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
  • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
  • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
• • 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
  • C10G32/00—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms
• • 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
  • Y10S435/00—Chemistry: molecular biology and microbiology
  • Y10S435/8215—Microorganisms
  • Y10S435/822—Microorganisms using bacteria or actinomycetales
• • 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
  • Y10S435/00—Chemistry: molecular biology and microbiology
  • Y10S435/8215—Microorganisms
  • Y10S435/911—Microorganisms using fungi
  • Y10S435/921—Candida
• • 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
  • Y10S435/00—Chemistry: molecular biology and microbiology
  • Y10S435/8215—Microorganisms
  • Y10S435/911—Microorganisms using fungi
  • Y10S435/921—Candida
  • Y10S435/923—Candida lipolytica
• • 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
  • Y10S435/00—Chemistry: molecular biology and microbiology
  • Y10S435/8215—Microorganisms
  • Y10S435/911—Microorganisms using fungi
  • Y10S435/921—Candida
  • Y10S435/924—Candida tropicalis
• • 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
  • Y10S435/00—Chemistry: molecular biology and microbiology
  • Y10S435/8215—Microorganisms
  • Y10S435/911—Microorganisms using fungi
  • Y10S435/944—Torulopsis

Definitions

• This invention relates to a process for the removal of straight chain hydrocarbons, wholly or in part, from a hydrocarbon mixture and to the production of a purified hydrocarbon fraction therefrom.
• This invention also relates to a process as hereinbefore described with growth and recovery of a micro-organism. 7
• a process which comprises cultivating a micro-organism which is capable of growing on at least some straight chain hydrocarbons, cultivation being carried out in the presence of a hydrocarbon feedstock which consists in part of straight chain hydrocarbons in the presence of an aqueous nutrient medium and in the presence of a gas containing free oxygen and thereafter separating from the cultivated mixture, through the use of a surfactant, a fraction containing, as the major proportion thereof, unconsumed hydrocarbons together with a minor proportion of water and a minor proportion of surfactant, heating said fraction, whereby the surfactant is rendered partially or substantially water-insoluble, separating a hydrocarbon phase containing surfactant from an aqueous phase and hydrogenating said hydrocarbon phase under conditions such that the surfactant is rendered less effective or ineffective as an emulsifying agent.
• stocks may be unrefined or may have undergone some refinery treatment, but must contain a proportion of straight chain hydrocarbons in order to fulfil the purpose of this invention.
• the petroleum fraction will contain 345% by weight of straight chain hydrocarbons.
• the process of the invention is of particular value for the treatment of petroleum gas oil fractions which contain straight chain hydrocarbons in the form of waxes, since by the process of the invention a gas oil of improved pour point is obtained while the waxes are converted to a valuable product.
• micro-organism used herein we include mixtures of micro-organisms.
• the micro-organism is capable of growing on at least some normal parafiins.
• Micro-organisms which are cultivated as herein described may be yeasts, moulds or bacteria.
• yeasts in this specification are classified according to the classification system outlined in The Yeasts, a Toxonomic Study by J. Lodder and N. J. W. Kreger- Van Rij, published by North Holland Publishing Co. (Amsterdam) (1952).
• a yeast is employed this is of the family Cryptococcoaceae and particularly of the sub-family Cryptococcocideae however, if desired there may be used, for example, ascosporogeneous yeasts of the subfamily Saccharomycoideae.
• Preferred genera of the Cryptococcocideae sub-family are Torulopsis (also known as Torula) and Candida.
• Preferred strains of yeast are as follows. In particular it is preferred to use the specific stock of indicated Baarne reference number; these reference numbers refer to CBS stock held by the Central Bureau vor Schimmelculture, Baarne, Holland and to INRA stock held by the Institut National de la Recherche Agronomique, Paris France.
• Candida lipolytica Candida pulcherrima CBS 610 Candida utilis Candida uzilis, Variati major CBS 841 Candida tropicalis CBS 2317 Torulopsis colliculosa CBS 133 Hansenula anomala CBS Oidium lactis Neurosporo sitophila Mycoderma cancoillote INRA: STV 11 Of the above Candida lipolytica is particularly preferred.
• the micro-organism may be a mould.
• Suitable moulds are Penicillium and preferably there is used peill cillillm expansum.
• Another suitable genus is Aspergil us.
• the micro-organism may be a bacterium.
• the bacteria are of one of the orders: Pseudomonadales, Eubacteriales and Actinomycetales.
• the bacteria which are employed are of the families Corynebacteriaceae, Micrococoaceae, Achromobacteraceae, Actincymycetaceae, Rhizobiaceae, Bacillaceae and Pseudomonadaceae.
• Preferred species are Bacillus megaterium, Bacillus subtilis and Pseudomonas aeruginosa.
• Other strains which may be employed include:
• X anthomonas begoniae Flavobacterium devorans Acetobacter sp. Actinomyces sp. Nocardia opaca The growth operation will usually be discontinued before the stationary phase. If desired the growth stage may be continuous.
• the micro-organism After the growth stage it will usually be possible to separate the micro-organism, contaminated with some unmetabolised feedstock and aqueous nutrient medium, from the bulk of the unmetabolised feedstock fraction. Preferably the separation is achieved by means of a decantation; additionally or alternatively centrifuging may be used.
• the fraction containing the micro-organism is now subjected to treatment with an aqueous treating medium comprising water, a metal salt and a surface active agent consisting of or containing a non-ionic detergent.
• the treatment is carried out using one or more of the process conditions as hereinafter described.
• the product recovered from the fermenter is decanted to separate a fraction, consisting of about two thirds by volume of the product and consisting mainly of spent nutrient medium, from a product fraction containing substantially all of the product micro-organism and of the residual hydrocarbon together with some spent nutrient medium.
• a product fraction consisting of about two thirds by volume of the product and consisting mainly of spent nutrient medium, from a product fraction containing substantially all of the product micro-organism and of the residual hydrocarbon together with some spent nutrient medium.
• To the product fraction is added a mixture of equal volumes of sea water and fresh water, this mixture being added in an amount such that there is obtained a resultant mixture containing about gmS./litre of mineral salts.
• a nonionic surface active agent To this resultant mixture is added a nonionic surface active agent and the resultant mixture is centrifuged, suitably in a Sharples DG2 machine.
• the mixture is centrifuged at 2535 C., for example at about 30 C.
• the non-ionic detergent comprises, in the molecule, a chain of ethylene oxide groups.
• the detergent has the formula A(CH CH O)H where A is an alcohol residual group or acid residual group, the compound HA being selected from the following alcohols and acids and the value of n lying in a range as hereinafter shown, the range varying according to the compound HA, selected:
• the fraction containing the micro-organism is obtained from the centrifuge as a paste or cream; this fraction is washed with fresh water and again centrifuged.
• the fraction containing the micro-organism so obtained may be treated either by (a) Drying, suitably by spray drying or drum drying and then extracted with an azeotropic mixture of hexane and alcohol, or
• This oil phase is heated whereby the surface active agent is transferred from the water phase to the oil phase and the emulsion is broken.
• the oil phase is heated above the cloud point of the surfactant in water.
• a temperature in the range 100 C. is employed.
• the oil phase which is recovered contains surfactant which, if retained, would have a deleterious effect on the properties of the oil since, in the presence of water (which might be introduced intentionally or accidentally), the oil would have foaming characteristics.
• the oil phase is subjected to hydrogenation under conditions such that the surfactant is rendered less effective or ineffective as an emulsifying agent.
• Suitable catalysts for use in the hydrogenation stage are compounds of cobalt and molybdenum with or without iron, nickel metal, nickel/tungsten sulphide, or any other conventional hydrogenation or desulphurising catalyst.
• the temperature may lie in the range -500 C., usually 300-500 C., according to the catalyst; pressure from 10 70 kgs./ sq. cm.; space velocity from 1-10 vol./ vol/hour, hydrogen/hydrocarbon ratio in the range 0.1/1 to 5/1.
• the hydrogenation stage may be carried out in liquid, gas or mixed phase.
• EXAMPLE 1 40 litres of an aqueous mineral nutrient medium having the composition given below were introduced in a stainless steel fermenter having an effective capacity of 60 litres.
• the aqueous nutrient medium had the composition:
• the temperature of the culture was kept at 30i1 C. pH at 4 and aeration and agitation giving 3 millimoles of 0 per litre of medium per minute. Ammonia solution was admitted by an automatic pH controller.
• This gas oil was tested for emulsion forming characteristics by the test method ASTM B.1400.01 56T. In this test is used ccs. of water, 8 cc. of kerosine (as diluent) and 32 ccs. of the gas oil undergoing test. Results were as shown in the following Table 1.
• the recorded gas oil containing trace amounts of water and detergent was heated to 90 C., whereby the detergent was dissolved in the oil phase, and centrifuged at 90 C. in a Sharples tubular centrifuge at 14,000 g. to remove water.
• Percent M00 12.6 by weight C00 2.45 by weight 200 ccs. of the catalyst was used in the form of 2.5 mm. x 2.5 mm. cylindrical pellets and hydrogenation conditions were:
• the treated gas oil was tested for emulsion forming characteristics by the test method ASTM B.1400-01 56 T. In this test is used 40 cc. of water, 8 cc. of kerosine (as diluent) and 32 ccs. of the gas oil undergoing test. Re-
• Non-metabolized gas oil 112 Paste of micro-organism 49 The non-metabolized gas oil had the following characteristics:
• the temperature of the culture was kept at 30il C., pH at 4, the conditions of aeration and stirring being maintained to give 3 millimoles of per litre of medium per minute.
• Ammonia solution was admitted by an automatic pH controller.
• Non-metabolized gas oil 112 49 Paste of micro-organism The non-metabolized gas oil had the following characteristics The trace amount of detergent was found to have led to undesirable emulsifying characteristics in the gas oil.
• This gas oil was tested for emulsion forming characteristics by the test method ASTM B.l400.01 56T. In thmis test is used 40 ccs. of water ,8 cc. of kerosine (as diluent) and 32 ccs. of the gas oil undergoing test. Results were shown in the following Table 2.
• the recovered gas oil containing trace amounts of water and detergent was heated to 90 0, whereby the detergent was dissolved in the oil phase, and centrifuged at 90 C. in a Sharples tubular centrifuge at 14,000 g. to remove water.
• a micro-organism was grown on a heavy gas oil and harvested using the conditions of growth and harvesting described in Example 2, except that the micro-organism employed was of the strain Hansenula suaveolens in place of the Candida utilis (employed according to Example 2) and that the aqueous nutrient medium contained 0.300 gram/ litre of yeast extract.
• the non-ionic detergent sold under the trade designation N1 29 is a product obtained by condensing a mixture of lauric alcohol and myristic alcohol with ethylene oxide, the product having an ethylene oxide chain of an average 8.5 units per terminal group.
• a process which comprises cultivating a micro-organism which is capable of growing on at least some straight chain hydrocarbons, cultivation being carried out in the presence of a hydrocarbon feedstock which consists in part of straight chain hydrocarbons in the presence of an aqueous nutrient medium and in the presence of a gas containing free oxygen and thereafter separating from the cultivated mixture, through the use of a surfactant, a fraction containing, as the major proportion thereof, unconsumed hydrocarbons together with a minor proportion of water and a minor proportion of surfactant, heating said fraction, whereby the surfactant is rendered partially or substantially water-insoluble, separating a hydrocarbon phase containing surfactant from an aqueous phase and hydrogenating said hydrocarbon phase under conditions such that the surfactant is rendered less effective or ineffective as an emulsifying agent.
• microorganism is a straight chain paraffinic hydrocarbon-consuming yeast.
• yeast is Candida lipolytica.
• nonionic detergent comprises, in the molecule, a chain of ethylene oxide groups.

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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)
• Life Sciences & Earth Sciences (AREA)
• Microbiology (AREA)
• Preparation Of Compounds By Using Micro-Organisms (AREA)

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Citations (2)

• 0
  • FR FR1511756D patent/FR1511756A/fr not_active Expired
• 1966
  • 1966-02-03 GB GB4763/66A patent/GB1168831A/en not_active Expired
• 1967
  • 1967-01-25 US US611561A patent/US3536585A/en not_active Expired - Lifetime
  • 1967-01-31 NL NL6701503A patent/NL6701503A/xx unknown
  • 1967-02-02 DE DE1967B0091002 patent/DE1645690B2/de active Granted
  • 1967-02-03 BE BE693611D patent/BE693611A/xx unknown

Patent Citations (2)

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