocarbons are separated from the solvent.
  • 'I'he separator 26 may be heated by suitable means, such as a steam coil 21.
  • the separated solvent is removed from the separator 26 through a line 28, condensed in cooler 29, and returned to the solvent storage tank 23 through line 30.
  • the aromatic hydrocarbons are removed from the separator 26 through a line 3
  • the solvent-free raffinate, comprising substantially paraflnic hydrocarbons, is removed from the stripper 33 through a line 31 and passed through a preheater 38 and a line 39 to a catalytic isomerizer 40 wherein the normal paraffinic hydrocarbons are converted to saturated. branched-chain hydrocarbons as hereinafter described.
  • the raflinate may be sent directly to the preheater 38 through the line 32A, since a small amount of the aluminum chloride-hydrocarbon complex in the raffinate is not detrimental to the conversion of normal parafns to the saturated branched-chain hydrocarbons.
  • the rainate passes from the stripper 33 through a preheater 38 to a catalytic isomerizer ⁇ 40 maintained at the desired temperature by suitable means such as a jacket heater 4I, wherein it is intimately contacted with HCl-activated aluminum chloride, or other aluminum halides activated by a hydrogen halide, introduced into the isomerizer 40 from a catalyst storage tank 42 through a line 43.
  • suitable means such as a jacket heater 4I, wherein it is intimately contacted with HCl-activated aluminum chloride, or other aluminum halides activated by a hydrogen halide, introduced into the isomerizer 40 from a catalyst storage tank 42 through a line 43.
  • Contact of the raffinate with the catalyst is preferably made in the presence of hydrogen introduced into the isomerizer 40 through lines 44 and 45.
  • the hydrogen used in the isomerizer 40 may be that obtained from the gas separator I8 and introduced into line 44 through lines I 9 that obtained from the hydrogen storage tank (not shown) and introduced into line 44 through lines I4, I5 and 41.
  • the isomerizer 40 When the reaction is carried out in the presence of hydrogen the isomerizer 40 is maintained at a temperature within the range of about F. to about 450 F. by suitable means, such as the jacket heater 4I and under a hydrogen pressure from about 800 to about 4000 pounds per square inch. However, at times it may be desirable to carry out the conversion of the raffinate in the absence of extraneous hydrogen or under a relatively low hydrogen pressure, in which case the isomerizer 40 is 'operated within the temperature range of about 180 F. to about and 46, and/or sired the streams may be 450 F. under a pressureranging from about 50 pounds to about 800 pounds per square inch.
  • the aluminum' chloride-hydrocarbon complex I separated in the separator 49 is removed therefrom through a line 51.
  • the complex When the complex is employed as the solvent for the removal of varomatic hydrocarbons from the parafns following by way of example,v 90Al203z10Cr2O3 (a mixunconverted low-boiling hydrocarbons, particuthe aromatization stage, it may be transferred from the separator to the extractor 22 through lines 58, 36, 30, solvent storage tank 23 and line 24. A portion of the complex may also berecycled to the isomerizer 40 through line 59.
  • , may be blendedwith the saturated branched-chain hydrocarbons through a line 00.
  • aluminum chloride-complex having substantially the following composition:
  • a petroleum fraction containing at least paraillns, and naphthenes, and having a boiling range between about F. and about 400 F., and preferably between about 150 F. and 300 paralns but is an excellent thereby' making it an ex- F., from .a source (not hown) ture of parts aluminum oxide by weight, and
  • the aromatization is carried out at a temperature of -about'500 F. to about 1000 F., and preferably about 850 F. under a hydrogen pressure of4 about 0.2 to about 10 atmospheres and at a space velocity of about 0.05 to about 5.0.
  • 02 are removed therefrom through a line
  • 06 is 'removed therefrom through a line
  • 06 are removed therefrom through a line
  • 2 is removed therefrom through a line
  • a hydrogen halide-activated aluminum halide but preferably HCl-activated aluminum chloride and/or a mixture of aluminum chloride and aluminum chloride-complex to form satu- -rated branched-chain hydrocarbons.
  • the aluminum chloride catalyst isintroduced from a storage tank
  • fresh aluminum chlo- Aride catalyst we may use in combinationtherewith the aluminum chloride-complex separated from the aromatica in the still H5.
  • 0I matic-free aluminum chloride-complex from the still H5 is removed therefrom through a line
  • 2 comprising substantially normal parafflns is converted in the isomerizer
  • 20 comprising substantially saturated branched-chain hydrocarbons and aluminum chloride-complex are removed therefrom through aline
  • the aluminum chloride-complex used to extract the aromatic hydrocarbons from the products obtained from the aromatization stage is Withdrawn from the bottom of the separator
  • 26 may be by-passed through a line
  • the hydrocarbons separated in the separator 26 are removed therefrom through a line 3
  • the isomerized products are removed as side cuts from fractionator
  • 32 may be recycled to the isomerizer
  • This method of alkylation as a means of separation is especially applicable to the separation of aromatics from a narrow boiling range hydrocarbon cut that is 150 to 250 F. in which case the alkylated aromatics formed will distill outside this distillation range.
  • the alkylation takes place at a temperature of from about F. to about 225 F. under a pressure of from about 15 pounds to about 100 pounds per square inch in the presence of a suitable catalyst, such as aluminum 'chloride activated with HC1 or ,the aluminum chloride-complex obtained in the isomerlzation of normal paraiins to saturated branched-chain hydrocarbons.
  • a suitable catalyst such as aluminum 'chloride activated with HC1 or ,the aluminum chloride-complex obtained in the isomerlzation of normal paraiins to saturated branched-chain hydrocarbons.
  • the parafilns and naphthenes are removed as a side stream. and the alkylated aromatics removed as bottoms. 'I'he paraflins and naphthenes removed as a side stage wherein the normal parailins are converted to branched-chain parans as hereinabove described.
  • a petroleum fraction of the type hereinabove specified containing at least paraln and aromatic hydrocarbons from a source (not shownlis passed through lines
  • the alkylation takes placeat a temperature in the range from about 50 F. to about 225 F. maintained by means of Jacket -bottom of reactor
  • the catalyst aluminum chloride activated'with HC1 for example, can ⁇ be' introduced into reactor 163' through lines
  • reactionproducts are withdrawn from the through line
  • the hydrocarbon complex formed in the isomerization reaction or both are the catalytic ma-
  • the upper stratumcomprising unreacted paraffin and naphthene hydrocarbons and alkylated aromatics is removed from separator
  • 61 is introduced into the isomerization stage, which, as'shown in Figure 3, is similar to that illustrated in Figure 2.
  • This isomerization feed is heated in preheater
  • the alluminum chloride catalyst is introduced into isomerizer
  • 81 The upper layer is introduced into fractionator
  • the liquid layer in separator 205 now relatively free from naphthenes.- and rich in paraflns and aromatics is removed to the alkylation reactor
  • vtor fuel fraction and a under a hydrogen pressure of about 0.2 to about atmospheres to convert the naphthenic hydrocarbons therein to aromatic hydrocarbons, removing hydrogen from the products from said aromatization step, contactingthe substantially hydrogen-free product from said aromatization step with a selective solvent to form an extract layer comprising principally aromatic hydrocarbons and solvent anda rafnate layer rich in straightchain paran hydrocarbons and containing not more than about 2 per cent by volume of aromatic hydrocarbons, heating said extract layer to a temperature suilicient to distill the aromatic hydrocarbons therefrom, vent from said railinate layer, subjecting the rafiinate in an isomerization step to the action of an aluminum halide catalyst and an activator affording a hydrogen halide in the presence of hydrogen under conditions effective to convert straight-chain paraflln hydrocarbons to branched-chain hydrocarbons, separating a mofraction containing hydrogen and normally gaseous hydrocarbons from the products from said isomerization step, and recycling at least a
  • the process oi.' obtaining a solvent naphtha rich in aromatic hydrocarbons and a motor fuel rich in branched-chain paramn hydrocarbons from a naphtha feed stock containing substantial amounts of aromatic, naphthenic and straightchain paraffin hydrocarbons which comprises treating said feed stock in a catalytic aromatization step in the presence of hydrogen at a temperature of about 500 F. to about 1000 F. and
  • a rainate layer rich in straight-chain paraiiln hydrocarbons and containing not more than about 2 per cent by volume of aromatic hydrocarbons heating said extract layer todistill aromatic hydrocarbons therefrom, subjecting said ramnate layer in an isomerization step to the action of aluminum chloride and hydrogen chloride in the presence of hydrogen at a temperature of about F. to about 450 F. and a pressure of about 800 to about 4000 pounds per square inch to form branched-chain parallin hydrocarbons and an aluminum chloride-hydrocarbon complex, and using at least a portion 'or said aluminum chloride-hydrocarbon complex as solvent for aromatic hydrocarbons in said extraction step.

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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)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US247132A 1938-12-21 1938-12-21 Catalytic conversion of hydrocarbons Expired - Lifetime US2260279A (en)

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NL63052D NL63052C (enrdf_load_html_response) 1938-12-21
US247132A US2260279A (en) 1938-12-21 1938-12-21 Catalytic conversion of hydrocarbons
FR861563D FR861563A (fr) 1938-12-21 1939-11-11 Conversion catalytique des hydrocarbures

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2417699A (en) * 1942-05-16 1947-03-18 Shell Dev Method for isomerizing naphthenes and paraffins in a hydrocarbon mixture
US2421524A (en) * 1944-04-22 1947-06-03 Shell Dev Purification of metal halide catalyst in catalytic hydrocarbon conversions
US2438211A (en) * 1946-05-04 1948-03-23 Socony Vacuum Oil Co Inc Process using aluminum bromide-hydrocarbon complex to promote alkylation of aromatic hydrocarbons by olefins of more than two carbon atoms per molecule
US2450652A (en) * 1944-07-20 1948-10-05 Socony Vacuum Oil Co Inc Alkyl benzenes
US2481843A (en) * 1947-01-02 1949-09-13 Standard Oil Dev Co Extraction of aromatics with aluminum halide-aromatic complexes
US2483492A (en) * 1946-08-12 1949-10-04 Phillips Petroleum Co Purification of benzene and homologues thereof
US2495850A (en) * 1946-12-27 1950-01-31 Standard Oil Co Process of extracting aromatic hydrocarbons
US2504280A (en) * 1943-04-30 1950-04-18 Standard Oil Co Isomerization of light hydrocarbons
US2588506A (en) * 1947-04-15 1952-03-11 Extractive fractionation pbocess
US2604494A (en) * 1945-12-29 1952-07-22 Phillips Petroleum Co Process for the manufacture of a hydrocarbon solvent
US2645672A (en) * 1948-08-02 1953-07-14 Phillips Petroleum Co Alkylation of aromatic hydrocarbons
US2694095A (en) * 1951-12-01 1954-11-09 American Cyanamid Co Alkylation of aromatic hydrocarbons
US2739925A (en) * 1951-10-24 1956-03-27 Standard Oil Co Refining of hydrocarbon distillates
US2842604A (en) * 1952-04-09 1958-07-08 Shell Dev Separation of mixtures of alkyl-substituted aromatic hydrocarbons with aluminum halides
US2917449A (en) * 1955-01-25 1959-12-15 Texaco Inc Method of upgrading a petroleum naphtha
US3060248A (en) * 1959-05-06 1962-10-23 Exxon Research Engineering Co Hydrocarbon conversion process
US4452708A (en) * 1982-02-18 1984-06-05 Exxon Production Research Co. Oil recovery method using sulfonate surfactants derived from extracted aromatic feedstocks

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2417699A (en) * 1942-05-16 1947-03-18 Shell Dev Method for isomerizing naphthenes and paraffins in a hydrocarbon mixture
US2504280A (en) * 1943-04-30 1950-04-18 Standard Oil Co Isomerization of light hydrocarbons
US2421524A (en) * 1944-04-22 1947-06-03 Shell Dev Purification of metal halide catalyst in catalytic hydrocarbon conversions
US2450652A (en) * 1944-07-20 1948-10-05 Socony Vacuum Oil Co Inc Alkyl benzenes
US2604494A (en) * 1945-12-29 1952-07-22 Phillips Petroleum Co Process for the manufacture of a hydrocarbon solvent
US2438211A (en) * 1946-05-04 1948-03-23 Socony Vacuum Oil Co Inc Process using aluminum bromide-hydrocarbon complex to promote alkylation of aromatic hydrocarbons by olefins of more than two carbon atoms per molecule
US2483492A (en) * 1946-08-12 1949-10-04 Phillips Petroleum Co Purification of benzene and homologues thereof
US2495850A (en) * 1946-12-27 1950-01-31 Standard Oil Co Process of extracting aromatic hydrocarbons
US2481843A (en) * 1947-01-02 1949-09-13 Standard Oil Dev Co Extraction of aromatics with aluminum halide-aromatic complexes
US2588506A (en) * 1947-04-15 1952-03-11 Extractive fractionation pbocess
US2645672A (en) * 1948-08-02 1953-07-14 Phillips Petroleum Co Alkylation of aromatic hydrocarbons
US2739925A (en) * 1951-10-24 1956-03-27 Standard Oil Co Refining of hydrocarbon distillates
US2694095A (en) * 1951-12-01 1954-11-09 American Cyanamid Co Alkylation of aromatic hydrocarbons
US2842604A (en) * 1952-04-09 1958-07-08 Shell Dev Separation of mixtures of alkyl-substituted aromatic hydrocarbons with aluminum halides
US2917449A (en) * 1955-01-25 1959-12-15 Texaco Inc Method of upgrading a petroleum naphtha
US3060248A (en) * 1959-05-06 1962-10-23 Exxon Research Engineering Co Hydrocarbon conversion process
US4452708A (en) * 1982-02-18 1984-06-05 Exxon Production Research Co. Oil recovery method using sulfonate surfactants derived from extracted aromatic feedstocks

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