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WO2012083999A1 - Procédé pour le craquage catalytique d'une charge de départ contenant des lipides issue de microalgues pour produire des hydrocarbures - Google Patents

Procédé pour le craquage catalytique d'une charge de départ contenant des lipides issue de microalgues pour produire des hydrocarbures Download PDF

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Publication number
WO2012083999A1
WO2012083999A1 PCT/EP2010/070214 EP2010070214W WO2012083999A1 WO 2012083999 A1 WO2012083999 A1 WO 2012083999A1 EP 2010070214 W EP2010070214 W EP 2010070214W WO 2012083999 A1 WO2012083999 A1 WO 2012083999A1
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Prior art keywords
lipid
feedstock
microalgae
cracking
containing feedstock
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Ceased
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PCT/EP2010/070214
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English (en)
Inventor
Colin John Schaverien
Nicolaas Wilhelmus Joseph Waij
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Priority to PCT/EP2010/070214 priority Critical patent/WO2012083999A1/fr
Publication of WO2012083999A1 publication Critical patent/WO2012083999A1/fr
Anticipated expiration legal-status Critical
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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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/62—Catalyst regeneration
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, 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
    • C10G3/42—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
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • 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
    • C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °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
    • C10G2300/10—Feedstock materials
    • C10G2300/1074—Vacuum distillates
    • 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
    • C10G2300/1077—Vacuum residues
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/301—Boiling range
    • 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
    • C10G2300/80—Additives
    • 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
    • C10G2400/02—Gasoline
    • 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
  • hydrocarbons are known in the art. In these processes, heavy hydrocarbons, such as heavy oils and vacuum
  • Plant and animal biomass are being used to produce liquid and gaseous fuels through the catalytic cracking process.
  • One of the advantages of using biomass is that the C0 2 balance is more favourable as compared with the0 conventional hydrocarbon feedstock.
  • the products obtained through5 this cracking process predominantly include a mixture of
  • EP1970425 describes a process for producing gaseous and liquid fuels by cracking lipids derived from high0 viscosity carbon-based energy carrier materials and WO-A- 2009/000838, describes a process for producing bio oils by cracking of lipids derived from aquatic biomass.
  • Kitazato et al describe in their article titled "Catalytic cracking of hydrocarbons from microalgae", International Chemical Engineering, Volume 31, no 3, July 1991, a process for the production of gasoline by catalytic cracking of hydrocarbons obtained from the microalgae Botryococcus braunii Berkeley (a green algae).
  • a commercial FCC zeolite was used for the catalytic cracking process.
  • Exemplified reaction conditions included temperatures in the range from 450 to 500°C.
  • Kitazato et al . teach, however, that low
  • the present invention provides a process for catalytic cracking of a lipid-containing feedstock, the process comprising contacting the lipid- containing feedstock with at least one cracking catalyst at a temperature of at least 450 °C, to obtain a product stream; and separating at least one hydrocarbon fraction from the product stream; wherein the lipid-containing feedstock comprises lipids derived from a diatomic microalgae species .
  • the present invention provides a gasoline product prepared from a hydrocarbon fraction of the at least one hydrocarbon fraction .
  • the present invention provides a liquefied gaseous fuel composition
  • a liquefied gaseous fuel composition comprising a liquefied gaseous fuel product prepared from a hydrocarbon fraction of the at least one hydrocarbon fraction, less than 1000 ppmw sulphur, and one or more additives .
  • the process according to the invention is further advantageous because diatomic microalgae have high growth rates, utilise a large fraction of solar energy and can grow in conditions that are not favourable for
  • diatomic microalgae consume C0 2 at a high rate, and may reduce the carbon footprint of the overall process. Further diatomic microalgae contain high concentrations of lipids.
  • Diatomic microalgae as referred to in the present invention are a large and diverse group of microorganisms living in an aquatic environment that have a cell wall comprising silica. They can be unicellular or
  • the diatomic microalgae preferably have a diameter smaller than 1 mm, more preferably a diameter smaller than 0.6 mm and still more preferably a diameter smaller than 0.4 mm. The diameter is measured at its largest point. Most preferably the diatomic microalgae comprise a diameter in the range from 0.5 to 200 micrometer, even more
  • the diatomic microalgae can be cultivated under difficult agro-climatic conditions, including cultivation in freshwater, saline water, moist earth, dry sand and other open-culture conditions known in the art.
  • the diatomic microalgae can also be cultivated and genetically engineered in controlled closed-culture systems, for example, in closed bioreactors .
  • the diatomic microalgae used in the present invention are marine diatomic microalgae cultivated in fresh water, saline water or other moist conditions, more preferably marine diatomic microalgae cultivated in saline water .
  • the marine diatomic microalgae are cultivated in open-culture conditions, for example, in open ponds.
  • Lipids as referred to in the present invention are a group of naturally occurring compounds that are usually hydrophobic in nature and contain long-chain aliphatic hydrocarbons and their derivatives such as fatty acids, alcohols, amines, amino alcohols and aldehydes.
  • the lipid-containing feedstock as disclosed in the invention includes lipids derived from marine diatomic microalgae. 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 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 26 carbon atoms, more
  • the fatty acid moiety includes 10 carbon atoms to 25 carbon atoms, again more preferably the fatty acid moiety includes 12 carbon atoms to 23 carbon atoms, and yet more preferably 14 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 may be composed of natural glycerides only.
  • the lipids may also include carotenoids, hydrocarbons, phosphatides, simple fatty acids and their esters, terpenes, sterols, fatty alcohols, tocopherols, polyisoprene, carbohydrates and proteins. It is to be understood that for the purpose of this invention, a mixture of lipids extracted from different diatomic microalgae sources can also be used in the lipid-containing feedstock.
  • the diatomic microalgae may be processed to extract lipids using processes known in the art.
  • the said processes may include the steps of harvesting the diatomic microalgae, dewatering the diatomic microalgae, disrupting the diatomic microalgae 's cell walls to liberate lipids, and then extracting the lipids using solvents, supercritical fluids or other extraction processes.
  • the diatomic microalgae are cultivated, harvested, dried, milled and then lipids are extracted using a water immiscible solvent at 25 °C.
  • Suitable solvents for the extraction are organic solvents such as aromatic or aliphatic hydrocarbons, higher alcohols, ethers and esters.
  • solvents examples include toluene, hexane, heptane, dimethyl ether, acetic acid ester and mixtures thereof.
  • solvents include supercritical liquids, such as supercritical carbon dioxide.
  • the extracted lipids may conveniently be isolated by evaporating the solvent, or by other methods, such as membrane separation.
  • the lipid-containing feedstock includes lipids in the range of 1 wt% to 50 wt%, more preferably in the range of 2 wt% to 40 wt%, more preferably in the range of 3 wt% to 30 wt%, and yet more preferably in the range of 5 wt% to 20 wt%, based on the total weight of lipid-containing feedstock.
  • the lipid-containing feedstock further preferably comprises a hydrocarbon feedstock. That is, the lipids (also referred to as lipid feedstock) may preferably be co-fed together with a hydrocarbon feedstock.
  • the co- feeding may be attained by blending the two feedstock streams prior to entry into the cracking unit, or alternatively, by adding them at different stages.
  • the hydrocarbon feedstock preferably comprises hydrocarbons with a boiling point of at least 220°C, as measured by Gas Chromatograph Distillation (GCD) according to ASTM D-6352-98.
  • the boiling points range from 220 °C to 650 °C, more preferably from 300 °C to 600 °C.
  • the hydrocarbon feedstock preferably has an initial boiling point above 180 °C, as measured by Gas Chromatograph Distillation (GCD) according to the methods described in ASTM D-6352-98.
  • the hydrocarbon feedstock includes hydrocarbons having a mineral origin.
  • such hydrocarbon feedstock comprises a mineral oil or a derivative of a mineral oil.
  • the hydrocarbon feedstock may be a conventional fluid catalytic cracking feedstock.
  • hydrocarbon feedstock examples include high boiling, non-residual oils such as straight run
  • the hydrocarbon feedstock may include a paraffinic feedstock, for example, an
  • hydrowax optionally hydroisomerised fraction of the synthesis product of a Fischer-Tropsch reaction, or the fraction boiling above the middle distillate boiling range of the effluent of fuel hydrocracker, also referred to as hydrowax.
  • lipids derived from other biomass sources such as plant and vegetable oils may also be added to the lipid-containing feedstock as an additional cracking feedstock .
  • the total feed going into the catalytic cracking unit may comprise the hydrocarbon feedstock in the range of 50 wt% to 99wt%, preferably in the range from 60 wt% to 98wt%, more preferably 70 wt% to 98 wt%, more preferably 70 wt% to 97 wt%, most preferably in the range of 80 wt% to 95 wt% based on the total weight of lipid-containing feedstock, the remainder being the lipid feedstock .
  • the catalytic cracking process includes a catalytic cracking step, in which the cracking reaction takes place in the presence of a catalyst; a regeneration step, in which the catalyst is regenerated, for example by burning off the coke deposited on the catalyst as a result of the reaction, to restore the catalytic
  • the heat generated in the exothermic regeneration step is preferably employed to provide energy for the endothermic cracking step.
  • the catalytic cracking step comprises contacting the lipid-containing feedstock with a cracking catalyst, preferably in the reaction zone of a fluidized catalytic cracking (FCC) apparatus.
  • the reaction temperature preferably ranges from equal to or more than 450 °C to equal to or less than 650 °C, more preferably from equal to or more than 480 °C to equal to or less than 600 °C, and most preferably from equal to or more than 480 °C to equal to or less than 560 °C.
  • the pressure in the reaction zone preferably ranges from equal to or more than 0.5 bar to equal to or less than 10 bar (0.05
  • MPa-1 MPa more preferably from equal to or more than 1.0 bar to equal to or less than 6 bar (0.15 MPa to
  • the residence time of the cracking catalyst in the reaction zone preferably ranges from equal to or more than 0.1 seconds to equal to or less than 15 seconds, more preferably from equal to or more than 0.5 seconds to equal to or less than 10 seconds.
  • the product stream obtained from the cracking step may be separated into one or more hydrocarbon fractions using, for example, a fractionator .
  • a catalyst to lipid-containing feedstock mass ratio ranging from equal to or more than 3 to equal to or less than 8 is used.
  • the catalyst to feedstock mass ratio used is at least 3.5. The use of a higher catalyst to feedstock mass ratio results in an increase in conversion.
  • the process according to the invention further preferably comprises a catalyst regeneration step.
  • a regeneration step preferably may comprise burning off the coke to restore the catalyst activity by combusting the cracking catalyst in the presence of an oxygen-containing gas in a regenerator.
  • the regeneration temperature preferably ranges from equal to or more than 575 °C to equal to or less than 950 °C, more preferably from equal to or more than 600 °C to equal to or less than 850 °C.
  • the pressure in the regenerator preferably ranges from equal to or more than 0.5 bar to equal to or less than 10 bar (0.05 Mpa to 1 MPa), more preferably from equal to or more than 1.0 bar to equal to or less than 6 bar (0.1 MPa to 0.6 MPa.
  • the cracking catalyst comprises a zeolitic component, and more preferably, an amorphous binder.
  • binder materials include silica, alumina, titania, zirconia and magnesium oxide, or combinations of two or more of them.
  • the zeolite is preferably a large pore zeolite.
  • the large pore zeolite includes a zeolite comprising a porous, crystalline aluminosilicate structure having a porous internal cell structure on which the major axis of the pores is in the range of 0.62 nanometer to
  • USY is preferably used as the large pore zeolite.
  • the cracking catalyst can also comprise a medium pore zeolite.
  • the medium pore zeolite that can be used according to the present invention is a zeolite
  • ZSM-5 is preferably used as the medium pore zeolite.
  • a blend of large pore and medium pore zeolites may be used.
  • the ratio of the large pore zeolite to the medium pore size zeolite in the cracking catalyst is preferably in the range of 99:1 to 70:30, more preferably in the range of 98:2 to 85:15.
  • the total amount of the large pore size zeolite and/or medium pore zeolite that is present in the cracking catalyst is preferably in the range of 5 wt% to 40 wt%, more preferably in the range of 10 wt% to 30 wt%, and even more preferably in the range of 10 wt% to 25 wt% relative to the total mass of the cracking catalyst, the remainder being amorphous binder .
  • the reaction zone is usually an elongated tube-like reactor, preferably a vertical reactor in which the lipid-containing feedstock and the cracking catalyst flow in an upward direction.
  • the lipid-containing feedstock and the cracking catalyst may also flow in a downward direction. Combinations of downward and upward flow are also within the scope of the present invention.
  • the lipid-containing feedstock and the cracking catalyst may be contacted in counterflow or crossflow configurations.
  • the C0 2 produced in the cracking step and the catalyst are identical to an embodiment of the invention. According to an embodiment of the invention, the C0 2 produced in the cracking step and the catalyst
  • regeneration step may be reused for cultivation and propagation of the diatomic microalgae being used in the process.
  • This process integration preferably mitigates the emissions from the overall process and facilitates cultivation of diatomic microalgae.
  • the product stream can comprise products that may include gaseous hydrocarbons with four or less carbon atoms, gasoline, diesel, cycle oils and other
  • the product stream, comprising cracked hydrocarbons, obtained from the FCC apparatus is preferably sent to a fractionation zone, where it is separated into one or more hydrocarbon fractions .
  • these hydrocarbon fractions include dry gas, propylene, Liquefied Petroleum Gas (LPG), gasoline, light cycle oils and coke.
  • the product stream composition includes a gasoline fraction ranging from 30 wt% to 60 wt%, preferably from 40 wt% to 50 wt%, based on the total product stream composition, as measured by Gas
  • the total product stream composition includes a LPG fraction ranging from 5 wt% to 20 wt%, preferably from 10 wt% to 15 wt% of the total product stream composition (ASTM D-2887) .
  • hydrocarbon fractions may undergo further processing before they are provided for commercial use.
  • processing may include
  • hydrocarbon fractions are also within the scope of the invention.
  • the gasoline fraction may be desulphurised to reduce the sulphur content to less than 1000 ppmw, preferably to less than 500 ppmw, more preferably to less than 200 ppmw to prepare a gasoline product.
  • One or more additives may be added to the desulphurised gasoline product to prepare a gasoline composition for commercial use.
  • the additives may include performance enhancers such as anti-oxidants, corrosion inhibitors, ashless detergents, dehazers, dyes, lubricity improvers, synthetic or mineral oil carrier fluids.
  • the one or more additives can be added separately to the gasoline product or can be blended with one or more diluents, forming an additive concentrate, and together added to the gasoline product .
  • the gasoline composition according to the invention preferably comprises a major amount (more than 50 wt%) of the gasoline product and a minor amount of the one or more additives described above, preferably ranging from 0.005 wt% to 10 wt%, more preferably from 0.01 wt% to 5wt%, and most preferably from 0.02 wt% to 1 wt%, based on the gasoline composition.
  • hydrocarbon fractions 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. These processes may include isomerisation, cracking into more valuable lighter products, blending with other fuels for commercial use, and other similar uses that have been disclosed in the art.
  • a blend of 20 wt% of these extracted lipids and 80 wt% of a mineral oil derived vacuum gas oil was mixed.
  • the Blend had the following metal content (see table 2 in mg/kg as determined by ICP-AES) .
  • Table 2 metal content in a blend of 20 wt% of extracted lipids with 80 wt% a mineral oil derived vacuum gas oil (in mg/kg)
  • the lipids obtained from experiment 1 were blended with mineral Vacuum Gas Oil (VGO) to form a first batch of the lipid-containing feedstock comprising 20%
  • VGO Vacuum Gas Oil
  • the first batch was subjected to catalytic cracking in a small-scale fluidised catalytic cracking reactor.
  • a commercial equilibrium catalyst comprising ultra stable zeolite Y (USY) in an amorphous alumina matrix was used as the cracking catalyst.
  • the reaction temperature was kept at 500 °C, and the pressure was maintained at 1.1 bar (0.11 MPa) .
  • a catalyst to oil ratio of about 8 was used for the feedstock containing 20wt% extracted lipids from microalgae and 80wt% VGO .
  • the product stream obtained was separated in a small-scale fractionator and analysed online using gas chromatography (GC) and inductively coupled plasma mass spectrometry (ICP-MS).
  • GC gas chromatography
  • ICP-MS inductively coupled plasma mass spectrometry
  • Dry gas includes ethylene and LPG includes propane and butane gas.
  • Gasoline is defined as the fraction starting with C5 isomers, and boiling up to 221 °C (EP); Light Cycle Oil (LCO) as the fraction boiling from 221- 370 °C (IBP-EP); Heavy Cycle Oil (HCO) as the fraction boiling from 370-425 °C (IBP-EP); and Slurry Oil as the fraction boiling above > 425 °C, determined according to ASTM 2887, using the total boiling point method.
  • VGO was used as the second batch and a blend of 20% rapeseed oil and 80% VGO was used as the third batch.
  • the experiments were conducted in the same fluidised catalytic cracking reactor and under the same conditions as were used in experiment 2, except that a different catalyst to oil ratio may be used to achieve the constant conversion rate of 67wt%.
  • the additional coke formed in the process according to the invention can be advantageous when co-processing a further paraffinic feedstock such as for example an optionally hydroisomerised fraction of the synthesis product of a Fisher-Tropsch reaction.

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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)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

La présente invention porte sur un procédé pour le craquage catalytique d'une charge de départ contenant des lipides, le procédé comprenant la mise en contact de la charge de départ contenant des lipides avec au moins un catalyseur de craquage à une température d'au moins 450°C, pour obtenir un courant de produit ; et la séparation d'au moins une fraction d'hydrocarbures du courant de produit ; la charge de départ contenant des lipides comprenant des lipides issus d'une espèce de microalgues diatomiques.
PCT/EP2010/070214 2010-12-20 2010-12-20 Procédé pour le craquage catalytique d'une charge de départ contenant des lipides issue de microalgues pour produire des hydrocarbures Ceased WO2012083999A1 (fr)

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Citations (11)

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Publication number Priority date Publication date Assignee Title
US4917790A (en) 1989-04-10 1990-04-17 Mobil Oil Corporation Heavy oil catalytic cracking process and apparatus
US5855629A (en) 1996-04-26 1999-01-05 Shell Oil Company Alkoxy acetic acid derivatives
US6905591B2 (en) 2002-01-10 2005-06-14 Stone & Webster Process Technology, Inc. Deep catalytic cracking process
EP1892280A1 (fr) * 2006-08-16 2008-02-27 BIOeCON International Holding N.V. Craquage catalytique en lit fluidisé de composés oxygénés
CN101200647A (zh) * 2007-11-28 2008-06-18 厦门大学 用杜氏藻藻粉制备燃料油气的方法
EP1970425A1 (fr) 2007-02-20 2008-09-17 BIOeCON International Holding N.V. Procédé amélioré pour la conversion d'un matériau support d'énergie à base de carbone
GB2447684A (en) * 2007-03-21 2008-09-24 Statoil Asa Biogasoline from marine oils
WO2009000838A2 (fr) 2007-06-25 2008-12-31 Kior, Inc. Combustible liquide pour biomasse aquatique
US20090026112A1 (en) * 2006-02-09 2009-01-29 Jan Lodewijk Maria Dierickx Fluid catalytic cracking process
US20090047721A1 (en) 2007-06-01 2009-02-19 Solazyme, Inc. Renewable Diesel and Jet Fuel from Microbial Sources
EP2053115A1 (fr) * 2006-08-18 2009-04-29 Nippon Oil Corporation Procédé de traitement de biomasse, combustible pour pile à combustible, essence, carburant diesel, gaz de pétrole liquéfiés et résine synthétique

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4917790A (en) 1989-04-10 1990-04-17 Mobil Oil Corporation Heavy oil catalytic cracking process and apparatus
US5855629A (en) 1996-04-26 1999-01-05 Shell Oil Company Alkoxy acetic acid derivatives
US6905591B2 (en) 2002-01-10 2005-06-14 Stone & Webster Process Technology, Inc. Deep catalytic cracking process
US20090026112A1 (en) * 2006-02-09 2009-01-29 Jan Lodewijk Maria Dierickx Fluid catalytic cracking process
EP1892280A1 (fr) * 2006-08-16 2008-02-27 BIOeCON International Holding N.V. Craquage catalytique en lit fluidisé de composés oxygénés
EP2053115A1 (fr) * 2006-08-18 2009-04-29 Nippon Oil Corporation Procédé de traitement de biomasse, combustible pour pile à combustible, essence, carburant diesel, gaz de pétrole liquéfiés et résine synthétique
EP1970425A1 (fr) 2007-02-20 2008-09-17 BIOeCON International Holding N.V. Procédé amélioré pour la conversion d'un matériau support d'énergie à base de carbone
GB2447684A (en) * 2007-03-21 2008-09-24 Statoil Asa Biogasoline from marine oils
US20090047721A1 (en) 2007-06-01 2009-02-19 Solazyme, Inc. Renewable Diesel and Jet Fuel from Microbial Sources
WO2009000838A2 (fr) 2007-06-25 2008-12-31 Kior, Inc. Combustible liquide pour biomasse aquatique
CN101200647A (zh) * 2007-11-28 2008-06-18 厦门大学 用杜氏藻藻粉制备燃料油气的方法

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KITAZATO H ET AL: "Catalytic cracking of hydrocarbons from microalgae", INTERNATIONAL CHEMICAL ENGINEERING, NEW YORK, NY, US, vol. 31, 1 July 1991 (1991-07-01), pages 523 - 529, XP008118619, ISSN: 0020-6318 *
MILNE THOMAS A ET AL: "Catalytic conversion of microalgae and vegetable oils to premium gasoline, with shape-selective zeolites", BIOMASS LONDON 1990, vol. 21, no. 3, 1990, pages 219 - 232, XP002603540 *
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