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
  • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
• • 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
  • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
  • C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
• • 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
• • 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
  • C10G3/47—Catalytic treatment characterised by the catalyst used containing platinum group 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
  • C10G3/50—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
  • C10G45/60—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 characterised by the catalyst used
• • 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
  • C10G45/60—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 characterised by the catalyst used
  • C10G45/62—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 characterised by the catalyst used containing platinum group 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
  • 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
  • C10G45/60—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 characterised by the catalyst used
  • C10G45/64—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 characterised by the catalyst used containing 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
  • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
  • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
  • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
  • C10G65/043—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a change in the structural skeleton
• • 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
  • 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
  • C10G2300/1011—Biomass
  • C10G2300/1018—Biomass of animal 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
  • C10G2300/20—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
  • C10G2300/4081—Recycling aspects
• • 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
  • C10G2400/08—Jet fuel
• • 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 hydrocarbons and particularly to the manufacture of hydrocarbon components suitable as aviation fuels or jet fuels and as blending stocks for aviation fuels.
• the present invention also relates to a process for the manufacture of hydrocarbons from renewable starting materials of biological origin.
• the invention provides an alternative process for the manufacture of high quality aviation fuels or blending stocks or components for aviation fuels, based on biological starting materials.
• Aviation fuels or jet fuels are traditionally manufactured from crude mineral oil, which is typically separated by means of distillation into straight run kerosene fraction boiling in the aviation fuel range, and if required, followed by optional conversion processes like cracking etc. well known in the art.
• Mineral oil derived kerosene meeting aviation fuel requirements may also be produced for example by hydroprocessing or by caustic washing of straight run kerosene.
• the Fischer-Tropsch process where carbon monoxide and hydrogen are reacted over an iron, cobalt, nickel or ruthenium containing catalyst to produce a mixture of straight and branched chain hydrocarbons and smaller amounts of oxygenates, is increasingly used for the manufacture of aviation fuels.
• Synthesis gas used as the starting material may be derived from coal, natural gas, biomass or heavy oil streams.
• the resulting mixtures, predominantly containing linear paraffins, are fractionated and the fraction boiling in the aviation fuel range is separated and used as a component in aviation turbine fuels, as described in WO 2007/110448.
• US 2006/0111599 describes a process where modified Low Temperature Fischer- Tropsch (LTFT) feedstock is fractionated and optionally blended to obtain low sulphur aviation turbine fuel.
• LTFT modified Low Temperature Fischer- Tropsch
• a product having a final boiling point of about 27O 0 C is obtained, typically containing a blend of isoparaffins and n-paraffins.
• WO 2007/027955 presents a method for preparing a hydrocarbon product suitable as jet fuel.
• a feedstock comprising C10-C20 fatty acids, originating from any source of triglycerides, is subjected to thermal decarboxylation, followed by combining the obtained product with olefin containing material and carrying out olefin metathesis and then performing dehydrogenation if the metathesis product is saturated, followed with optional hydrogenation.
• WO 2007/027669 teaches a process for preparing a hydrocarbon product suitable as jet fuel.
• a feedstock comprising C10-C20 fatty acids, originating from any source of triglycerides is subjected to Kolbe electrolysis, yielding a product, which is combined with olefin containing material and carrying out olefin metathesis and then performing dehydrogenation if the metathesis product is saturated, followed with optional isomerisation.
• aviation turbine fuels comprise blends of fractions and components obtained using different processes.
• Aviation fuel is a product boiling for more than 90 vol% at from 130 to 300 0 C (ASTM
• Jet A-I requirements in the standard DEF STAN 91-91 (British Ministry of Defense Standard DEF STAN 91-91 /Issue 6 of 8 April 2008 for Turbine Fuel, Aviation Kerosine Type, Jet A-I, NATO code F-35, Joint Service Designation AVTUR, or versions current at the time of testing) or in the "Check List" (Aviation Fuel Quality Requirements for Jointly Operated Systems, AFQRJOS), are based on the most stringent requirements of ASTM D1655, DEF STAN 91-91 and IATA, Guidance Material for Aviation Turbine Fuels Specifications, some airport handling requirements.
• Static dissipator additive is always required for adjusting and maintaining the electric conductivity above 50 pS/m during the operating conditions. It is particularly important during the refuelling conditions when modern rapid refuelling equipment is used. Said equipment may cause formation of static electricity, which may result sparking and even serious refuelling fires if the electric conductivity of the fuel is not sufficient.
• Antioxidants are generally used for improving the stability of the fuels and they decrease or prevent the formation of precipitates during the storage of the fuel.
• Lubricity improving additives are used for improving the lubricity and simultaneously they act as corrosion inhibitors in aviation fuels, particularly in military use and when the product contains more than 95 % of hydroprocessed product.
• Metal deactivators prevent metals from reacting with fuels, which decreases thermal stability significantly.
• Fuel system icing inhibitors are used predominantly in military practice.
• An object of the invention is a process for the manufacture of hydrocarbons.
• a further object of the invention is a process for the manufacture of hydrocarbon components suitable as aviation fuels or blending stocks for aviation fuels.
• a still further object of the invention is a process for the manufacture of aviation fuels or blending stocks for aviation fuels from biological and renewable starting materials.
• a still further object of the invention is a process for the manufacture of components or blending stocks for aviation fuels complying with Jet A-I requirements, from biological and renewable starting materials.
• aviation fuel is understood to mean aviation turbine fuel or jet fuel, suitable for aviation purposes.
• Bio jet fuel means aviation fuel derived from biological starting materials.
• hydroprocessing is understood as catalytic processing of organic material by all means of molecular hydrogen.
• hydrotreatment is understood as a catalytic process, which removes oxygen from organic oxygen compounds as water (hydrodeoxygenation, HDO), sulphur from organic sulphur compounds as dihydrogen sulphide (H 2 S) (hydrodesulphurisation, HDS), nitrogen from organic nitrogen compounds as ammonia (NH 3 ) (hydrodenitrogenation, HDN) and halogens, such as chloride from organic chloride compounds as hydrochloric acid (HCl) (hydrodechlorination, HDCl), typically under the influence of a catalyst.
• deoxygenation is understood to mean removal of oxygen from organic molecules, such as fatty acid derivatives, alcohols, ketones, aldehydes or ethers by any means previously described.
• hydrodeoxygenation (HDO) of triglycerides or other fatty acid derivatives or fatty acids is understood to mean the removal of carboxyl oxygen as water by the means of molecular hydrogen under the influence of a catalyst.
• decarboxylation and/or decarbonylation of triglycerides or other fatty acid derivatives or fatty acids is understood to mean removal of carboxyl oxygen as CO 2 (decarboxylation) or as CO (decarbonylation) with or without the influence of molecular hydrogen.
• hydrocracking is understood as catalytic decomposition of organic hydrocarbon materials using molecular hydrogen at high pressures.
• hydrogenation means saturation of carbon-carbon double bonds by the means of molecular hydrogen under the influence of a catalyst.
• n-paraffins mean normal alkanes or linear alkanes containing no side chains.
• isoparaffins means alkanes having one or more Ci - C9 , typically Ci - C 2 alkyl side chains, typically mono-, di-, tri- or tetramethylalkanes.
• the feed (total feed) to the first process step is to be understood comprising fresh feed and optionally at least one dilution agent.
• Typical boiling range of gas is from -162 to 40 C, typically comprising C 1 -C 5 hydrocarbons.
• Typical boiling range of gasoline is from 40 to 210 C, typically comprising C5-C10 hydrocarbons.
• aviation fuel typically comprises Cs-Ci 6 hydrocarbons, and typically the initial boiling point being in the range 130 to 16O 0 C and final boiling point in the range 220 to 300 0 C.
• Typical boiling range of diesel fuel is from 160 to 360 C, typically comprising C10-C28 hydrocarbons.
• Boiling temperatures refer to temperatures under normal atmospheric pressures unless otherwise provided.
• the present invention is directed to a process for the manufacture of hydrocarbons and hydrocarbon components.
• the resulting hydrocarbon components are useful as high quality aviation fuels and as blending stocks or components for high quality aviation fuels.
• hydrocarbon components useful as diesel fuels are obtained as well as components suitable as gas and gasoline.
• the process comprises the stages where a feed derived from renewable sources is hydrodeoxygenated and isomerised, followed by separation of the fractions boiling in the gas range, in the gasoline range, in the aviation fuel range and optionally separating the fraction boiling in the diesel fuel range, and then subjecting the fraction boiling at a temperature at or above 200 0 C (particularly from > 200 0 C to 65O 0 C) under atmospheric pressure (heavy recycle stream from the isomerisation) and optionally the faction boiling in the diesel fuel range to second isomerisation.
• the product is separated into components using any suitable separation technique.
• Hydrocarbon components comprising isoparaff ⁇ ns are obtained, the component boiling in the aviation fuel range being particularly suitable as isoparaffinic aviation fuel or as blending stock for aviation fuels.
• the process according to the invention comprises a hydrodeoxygenation stage followed by an isomerisation stage, separating then the lighter fractions from the isomerised product and reisomerising the fraction boiling at a temperature at or above 200 0 C (heavy recycle stream).
• the process comprises the stages, wherein in the first stage (hydrodeoxygenation) an oil feed of biological origin and hydrogen gas are subjected to conditions sufficient to effect hydrodeoxygenation in the presence of a hydrodeoxygenation catalyst to yield n-paraffms; in the second stage (isomerisation) the n-paraffms and hydrogen gas are subjected to conditions sufficient to effect isomerisation in the presence of an isomerisation catalyst to yield isoparaffms; and separating the fractions boiling in the gas range, in the gasoline range, in the aviation fuel range and optionally separating the fraction boiling in the diesel fuel range, reisomerising (2 nd isomerisation) the fraction boiling at a temperature at or above 200 0 C (heavy recycle stream) and optionally the faction boiling in the diesel fuel range in the presence of an isomerisation catalyst; and then separating the obtained isoparaff ⁇ nic hydrocarbon components.
• the reisomerisation may be carried out in three alternative ways:
• the combined stream 9 enters the reaction section C comprising an isomerisation catalyst.
• the reaction section C may comprise one or several catalysts beds.
• the isomerised liquid effluent 10 from the reaction section C is passed to fractionator D where fractions boiling in the gas range 12, gasoline range 13, aviation fuel range 14 and optionally the fraction boiling in the diesel fuel range 15 or part of it are separated by distillation.
• the heavy recycle stream, fraction 16, optionally combined with the fraction 15 or part of it, is recycled as stream 17, which is combined with stream 9.
• the vapour stream 11 containing hydrogen, light gases, CO 2 and water, is passed to gas purification section F for gas purification and recycling.
• part of stream 16 is taken out as stream 18 to be used as diesel fuel component.
• vapour stream 6 from the separator B is passed to gas purification section F for gas purification and recycling, and the liquid stream 7 is combined with hydrogen stream 8.
• the combined stream 9 enters the catalyst bed of the second subsection C 2 of the reaction section
• reaction section C comprising at least two subsections Ci and C 2 , comprising an isomerisation catalyst.
• Reaction section C may comprise one or several catalysts beds in each subsection Ci and C 2 .
• the isomerised liquid effluent 10 from the reaction section C is passed to fractionator D where fractions boiling in the gas range 12, gasoline range 13, aviation fuel range 14 and optionally the fraction boiling in the diesel fuel range 15 or part of it are separated by distillation.
• the heavy recycle stream, fraction 16, optionally combined with the fraction 15 or part of it, is recycled as stream 17, which is combined with hydrogen stream 8 and the combined stream 19 is passed to the catalyst bed of the first subsection Ci of the reaction section C.
• the vapour stream 11 containing hydrogen, light gases, CO 2 and water, is passed to gas purification section F for gas purification and recycling.
• part of stream 16 is taken out as stream 18 to be used as diesel fuel component.
• the combined stream 9 enters the reaction section C comprising an isomerisation catalyst.
• Reaction section C may comprise one or several catalysts beds.
• the isomerised liquid effluent 10 from the reaction section C is passed to fractionator D where fractions boiling in the gas range 12, gasoline range 13, aviation fuel range 14 and optionally the fraction boiling in the diesel fuel range 15 or part of it are separated by distillation.
• the heavy recycle stream, fraction 16, optionally combined with the fraction 15 or part of it, is recycled as stream 17, which is combined with hydrogen gas stream 8.
• the combined stream 19 is passed to the reaction section E comprising an isomerisation catalyst.
• Reaction section E may comprise one or several catalysts beds.
• the isomerised liquid effluent 20 is combined with stream 10 and passed to fractionator D and the vapour stream 21 is passed to gas purification section F for gas purification and recycling.
• Optionally part of stream 16 is taken out as stream 18 to be used as diesel fuel component.
• Each reaction section may comprise one or several catalyst beds.
• liquid effluent 10 from the reaction section C may be recycled and combined with stream 9 (not shown in the figures).
• fraction in the diesel duel range or part of it may be combined with the heavy recycle stream and resiomerised, depending of the optimisation and operation of the process.
• hydrocarbons and particularly isoparaffmic hydrocarbon components suitable as high quality aviation fuel or components or blending stocks for high quality aviation fuels can be obtained with the process according to the invention, which comprises the stages, wherein in the first stage an oil feed of biological origin and hydrogen gas are subjected to conditions sufficient to effect hydrodeoxygenation in the presence of a hydrodeoxygenation catalyst to yield n-paraff ⁇ ns; in the second stage the n-paraffms and hydrogen gas are subjected to conditions sufficient to effect isomerisation in the presence of an isomerisation catalyst to yield isoparaffms; and recycling the fraction boiling at a temperature at or above 200 0 C (particularly from > 200 0 C to 65O 0 C) under atmospheric pressure (heavy recycle stream), obtained from the second stage, optionally combined with the fraction boiling in the diesel fuel range or part of it, to reisomerisation, where isomerisation is effected in the presence of an isomerisation catalyst.
• the heavy recycle stream may be comprise the fraction boiling at a temperature at or above 25O 0 C or the fraction boiling at a temperature at or above 29O 0 C, the upper limit of the boiling range being 65O 0 C in both cases, if required.
• the reisomerisation may be carried out in three alternative ways:
• the process according to the invention comprises at least two stages, each stage having at least one reaction zone, said process comprising the steps: a) combining an oil feed of biological origin with a hydrogen containing gas stream to form a feedstock; b) passing the feedstock to a reaction zone of the first stage, which is maintained at conditions sufficient to effect hydrodeoxygenation and contacting it with a hydrodeoxygenation catalyst; c) passing the effluent from step (b) to a separator where it is separated into an overhead fraction and bottoms fraction; d) mixing the bottoms fraction from step (c) with a hydrogen containing gas stream; e) passing the combined stream from step (d) to a reaction section of the second stage, which is maintained at conditions sufficient to effect isomerisation and contacting it with an isomerisation catalyst; f) passing the effluent from step (e) to fractionation, thereby producing isomerized product streams, removing the stream boiling in the gas range, the stream boiling in the gasoline range
• the bio oil and/or fat used as the fresh oil feed in the process of the present invention originates from biological and renewable sources, such as plants and/or animals and/or fish and/or insects, and from processes utilizing microbes, such as algae, bacteria, yeasts and moulds, and suitable are also compounds derived from said fats and oils and mixtures thereof.
• the species yielding the bio oils or fats may be natural or genetically engineered.
• the bio oils and fats may be virgin oils and fats or recycled oils and fats.
• the basic structural unit of a typical plant or animal oil/fat is a triglyceride, which is a triester of glycerol with three fatty acid molecules, having the structure presented in the following formula I: O 1
• R 2 and R 3 are alkyl chains. Fatty acids found in natural triglycerides are almost solely fatty acids of even carbon number. Therefore Ri, R 2 , and R3 typically are C5 - C23 alkyl groups, mainly C11-C19 alkyl groups and most typically C 15 or Cn alkyl groups. Ri, R 2 , and R 3 may contain carbon-carbon double bonds. These alkyl chains can be saturated, unsaturated or polyunsaturated.
• Suitable bio oils containing fatty acids and/or fatty acid esters and/or fatty acid derivatives are wood-based and other plant-based and vegetable-based fats and oils such as rapeseed oil, colza oil, canola oil, tall oil, Jatropha seed oil, sunflower oil, soybean oil, hempseed oil, olive oil, linseed oil, mustard oil, palm oil, peanut oil, castor oil, coconut oil, as well as fats contained in plants bred by means of gene manipulation, animal-based fats such as lard, tallow, train oil, and fats contained in milk, as well as recycled fats of the food industry and mixtures of the above, as well as fats and oils originating from processes utilizing microbes, such as algae, bacteria, yeasts and moulds.
• microbes such as algae, bacteria, yeasts and moulds.
• Bio oil and fat suitable as fresh feed may comprise Ci 2 - C 24 fatty acids, derivatives thereof such as anhydrides or esters of fatty acids as well as triglycerides and diglycerides of fatty acids or combinations of thereof.
• Fatty acids or fatty acid derivatives, such as esters may be produced via hydrolysis of bio oils or by their fractionalization or transesterification reactions of triglycerides or microbiological processes utilizing microbes.
• the feed complies with the following requirements:
• the amount of alkaline and alkaline earth metals, calculated as elemental alkaline and alkaline earth metals, in the feed is below 10, preferably below 5 mg/kg.
• the amount of other metals, calculated as elemental metals, in the feed is below 10, preferably below 5 mg/kg.
• the amount of phosphorus, calculated as elemental phosphorus is below 30, preferably below 15 mg/kg.
• the oil feed such as crude plant oil or animal fat
• the feed is preferably pretreated using one or more conventional purification procedures before introducing it to the hydrodeoxygenation step of the process. Examples of some conventional purification/ pretreatment procedures are provided below.
• Degumming of plant oils/fats and animal oils/fats means the removal of phosphorus compounds, such as phospholipids.
• Solvent extracted vegetable oils often contain significant amounts of gums, which are mostly phosphatides (phospholipids). Iron and also other metals may be present in the form of metal- phosphatide complexes.
• Degumming is typically performed by washing the feed at an elevated temperature and pressure with an acid, base and soft water and separating the formed gums, also a major amount of metal components are removed.
• a feed which is optionally degummed or refined in another conventional way, may be bleached with natural or acid activated bleaching clay.
• Bleaching removes various impurity traces left from other pretreatment steps, such as chlorophyll, carotenoids, phosphoipids, metals, soaps and oxidation products.
• the goal of bleaching is to reduce the color pigments and to reduce the oxidation tendency of oil.
• the triglyceride structures of the feed may be decomposed by prehydrogenating the double bonds using reduced reaction temperature with suitable catalyst, prior to the hydrodeoxygenation in order to prevent double bond polymerisation of unsaturated triglycerides.
• fatty acids, triglycerides and other fatty acid derivatives comprised in the feed are deoxygenated, denitrogenated and desulphurisated.
• the reaction conditions include a pressure between 10 and 150 bar, preferably between 30 and 70 bar; a temperature between 200 and 400 °C, preferably between 250 and 350 °C and most preferably between 280 and 340 0 C; and a feed rate (LHSV) of 0.1 -10 hr-l(v/v).
• known hydrogenation catalysts containing metals from Group VIII and/or VIB of the Periodic System of Elements may be used.
• the hydrogenation catalyst is supported Pd, Pt, Ni, NiMo or a CoMo catalyst, the support being alumina and/or silica, as described for instance in FI 100248.
• NiMo/Al 2 O 3 and CoMo/Al 2 O 3 catalysts are used.
• Hydrodeoxygenation of triglycerides facilitates controlled decomposition of the triglyceride molecule contrary to uncontrolled cracking. Double bonds are also hydrogenated during the controlled hydrotreatment.
• Light hydrocarbons and gases formed mainly propane, water, CO 2 , CO, H 2 S and NH 3 are removed from the hydrodeoxygenated product.
• the feed may comprise fresh feed and at least one dilution agent selected from hydrocarbons and recycled product of the process.
• Organic or inorganic sulphur compound may optionally be fed along with hydrogen or with the feed to promote deoxygenation through decarb-reactions if desired.
• the hydrodeoxygenation stage is followed by an isomerisation stage.
• the feed into the isomerisation reactor is a mixture of n-paraffins and the composition of it can be predicted from the fatty acid distribution of individual bio oils of the feed.
• triglyceride oils and other fatty acid derivatives and fatty acids are almost theoretically converted to n-paraffins.
• propane is formed from the glycerol part of triglycerides, water and COx from carboxylic oxygen, H 2 S from organic sulphur compounds and NH3 from organic nitrogen compounds. It is advantageous for the process that these gas phase impurities are removed before the hydrocarbons are contacted with the isomerisation catalyst.
• reaction product from the hydrodeoxygenation stage is subjected to separation and the effluent containing the n-paraffins is passed to the second stage, isomerisation.
• the reaction conditions include a pressure between 10 and 150 bar, preferably between 30 and 100 bar; a temperature between 200 and 500 °C, preferably between 280 and 400 °C; and a feed rate (LHSV) of 0.1-10 hr- l(v/v).
• isomerisation catalysts known in the art may be used. Suitable isomerisation catalysts contain a molecular sieve and/or a metal selected from Group VIII of the Periodic Table of Elements and/or a carrier. Preferably, the isomerisation catalyst contains SAPO-I l or SAPO-41 or ZSM-22 or ZSM-23 or ferrierite and Pt, Pd or Ni and AI2O3 or SiO 2 . Typical isomerisation catalysts are, for example, Pt/S APO- 11/Al 2 O 3 , Pt/ZSM-22/Al 2 O 3 , Pt/ZSM-23/Al 2 O 3 and Pt/S APO- 11/SiO 2 . Most of these catalysts require the presence of hydrogen to reduce the catalyst deactivation.
• the reisomerisation is carried out as a third stage (isomerisation) according to the embodiment described in Figure 3, same or different catalysts and same or different reaction conditions may be used in each isomerisation stage.
• the catalyst and/or reaction conditions may be selected as not favouring cracking and the catalyst and/or reaction conditions in the second isomerisation stage may be selected as promoting cracking, resulting in increased yields of the components or product with the desired cold properties.
• the process yields hydrocarbon components suitable as bio jet fuels and as blending stocks for aviation fuels, and also components suitable as diesel fuel, gasoline and gas may be obtained.
• Aviation fuels meeting the requirements of Jet A-I may be obtained, containing the component manufactured using the process according to the invention, blended with conventional aviation fuels. It was surprisingly found that isoparaffinic hydrocarbon components particularly suitable as high quality aviation fuels and components for aviation fuels can be obtained with very good yields from biological and renewable material and from any mixtures thereof. The aviation fuel yields are remarkably high.
• the heavy components formed during the hydrodeoxygenation stage are utilised in an efficient and economical way and they are converted to more valuable components having particularly good properties also at low temperatures, thus making them particularly suitable for aviation fuels.
• the conversion of Cl 8 and C20 components in the process according to the invention is significantly higher when compared to a process where isomerisation is carried out once.
• the heavy components are subjected to isomerisation and also to some extent cracking.
• the process comprising hydrodeoxygenation, isomerisation and reisomerisation results in a significant decrease of the freezing point of the product, which comprises highly branched isoparaff ⁇ ns.
• the components boiling at higher temperatures and decreasing the freezing point and pour point are further processed to components having more favourable properties.
• the product contains no olefins, no aromatic compounds or naphthenes, which decreases significantly the scaling of engines.
• the product is based on renewable materials and it contains no sulphur compounds.
• the product obtained from the isomerisation stage was fractionated and the heavy recycle stream (fraction boiling at and above 29O 0 C) was fed to the third stage (second isomerisation) where the reisomerisation was carried out in a fixed bed tube reactor in the presence of Pt-SAPO-catalyst under a pressure of 40 bar, with WHSV of 1.5 1/h and hydrogen to oil ratio of 300 normal liters H 2 per liter oil fed.
• the reaction temperature of 315°C was used in the case the product was fractionated to diesel fuel EN590, 322°C for aviation fuels, jet fuel 1 and 340 0 C for jet fuel 2.

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