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WO2011073427A1 - Procédé de production d'hydrocarbures à partir de lipides microbiens - Google Patents

Procédé de production d'hydrocarbures à partir de lipides microbiens Download PDF

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Publication number
WO2011073427A1
WO2011073427A1 PCT/EP2010/070154 EP2010070154W WO2011073427A1 WO 2011073427 A1 WO2011073427 A1 WO 2011073427A1 EP 2010070154 W EP2010070154 W EP 2010070154W WO 2011073427 A1 WO2011073427 A1 WO 2011073427A1
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Prior art keywords
range
lipids
catalyst
process according
paraffinic hydrocarbons
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Inventor
Carolina Botella-Franco
Hans De Lang
Lavanya Meesala
Argi Joachim Antonio Moppi
Colin John Schaverien
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
    • C10G3/46—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof in combination with chromium, molybdenum, tungsten metals or compounds thereof
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °C
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4012—Pressure
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates to a process for converting microbial lipids, in particular those derived from oleaginous microorganisms, to produce hydrocarbon fuel components.
  • renewable energy sources is becoming increasingly important as a feedstock for production of hydrocarbon compounds .
  • Microbial biomass includes components such as lipids, sugars,
  • microorganisms like algae, yeast, fungi and bacteria. These microorganisms are being explored as feed for the production of hydrocarbon compounds primarily due to their easy cultivation and high purity yields .
  • US-A-20090047721 describes the use of fungi, algae and yeast for the production of fuels such as renewable diesel.
  • the lipids present in the microorganisms are often extracted and further processed by transesterification for the
  • the present invention provides a process for producing hydrocarbons from microbial lipids, comprising the steps of:
  • microbial lipids comprise a triglyceride content in the range of from 40 wt% to 70 wt% and a free fatty acid content in the range of from 10 wt% to 30 wt%, with a hydrogenation catalyst and hydrogen at a temperature in the range of from 250 to 380 °C and a total pressure in the range of from 20 to 160 bar (absolute), to obtain an effluent comprising paraffinic hydrocarbons and water;
  • step (b) optionally separating a liquid stream rich in paraffinic hydrocarbons from the effluent obtained in step (a) ;
  • step (d) separating at least one product fraction from the product stream obtained in step (c) .
  • microbial lipids obtained from oleaginous microorganisms preferably yeasts
  • Such a process allows one to convert the microbial lipids to hydrocarbons without needing a conversion to C14-C18 alkyl esters as described in US2009/0047721.
  • Microbial oils produced by oleaginous microorganisms including bacteria, algae and yeasts, have become a promising potential source for biodiesel production.
  • Oleaginous microorganisms are defined as being able to accumulate lipids over 20wt% of their dry biomass. A proportion of those lipids are m the form of trlacylglycerols (TAGs), containing fatty acids that are comparable to those found in conventional vegetable oils.
  • TAGs trlacylglycerols
  • Yeasts are eukaryotic micro-organisms classified in the kingdom Fungi. Oleaginous yeasts or oil- producing yeasts produce and store lipids similar to vegetable oils and fats.
  • Microbial lipids as referred to in the present invention are a group of naturally occurring compounds that are usually hydrophobic and contain long-chain aliphatic hydrocarbons and their derivatives such as fatty acids, alcohols, amines, amino alcohols and aldehydes .
  • These lipids include monoglycerides, diglycerides and triglycerides, which are esters of glycerol and fatty acids, and phospholipids, which are esters of glycerol and phosphate group-substituted fatty acids.
  • the fatty acid moiety in the lipids used in the present invention ranges from 4 carbon atoms to 30 carbon atoms, and includes saturated fatty acids containing one, two or three double bonds.
  • the fatty acid moiety includes 8 carbon atoms to 25 carbon atoms, more preferably 12 carbon atoms to 20 carbon atoms.
  • the lipids may contain variable amounts of free fatty acids and/or esters, both of which may also be converted into hydrocarbons during the process of this invention.
  • the lipids typically also include carotenoids, hydrocarbons, phosphatides, simple fatty acids and their esters, terpenes, sterols , fatty alcohols, tocopherols, polyisoprene, carbohydraes and proteins, glycolipids and phospholidips .
  • the most preferred lipids as feedstock for the subject process are those obtained from the culturing of oleaginous yeasts such as Cryptococcus curvatus, Cryptococcus terricolus, Candida sp., Lipomyces starkeyi, Lipomyces lipofer, Endomycopsis vernalis, Rhodotorula glutinis, Rhodotorula gracilis, Rhodosporidium toruloides and Yarrowia lipolytica in suitable conditions of pH and temperature and in the presence of a suitable culture medium.
  • yeasts such as Cryptococcus curvatus, Cryptococcus terricolus, Candida sp., Lipomyces starkeyi, Lipomyces lipofer, Endomycopsis vernalis, Rhodotorula glutinis, Rhodotorula gracilis, Rhodosporidium toruloides and Yarrowia lipolytica in suitable conditions of pH and
  • Rhodosporidium toruloides A particularly interesting oleaginous yeast, Rhodosporidium toruloides, was found to be one of the most promising microorganisms for the conversion of sugars to lipid considering variables such as lipid content, carbon efficiency, volumetric productivity and product yield.
  • R . toruloides 444 accumulated higher lipid content than other species of the strain tested, and to the high saturated content of the fatty acids in the lipids .
  • the subject process preferably also comprises the steps of (i) cultivating the oleaginous microbe at suitable conditions and with a suitable medium to produce microbial lipids, and (ii) extracting the microbial lipids from the microbe, prior to subjecting the lipids to step (a) .
  • the oleaginous microbe more particularly the oleaginous yeast is preferably cultured in a fermentor at pH conditions in the range of from 5 to 6.
  • the temperature maintained in the fermentor is preferably in the range of from 20 to 40 °C, more preferably in a range of from 25 to 35°C .
  • An aeration of preferably about 1 vvm is preferably maintained in the fermenter.
  • a basal medium comprising a carbon source such as glucose, sucrose, xylose or any other suitable carbon source in a concentration of from 50 to 70 g/L, more preferably 60 g/L, peptone in a range of from 15 to 25, more preferably 19 to 21 g/L) and more preferably, yeast extract in a range of from 15 to 25, more preferably 19 to 21 g/L) .
  • the fermentor is preferably inoculated with a seed inoculum which has grown in two stage culture preferably in a YMY medium with a glucose source.
  • the fermentation may preferably be run in fed-batch mode preferably using a concentrated carbon source solution, which is preferably fed when the initial carbon source is consumed. Several; different feeds may be added during the fermentation to increase carbon source concentration up to 100 g/L.
  • Suitable fermentation media includes Brazilian sugar cane juice, preferably diluted for the basal media up to 60 g/L and concentrated up to 800 g/L as a feeding solution.
  • lipids thus obtained from the aforementioned fermentation process are preferably isolated from the microbial population for further processing.
  • the lipids obtained from the oleaginous microbial species will be referred to as lipids for the purpose of the present invention.
  • the microbial lipids preferably have a triglyceride content in the range of from 40 wt% to 70 wt% and a free fatty acid content in the range of from 10 wt% to 30 wt%.
  • the microbial lipids are then suitably extracted from the microbial cells. This may be done by any method that is suitable. Such methods are well known in the art, see for instance US 6,727,373, US-A-200125114 and CA-A-2579516.
  • the thus obtained microbial lipids are subjected to a hydrogenation in the presence of a suitable hydrogenation catalyst, and optionally a hydrocarbon feed in a suitable hydrotreatment reactor .
  • step (a) hydrogen and the feedstock comprising lipids are first contacted with a hydrogenation catalyst under hydro-deoxygenation conditions in step (a) .
  • a hydrogenation catalyst under hydro-deoxygenation conditions in step (a) .
  • triglycerides, diglycerides, monoglycerides and/or free fatty acids in the feedstock are converted into hydrocarbons, water and carbon oxides .
  • the extent to which decarboxylation occurs depends on the hydrogenation catalyst used and the process conditions applied.
  • the hydro-deoxygenation conditions comprise a temperature in the range of from 250 to 380 °C and a pressure in the range of from 20 to 160 bar (absolute) .
  • the hydro-deoxygenation temperature in step (a) is in the range of from 280 to 340 °C.
  • Reference herein to the hydro- deoxygenation temperature is to the maximum temperature that is occurring in hydro-deoxygenation step (a) .
  • the temperature in the upper part of the catalyst bed will typically be higher than the temperature in the upper lower part of the catalyst bed.
  • An effluent comprising paraffinic hydrocarbons and water is obtained in step (a) .
  • the effluent further comprises carbon oxides, unconverted hydrogen, and, if the feedstock comprises sulphur and/or nitrogen-containing compounds also hydrogen sulphide and/or ammonia.
  • a suitable catalyst will be present in the hydrotreatment unit.
  • the feed to the hydrodeoxygenation reactor may include hydrocarbons derived from mineral crude oil or refinery streams.
  • the hydrocarbon feed used has a boiling point of at least 220°C, as measured by Gas Chromatograph Distillation (GCD) according to ASTM D-2887. More preferably, the boiling point range from 220°C to 650°C, yet more preferably from 300°C to 600°C.
  • the hydrocarbon feed for the purpose of the present invention includes high boiling, non- residual oils such as straight run (atmospheric) gas oils, flashed distillate, coker gas oils, or atmospheric residue ('long residue') and vacuum residue ('short residue').
  • mainly paraffinic and/or naphthtenic compounds such as dodecane or hydrotreated gas oil can be used as hydrocarbon feed, since they are reasonably inert and only exhibit minor cracking and/or hydrogenation at the conditions of the hydrodeoxygenation, but permit to dilute the heat of the reaction to avoid hotspots.
  • part of the liquid product stream obtained in optional step (b) can be recycled as diluents to step (a) .
  • the hydrotreatment unit includes an arrangement of heaters, heat exchangers, reactors, compressors and boilers that are set at different temperatures and pressures.
  • the yeast lipids and the hydrocarbon feed can be blended and introduced into the hydrotreatment unit as the feedstock through a charge pump.
  • the hydrocarbon feed may also be introduced in the hydrotreatment unit at different stages.
  • the hydrocarbon feed to the yeast lipids ratio ranges from 1: 100 to 100:1, preferably 20:1 to 1:20, more preferably from 5:1 to 1:5.
  • the feedstock, whether neat lipids or blended with a hydrocarbon feed is preferably mixed with hydrogen gas which can be directed from a catalytic reforming unit or a hydrogen plant.
  • the feedstock and the hydrogen mixture are preferably heated in succession through heat exchange with reactor effluent in a heat exchanger unit and a fired heater.
  • the number of reactor volumes of feed that can be treated in a unit time is indicative by space velocity which is preferably 0.5 kg/l/h to 2 kg/l/h and rate at which the hydrogen gas flows also referred to as gas rate is kept preferably at 800 to 2000 Nl/kg/h.
  • Catalysts suitable for use in step (a) of the process according to the invention are well known in the art.
  • the catalyst usually comprise two parts, a catalyst support and active elements.
  • the support comprises solid substances with high porosity and able to withstand the temperature, pressure and the environment encountered in the hydrotreatment unit.
  • alumina in the form of balls or extrudates can be used as a support for the active elements in the catalyst.
  • the active elements used are preferably cobalt, more preferably, nickel, molybdenum, tungsten and its combinations thereof .
  • the hydrogenation catalyst comprises sulphided hydrogenation compounds, typically sulphided nickel or cobalt in combination with sulphided molybdenum or tungsten.
  • a sulphur source will typically be supplied to the hydrogenation catalyst in order to keep the catalyst in sulphided form during hydrodeoxygenation step (a) .
  • the effluent of step (a) then comprises hydrogen sulphide.
  • the hydrogenation catalyst of step (a) may be any hydrogenation catalyst known in the art that is suitable for hydro-deoxygenation, typically a catalyst comprising metals of Group VIII and/or Group VIB of the Periodic Table of Elements or compounds thereof.
  • catalysts are catalysts comprising Pd, Pt, reduced Ni, or sulphided CoMo, NiMo or NiW as hydrogenation components on a carrier.
  • the carrier typically comprises a refractory oxide, preferably alumina, amorphous silica-alumina, titania or silica.
  • the carrier may comprise a zeolitic compound.
  • the catalyst may be sulphided in-situ or ex-situ.
  • In-situ sulphiding may be achieved by supplying a sulphur source, usually hydrogen sulphide or a hydrogen sulphide precursor, i.e. a compound that easily decomposes into hydrogen sulphide such as for example dimethyl disulphide, di-tert-nonyl polysulphide or di-tert-butyl polysulphide , to the catalyst of step (a) during operation of the process.
  • the sulphur source may be supplied with the feedstock, the hydrogen or separately.
  • An alternative suitable sulphur source is a sulphur-comprising hydrocarbon stream boiling in the diesel or kerosene boiling range that is be co-fed with the feedstock.
  • an amount of in the range of from 100 to 5,000 ppmv hydrogen sulphide, more preferably of from 500 to 2,000 ppmv, or an equivalent amount of a hydrogen sulphide precursor, based on the volume of hydrogen supplied, is supplied to step (a) .
  • separation step (b) a liquid stream rich in paraffinic hydrocarbons is separated from the effluent obtained in step (a) .
  • separation step (b) is carried out at a high pressure, i.e. a pressure in the range of from 0.5 to 10 bar lower, preferably of from 1 to 5 bar lower, than the pressure at the outlet of the reactor vessel in which step (a) is carried out.
  • Step (b) may be carried out in a low temperature, high pressure separator to separate a gaseous stream depleted in water, a liquid water-rich stream and the liquid stream rich in paraffinic hydrocarbons from the effluent obtained in step (a) .
  • Low temperature, high pressure separators are known in the art.
  • the effluent of step (a) is first cooled, preferably to a temperature in the range of from 10 to 150 °C, and the cooled effluent is then, in a separation vessel, separated into a gaseous phase depleted in water and a liquid phase. Due to a difference in density, the liquid phase separates into a water-rich liquid phase and hydrocarbon-rich liquid phase.
  • the pressure in the separation vessel is preferably in the range of from 0.5 to 10 bar lower, more preferably in the range of from 1 to 5 bar lower, than the total pressure at the outlet of the reactor vessel wherein step (a) is carried out .
  • step (b) may be recycled, optionally after removal of impurities like hydrogen sulphide, ammonia, carbon oxides, light hydrocarbons or steam, to step (a) and/or step (c) to provide part of the hydrogen needed in step (a) and/or step (c) .
  • step (b) may be carried out in a high temperature, high pressure separator to separate a gaseous stream rich in water and the liquid stream rich in paraffinic hydrocarbons from the effluent obtained in step (a) .
  • High temperature, high pressure separators are known in the art.
  • the temperature in the high temperature, high pressure separator is chosen such that there is sufficient separation between water and paraffinic hydrocarbons whilst the temperature is as little as possible below the inlet temperature of hydroisomerisation step (c).
  • the temperature in the high temperature, high pressure separator is in the range of from 160 to 350 °C, usually of from 180 to 320 °C.
  • the gaseous stream rich in water will contain the major part of the water that was present in the effluent of step (a) . If the gaseous stream is to be recycled to step (a) and/or step (c), it is therefore preferred that water is removed from it prior to recycling. Water removal from the gaseous stream rich in water is suitably done in a low temperature, high pressure separator.
  • a gaseous stream depleted in water is obtained that may be recycled, optionally after removal of impurities like hydrogen sulphide, ammonia, carbon oxides, light hydrocarbons or steam, to step (a) and/or step (c) to provide part of the hydrogen needed in step (a) and/or step (c) .
  • step (b) If no separation according to step (b) applied then care has to be taken to not allow the water to condense as this may negatively impact the catalyst particle strength, and lead to metal leaching in step (c) .
  • the catalyst of step (c) may comprise a zeolitic compound.
  • Any acidic zeolitic compound having hydro- isomerising activity may suitably be used.
  • Such zeolitic compounds are known in the art. Examples of such zeolitic compounds include, but are not limited to, zeolite Y, zeolite beta, ZSM-5, ZSM-12, ZSM-22, ZSM-23, ZSM-48, SAPO-11, SAPO- 41, and ferrierite .
  • hydrogenation step comprises mainly normal paraffins in the range of C 8 to C 2 o and is further subjected to a catalytic isomerisation step.
  • Catalytic isomerisation as referred to in the present invention is the rearrangement of atoms within a molecule in the presence of a catalyst. It is typically used for upgrading of hydrocarbons such that they can effectively be used as fuels.
  • the catalytic isomerisation of longer chain hydrocarbons is used to increase the cold flow properties.
  • the liquid stream rich in paraffinic hydrocarbons obtained in optional separation step (b), or the total effluent of step (a) is hydroisomerised in step (c) .
  • step 9b) preferably, the liquid stream comprises less than 30 wt%, more preferably less than 10 wt%, even more preferably less than 5 wt%, of the water comprised in the effluent of step (a) .
  • the liquid stream may further comprise impurities like propane, dissolved hydrogen sulphide, and carbon oxides . It will be appreciated that the lower the temperature in separation step (b), the higher the amount of low-molecular weight compounds dissolved in the liquid stream rich in paraffinic hydrocarbons .
  • the catalytic isomerisation is typically conducted in the presence of an isomerisation catalyst which maybe a molecular sieve-based catalyst which exhibits selective and substantial isomerisation activity under the operating conditions of the isomerisation zone.
  • the isomerisation catalyst used is preferably a nickel/ tungsten (Ni/W) based catalyst, while under sulphur free conditions a platinum based dewaxing catalyst may be used.
  • the catalyst composition comprises at least a hydrogenation component, a binder and zeolite crystallites, wherein the zeolite has pores consisting of 12 oxygen atoms and has a constrain index (CI) larger than 1.
  • Constraint Index seems to vary somewhat with severity of operations (conversion) and the presence or absence of binders. Likewise, other variables, such as crystal size of the zeolite, the presence of occluded contaminants, etc., may affect the Constraint Index.
  • a zeolite is considered to have a Constraint Index of larger than 1 if when tested at at least one temperature within the range of 550 °F (290 °C) to
  • the zeolite used in the present invention is not a typical large pore zeolites such as zeolite beta (BEA type) or mordenite (MOR type) because typically such large pore zeolites have a CI value of less than 1.
  • BEA type zeolite beta
  • MOR type mordenite
  • the three letter code describing the zeolite is according to the Structure Type Codes as defined by the IZA Structure Commission and described in detail in Zeolites 17:1-230, 1996 pages 5-12.
  • the zeolite a typical medium pore zeolite because medium pore zeolites typically have pores consisting of 10 oxygen atoms as the largest pore opening.
  • Such medium pore zeolites typically have a CI value larger than 1, for example
  • ZSM-23 (MTT Type) having a CI value of 9.1.
  • the zeolite has 12 oxygen-ring defined pores, wherein the largest pore axis of these pores is between 5 and 7 A. This axis length should be determined by X-ray diffraction. Typical values for such axis are described for different zeolites in Zeolites 17:1-230, 1996 page 9.
  • zeolites which can be used in the present invention having the above properties, are zeolites of the OFF Type and MTW type zeolites. Both these 12-oxygen ring zeolites have CI value's of above 1 and more preferably above
  • Examples of OFF type zeolites are Linde T, LZ-217 and TMA-0. Reference is also made to US-A-4503023 describing an OFF Type zeolite. More preferably MTW type zeolites are used. This class of zeolites includes ZSM-12 as described in US-A- 3,832,449, CZH-5 as described in GB-A-2079735, Gallosilicate MTW as described m Y.X. Zhi, A. Tuel, Y. Bentaarit and C.
  • the average crystal size of the zeolite is preferably smaller than 0.5 ⁇ and more preferably smaller than 0.1 ⁇ as determined by the well-known X-ray diffraction (XRD) line broadening technique using the high intensity peak at about 20.9 2-theta in the XRD diffraction pattern .
  • XRD X-ray diffraction
  • the binder in the catalyst may be any binder usually used for such an application.
  • a possible binder includes alumina or alumina containing binders.
  • Applicants have found that low acidity refractory oxide binder material that is essentially free of alumina provides more improved catalyst. Examples are low acidity refractory oxides such as silica, zirconia, titanium dioxide, germanium dioxide, boria and mixtures of two or more of these.
  • the most preferred binder is silica.
  • the weight ratio of the molecular sieve and the binder can be anywhere between 5:95 and 95:5. Lower zeolite content, suitable between 5 and 35 wt%, may in some cases be advantageous for achieving an even higher selectivity.
  • the silica to alumina molar ratio of the zeolite prior to dealumination is preferably larger than 50 and more preferably between 70 and 250 and most preferably between 70 and 150.
  • the zeolite has been subjected to a dealumination treatment.
  • the dealumination of the zeolite results in a reduction of the number of alumina moieties present in the zeolite and hence in a reduction of the mole percentage of alumina.
  • alumina moiety refers to an Al 2 0 3 -unit which is part of the framework of the aluminosilicate zeolite, i.e.
  • the mole percentage of alumina present in the aluminosilicate zeolite is defined as the percentage of moles A1 2 0 3 relative to the total number of moles of oxides
  • dealumination is performed such that the reduction in alumina moieties in the framework is between 0.1 and 20%.
  • Dealumination may be performed by means of steaming.
  • the surface of the zeolite crystallites are selectively dealuminated .
  • a selective surface dealumination results in a reduction of the number of surface acid sites of the zeolite crystallites, whilst not affecting the internal structure of the zeolite crystallites.
  • the reduction of alumina moieties in the framework will be lower and preferably between 0.1 and 10%.
  • Dealumination using steam results is a typical nonselective dealumination technique .
  • Dealumination can be attained by methods known in the art. Particularly useful methods are those, wherein the dealumination selectively occurs, or anyhow is claimed to occur selectively, at the surface of the crystallites of the molecular sieve. Examples of dealumination processes are described in WO-A-9641849. US-A-5015361 describes a method wherein the zeolites are contacted with sterically hindered amine compound.
  • dealumination is performed by a process in which the zeolite is contacted with an aqueous solution of a fluorosilicate salt wherein the fluorosilicate salt is represented by the formula:
  • 'A' is a metallic or non-metallic cation other than H + having the valence y b'.
  • cations y b' are alkylammonium, NH4 + , Mg ++ , Li + , Na + , K + , Ba ++ , Cd ++ , Cu + , Ca ++ , Cs + , Fe ++ , Co ++ , Pb ++ , Mn ++ , Rb + , Ag + , Sr ++ , Tl + , and Zn ++ .
  • 'A' is the ammonium cation.
  • the zeolite material may be contacted with the fluorosilicate salt at a pH of suitably between 3 and 7.
  • a dealumination process is for example described in US-A-5157191. The dealumination
  • the catalyst composition is preferably prepared by first extruding the zeolite with the low acidity binder and subsequently subjecting the extrudate to a dealumination treatment, preferably the AHS treatment as described above. It has been found that an increased mechanical strength of the catalyst extrudate is obtained when prepared according to this sequence of steps. It is believed that by maintaining the acidity of the catalyst at a low level conversion to products boiling outside the lube boiling range is reduced. Applicants found that the catalyst should have an alpha value below 50 prior to metals addition, preferably below 30, and more preferably below 10. The alpha value is an approximate indication of the catalytic cracking activity of the catalyst compared to a standard catalyst.
  • the alpha test is
  • the hydrogenation component in step (c) suitably comprises at least one Group VIB metal component and/or at least one Group VIII metal component.
  • Group VIB metal components include tungsten, molybdenum and/or chromium as sulphide, oxide and/or in elemental form. If present, a Group IB metal component and/or tungsten, molybdenum and/or chromium as sulphide, oxide and/or in elemental form. If present, a Group VIB metal components include tungsten, molybdenum and/or chromium as sulphide, oxide and/or in elemental form. If present, a Group IVB metal components.
  • VIB metal component is suitably present in an amount of from 1 to 35% by weight, more suitably from 5 to 30% by weight, calculated as element and based on total weight of support, i.e. modified molecular sieve plus binder.
  • Group VIII metal components include those components based on both noble and non-noble metals.
  • Group VIII metal components are palladium, platinum, nickel and/or cobalt in sulphidic, oxidic and/or elemental form.
  • Nickel and/or cobalt if present at all, may be present in an amount in the range of from 1 to 25% by weight, preferably 2 to 15% by weight, calculated as element and based on total weight of support.
  • the total amount platinum or palladium will suitably not exceed 10% by weight calculated as element and based on total weight of support, and preferably is in the range of from 0.1 to 5.0% by weight, more preferably from 0.2 to 3.0% by weight.
  • the weight ratio of platinum to palladium may vary within wide limits, but suitably is in the range of from 0.05 to 10, more suitably 0.1 to 5.
  • Catalysts comprising palladium and/or platinum as the hydrogenation component are preferred. Most preferred is when platinum is used as the sole hydrogenation component.
  • the hydrogenation component is suitably added to the catalyst extrudate comprising the dealuminated
  • aluminosilicate zeolite crystallites by known techniques.
  • Step (c) is typically performed at a temperature in the range of from 280 to 450 °C and a total pressure in the range of from 20 to 160 bar (absolute) .
  • the hydro- isomerisation temperature is in the range of from 300 to 400 °C, more preferably of from 330 to 380 °C.
  • the total pressure in each of steps (a) and (c) is preferably in the range of from 40 to 120 bar (absolute), more
  • the weight hourly space velocities (WHSV) in the range of from 0.1 to 10 kg of oil per litre of catalyst per hour
  • step a) and catalytic isomerisation (step c) can be carried out simultaneously in a reactor with a stacked bed single stage configuration that enables the step (a) to take place on one bed with the hydrogenation catalyst stacked on the bed.
  • the product stream obtained in step (a) is then fed to another bed of the reactor stacked with isomerisation catalyst where it is subjected to step (c) .
  • the product stream, obtained from step (c) is further subjected to a separation process (d) to primarily obtain renewable diesel and/or kerosene fractions along with other hydrocarbons that may be processed further.
  • a separation process (d) to primarily obtain renewable diesel and/or kerosene fractions along with other hydrocarbons that may be processed further.
  • the commercial products obtained from these hydrocarbons are also within the scope of the invention. It may be understood that processing of the aforementioned hydrocarbon products is well known in the art and is in no way limiting to the scope of the invention. While some of the methods have been described herein, several other processes may be used to convert the hydrocarbon fractions into commercially usable products.
  • the oleaginous yeast R. toruloides 444 was cultured in a fermentor at pH conditions in the range of from 5 to 6, at a temperature maintained of 30 °C. An aeration of about 1 vvm was maintained in the fermentor.
  • the culture medium used comprised a basal media comprising a carbon source based on glucose in a concentration of 60 g/L, peptone (20.3 g/L) and yeast extract (20.3 g/L) .
  • the fermentor was inoculated with a seed innoculum which has grown in two stage culture
  • the fermentation was operated in fed-batch mode using a
  • concentrated carbon source solution was fed when the initial carbon source was consumed. Three different feeds were added during the fermentation to increase carbon source
  • the yeast After the first feeding when the concentration of nitrogen was consumed, the yeast started accumulate lipids . The yeast was able to accumulated between 40-70% depending on the feedstock used obtaining a yield of 26 g lipid per g of C source.
  • the yeast lipids were extracted after cell disruption and centrifugation to remove the lipids, followed by a solvent extraction from the aqueous medium.
  • the yeast lipids comprised of 54 wt % triacylglycerides (TAGs), 3.9 wt % diglycerides , 0.2 wt % monoglycerides and 19.5 wt % of free fatty acids.
  • TAGs triacylglycerides
  • the total metal content of the yeast lipids was 710 ppm, in particular phosphorus 300 ppm, silicon 250 ppm, sodium 90 ppm and calcium 41 ppm.
  • the yeast lipids were diluted (18 wt %) in dodecane and fed to the supplied to the top bed of a fixed bed microflow unit at 300°C, 60 bar and WHSV (Weight by hour space velocity) of 1.0 g oil per mL catalyst of the top bed per hour. From the liquid sample analysis, the conversion of TAGs was 100%.
  • a gas stream comprising 2.5 vol% hydrogen sulphide and 97.5 vol% hydrogen was supplied to the top bed at a gas-to- oil ratio of 2000 NL/kg.
  • the total pressure was 60 bar (a) in both beds .
  • the reactor contained 10 mL of a conventional
  • hydrotreating catalyst comprising 3.5 wt% NiO and 15 wt% M0O 3 on a support of alumina, was placed above 10 mL of a catalyst comprising 5 wt% NiO and 21 wt% W 2 0 3 on amorphous silica- alumina. Both catalysts were 1:1 diluted with 0.1 mm diameter silicon carbide spheres .
  • the temperature of each bed was independently controlled by means of an oven. The temperature of the top bed was set at 300 °C; the temperature of the bottom bed at 350 - 370 °C. The degree of isomerisation of the liquid effluent of the reactor was determined by gas chromatography .
  • paraffinic products obtained after the hydrogenation stage were not considered suitable as fuel components for diesel and/or kerosene fuels since the cold flow properties of the mainly n-paraffinic feed are not suitable for diesel or kerosene use.
  • diesel and kerosene fractions of the liquid stream obtained after the two-stage process showed strongly improved cold flow properties.

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  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

La présente invention porte sur un procédé de production d'hydrocarbures à partir de lipides microbiens, comprenant les étapes consistant à : (a) mettre en contact une charge comprenant des lipides microbiens, les lipides microbiens comprenant une teneur en triglycérides dans la plage de 40 % en poids à 70 % en poids et une teneur en acides gras libres dans la plage de 10 % en poids à 30 % en poids, avec un catalyseur d'hydrogénation et de l'hydrogène à une température dans la plage de 250 à 380°C et une pression totale dans la plage de 20 à 160 bars (absolus), pour obtenir un effluent comprenant des hydrocarbures paraffiniques et de l'eau ; (b) éventuellement séparer un courant liquide riche en hydrocarbures paraffiniques de l'effluent obtenu dans l'étape (a) ; (c) mettre en contact les hydrocarbures paraffiniques présents dans le courant liquide riche en hydrocarbures paraffiniques ou dans l'effluent comprenant des hydrocarbures paraffiniques par mise en contact d'hydrogène et du courant liquide avec un catalyseur d'hydroisomérisation à une température dans la plage de 280 à 450°C et une pression totale dans la plage de 20 à 160 bars (absolus) ; et (d) séparer au moins une fraction du produit du courant de produit obtenu dans l'étape (c).
PCT/EP2010/070154 2009-12-17 2010-12-17 Procédé de production d'hydrocarbures à partir de lipides microbiens Ceased WO2011073427A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8785709B2 (en) 2011-03-30 2014-07-22 University Of Louisville Research Foundation, Inc. Catalytic isomerisation of linear olefinic hydrocarbons
EP4450599A3 (fr) * 2015-02-09 2025-01-01 Neste Oyj Procédé de production d'hydrocarbures à partir d'une charge d'huile renouvelable

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* Cited by examiner, † Cited by third party
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CN103911297B (zh) * 2014-02-28 2015-10-28 中国科学院南海海洋研究所 一种圆红冬孢酵母菌y0及其应用

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US125114A (en) 1872-04-02 Improvement in liquid-meters
US3354078A (en) 1965-02-04 1967-11-21 Mobil Oil Corp Catalytic conversion with a crystalline aluminosilicate activated with a metallic halide
US3832449A (en) 1971-03-18 1974-08-27 Mobil Oil Corp Crystalline zeolite zsm{14 12
US4016218A (en) 1975-05-29 1977-04-05 Mobil Oil Corporation Alkylation in presence of thermally modified crystalline aluminosilicate catalyst
GB2079735A (en) 1980-07-07 1982-01-27 Chevron Res Novel zeolite designated CZH-5
EP0059059A1 (fr) 1981-02-23 1982-09-01 Imperial Chemical Industries Plc Zéolites
US4503023A (en) 1979-08-14 1985-03-05 Union Carbide Corporation Silicon substituted zeolite compositions and process for preparing same
EP0162719A2 (fr) 1984-05-24 1985-11-27 The British Petroleum Company p.l.c. Theta-3, un silicate d'aluminium cristallin et sa préparation
US4557919A (en) 1983-04-12 1985-12-10 Teijin Petrochemical Industries Ltd. Production of crystalline zeolites
US5015361A (en) 1989-01-23 1991-05-14 Mobil Oil Corp. Catalytic dewaxing process employing surface acidity deactivated zeolite catalysts
US5157191A (en) 1986-01-03 1992-10-20 Mobil Oil Corp. Modified crystalline aluminosilicate zeolite catalyst and its use in the production of lubes of high viscosity index
WO1996041849A1 (fr) 1995-06-13 1996-12-27 Shell Internationale Research Maatschappij B.V. Procede catalytique de deparaffinage et composition de catalyseur
CA2579516A1 (fr) 1996-03-28 1997-10-09 Hendrik Louis Bijl Procede pour la preparation d'une biomasse microbienne granulaire et isolation de composes interessants a partir de cette derniere
US6727373B2 (en) 1996-03-28 2004-04-27 Dsm N.V. Preparation of microbial polyunsaturated fatty acid containing oil from pasteurised biomass
US20070010682A1 (en) * 2005-07-05 2007-01-11 Neste Oil Oyj Process for the manufacture of diesel range hydrocarbons
US20090047721A1 (en) 2007-06-01 2009-02-19 Solazyme, Inc. Renewable Diesel and Jet Fuel from Microbial Sources
EP2141217A1 (fr) * 2008-07-01 2010-01-06 Neste Oil OYJ Processus de fabrication d'hydrocarbures d' origine biologique

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101617029A (zh) * 2007-02-20 2009-12-30 国际壳牌研究有限公司 生产链烷烃的方法

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US125114A (en) 1872-04-02 Improvement in liquid-meters
US3354078A (en) 1965-02-04 1967-11-21 Mobil Oil Corp Catalytic conversion with a crystalline aluminosilicate activated with a metallic halide
US3832449A (en) 1971-03-18 1974-08-27 Mobil Oil Corp Crystalline zeolite zsm{14 12
US4016218A (en) 1975-05-29 1977-04-05 Mobil Oil Corporation Alkylation in presence of thermally modified crystalline aluminosilicate catalyst
US4503023A (en) 1979-08-14 1985-03-05 Union Carbide Corporation Silicon substituted zeolite compositions and process for preparing same
GB2079735A (en) 1980-07-07 1982-01-27 Chevron Res Novel zeolite designated CZH-5
EP0059059A1 (fr) 1981-02-23 1982-09-01 Imperial Chemical Industries Plc Zéolites
US4557919A (en) 1983-04-12 1985-12-10 Teijin Petrochemical Industries Ltd. Production of crystalline zeolites
EP0162719A2 (fr) 1984-05-24 1985-11-27 The British Petroleum Company p.l.c. Theta-3, un silicate d'aluminium cristallin et sa préparation
US5157191A (en) 1986-01-03 1992-10-20 Mobil Oil Corp. Modified crystalline aluminosilicate zeolite catalyst and its use in the production of lubes of high viscosity index
US5015361A (en) 1989-01-23 1991-05-14 Mobil Oil Corp. Catalytic dewaxing process employing surface acidity deactivated zeolite catalysts
WO1996041849A1 (fr) 1995-06-13 1996-12-27 Shell Internationale Research Maatschappij B.V. Procede catalytique de deparaffinage et composition de catalyseur
CA2579516A1 (fr) 1996-03-28 1997-10-09 Hendrik Louis Bijl Procede pour la preparation d'une biomasse microbienne granulaire et isolation de composes interessants a partir de cette derniere
US6727373B2 (en) 1996-03-28 2004-04-27 Dsm N.V. Preparation of microbial polyunsaturated fatty acid containing oil from pasteurised biomass
US20070010682A1 (en) * 2005-07-05 2007-01-11 Neste Oil Oyj Process for the manufacture of diesel range hydrocarbons
US20090047721A1 (en) 2007-06-01 2009-02-19 Solazyme, Inc. Renewable Diesel and Jet Fuel from Microbial Sources
EP2141217A1 (fr) * 2008-07-01 2010-01-06 Neste Oil OYJ Processus de fabrication d'hydrocarbures d' origine biologique

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
J. CATALYSIS, vol. 4, 1965, pages 527
J. CATALYSIS, vol. 61, 1980, pages 395
K. M. REDDY; I. MOUDRAKOVSKI; A. SAYARI, J. CHEM. SOC., CHEM. COMMUN. 1994, vol. 1491, 1994
MATHEW A RUDE, ANDREAS SCHIRMER: "New microbial fuels: a biotech perspective", CURRENT OPINION IN MICROBIOLOGY, vol. 12, 18 May 2009 (2009-05-18), pages 274 - 281, XP002588933, DOI: 10.1016/j.mib.2009.04.004 *
Y.X. ZHI; A. TUEL; Y. BENTAARIT; C. NACCACHE, ZEOLITES, vol. 12, 1992, pages 138
ZEOLITES, vol. 17, no. 1-230, 1996, pages 5 - 12
ZEOLITES, vol. 17, no. 1-230, 1996, pages 9

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8785709B2 (en) 2011-03-30 2014-07-22 University Of Louisville Research Foundation, Inc. Catalytic isomerisation of linear olefinic hydrocarbons
EP4450599A3 (fr) * 2015-02-09 2025-01-01 Neste Oyj Procédé de production d'hydrocarbures à partir d'une charge d'huile renouvelable

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