SE2250087A1 - Catalytic cracking of tall oil pitch-origin feedstock - Google Patents
Catalytic cracking of tall oil pitch-origin feedstockInfo
- Publication number
- SE2250087A1 SE2250087A1 SE2250087A SE2250087A SE2250087A1 SE 2250087 A1 SE2250087 A1 SE 2250087A1 SE 2250087 A SE2250087 A SE 2250087A SE 2250087 A SE2250087 A SE 2250087A SE 2250087 A1 SE2250087 A1 SE 2250087A1
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- Prior art keywords
- feedstock
- origin
- cracking
- boiling point
- range
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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
- C10G3/42—Catalytic treatment
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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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
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- 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
- C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
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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
- 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
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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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
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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
- 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
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1074—Vacuum distillates
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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
- 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
- C10G2300/302—Viscosity
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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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
- C10G3/42—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
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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
- C10G3/54—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed
- C10G3/55—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed with moving solid particles, e.g. moving beds
- C10G3/57—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed with moving solid particles, e.g. moving beds according to the fluidised bed technique
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- 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
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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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A process for producing a fuel component. The process comprises providing a petroleum derived feedstock comprising vacuum gas oil (VGO) and/or unconverted oil (UCO) and providing a tall oil pitch-origin (TOP-origin) feedstock comprising fatty acids and resin acids, and/or derivatives thereof. The TOP-origin feedstock has a boiling point distribution in which at least 40 wt% of the TOP-origin feedstock has a boiling point in the range of 100-500 °C. The process further comprises combining the petroleum derived feedstock with the TOP-origin feedstock to provide a combined feedstock, catalytically cracking the combined feedstock in a catalytic cracking unit to provide a cracking product. A cracking product. Use of a tall oil pitch-origin (TOP-origin) feedstock. Use of a fluid catalytic cracking unit.
Description
CATALYTIC CRACKING OF TALL OIL PITCH-ORIGIN FEEDSTOCK Technical field The present invention relates to a process for producing a fuel component, the process comprising provision of a tall oil pitch origin feedstock; to a fuel component; and a use of tall oil pitch origin feedstock to produce a fuel component.
Background Transportation fuels has conventionally been produced from crude oil of fossil origin. Demand for renewable/sustainable energy is vastly increasing. For example, the European Union requires renewable energy to have at least a 10% share of transport energy by 2020, and even higher shares are being attempted regionally.
For a renewable bio-based gasoline, efforts to date have been devoted mostly to ethanol. Other gasoline biocomponents similar to ethanol in terms of technical specifications for fuel include, for example, biobutanol and biomethanol and bioethers manufactured from it, such as methyl tert-butyl ether (MTBE). Although ethanol is the dominant liquid biofuel globally, technical restrictions limit its use in conventional gasoline cars to 10-15 v/v% (bio-energy 7-10%). The use of other alcohols and ethers as oxygenated fuels is limited by the same restrictions. Since current conventional cars will continue to take the major share of gasoline car fleets for at least the next 10-20 years, it is necessary to establish and assess biocomponent options for them.
WO2017/114715 discloses a process for the formation of a gasoline product from the thermal catalytic cracking of a feedstock comprising vacuum gas oil and tall oil pitch (TOP). The use of TOP is limited, firstly by its high viscosity (3000 cP/50 C.), and secondly, by the fact that TOP is never totally rigid. To better utilize the current transportation fuel production infrastructure in the production of fuels comprising biocomponents, there is a need in the art for improved processes that can be run in various types of catalytic cracking units, as well as a need for processes that can be run with other renewable feedstocks.
Summary of the invention An object of the invention is to provide a process for catalytic cracking of a combined feedstock comprising a fossil and feedstock and a renewabie feedstock to produce a gasoline product. This object of the invention, as well as other objects apparent to a person skilled in the art after having studied the description below, are accomplished by a process for producing a fuel component, comprising - providing a petroleum derived feedstock comprising vacuum gas oil (VGO) and/or unconverted oil (UCO); - providing a tall oil pitch-origin (TOP-origin) feedstock comprising fatty acids and resin acids, and/or derivatives thereof, wherein said TOP-origin feedstock has a boiling point distribution in which at least 40 wt% of the TOP- origin feedstock has a boiling point in the range of 100-500 °C; - combining the petroleum derived feedstock with the TOP-origin feedstock to provide a combined feedstock; - catalytically cracking the combined feedstock in a catalytic cracking unit to provide a cracking product.
The invention solves the problem of providing a process for producing a transportation fuel feedstock which can be run in existing infrastructure for upgrading transportation fuel precursor, such as in catalytic cracking units, and in particularfluid catalytic cracking units. By providing a tall oil pitch origin (TOP-origin) feedstock comprising fatty acids and resin acids, and/or derivatives thereof, wherein said TOP-origin feedstock boiling point distribution in which at least 40 wt% of the TOP-origin feedstock has a boiling point in the range of 100-500 °C, a renewabie co-processing feedstock that is processable with a fossil feedstock such as vacuum gas oil (VGO) or unconverted oil (UCO) can be obtained. The combined feedstock of said TOP-origin feedstock and fossil feedstock is highly suitable for conversion using catalytic cracking units, and in particular fluid catalytic cracking units.
Thus, a gasoline component having a substantial biological content can be obtained using current catalytic cracking infrastructure.
Cataiytic cracking is a well-known process in refinery used for c|eaving larger hydrocarbon components into smaller shortchain hydrocarbons which are usable as traffic fuel components. Cracking is achieved by breaking the carbon-carbon bonds in the hydrocarbon chain of C15 to C45 typically in the presence of a cracking catalyst. The nature of the end products is dependent on the nature of the feed and on the process conditions under which the process is carried out, such as temperature, pressure and the nature of the catalyst.
Herein, the terms “fossil feedstock” and “petroleum derived feedstock” are used interchangeably. Both terms refer to that substantially 100 wt% of the feedstock is derived from petroleum.
Vacuum gas oil (VGO) is a hydrocarbon stream recovered from one or more petrochemical refinery unit operations typically as a side cut from a vacuum column, a crude column and/or a coker column. VGO contains a large quantity of cyclic and aromatic compounds as well as heteroatoms, such as sulphur and nitrogen, and other heavier compounds, depending on the crude source and VGO cut. VGO can include, for example, light vacuum gas oil, heavy vacuum gas oil, heavy coker gas oil, light coker gas oil, and/or heavy atmospheric gas oil.
Unconverted oil (UCO) is a bottom or residue from distillation or isocracking of vacuum gas oil.
The tall oil pitch-origin (TOP-origin) feedstock of the present invention is of renewable, or non-fossil or non-petroleum derived origin. lt is derived from tall oil pitch. Tall oil pitch (TOP) is a non-volatile fraction that is separated at crude tall oil vacuum distillation. Tall oil is lignocellulosic raw material oil obtained as a byproduct from cellulosic pulp cooking process. lt comprises of resin acids, fatty acids, neutral materials, i.e. mainly sterols, and esters of these alcohols and acids. Tall oil is generally refined by distillation at a low pressure. Primary oil, fatty acids and resin acids are recovered as a surplus of the distillation, and TOP is generated as a distillation residue.
At least 50 wt% of the TOP-origin feedstock may consist of fatty acids and resin acids, and/or derivatives thereof, or at least 60 wt% of the TOP- origin feedstock may consist of fatty acids and resin acids, and/or derivatives thereof, or at least 70 wt% of the TOP-origin feedstock may consist of fatty acids and resin acids, and/or derivatives thereof. Additionally, the TOP-origin feedstock typically comprises unsaponifiables and/or derivatives thereof, water, spirits, hydrocarbons, etc. However, the TOP-origin feedstock is of 100 wt% renewable origin.
The TOP-origin feedstock of the invention differs from tall oil pitch at least by having a different boiling point distribution. The TOP-origin feedstock has a boiling point distribution in which at least 40 wt% of the TOP-origin feedstock has a boiling point in the range of 100-500 °C. The boiling point distribution may be determined according to the standard test method ASTM D7169. ln comparison, tall oil pitch (TOP) typically has a boiling point distribution in which no more than 30 % of its constituents boils at a temperature in the range of 100-500 °C. More than 70 wt% of tall oil pitch has a boiling point of above 500 °C.
The TOP-origin feedstock may have a boiling point distribution in which at least 50 wt.-% has a boiling point in the range of 100-500 °C, such as a boiling point distribution in which at least 60 wt.-% has a boiling point in the range of 100-500 °C.
Additionally, the TOP-origin feedstock may have a boiling point distribution in which at least 20 wt.-% has a boiling point in the range of 200- 400 °C, such as a boiling point distribution in which at least 30 wt.-% has a boiling point in the range of 200-400 °C. ln comparison, TOP has a boiling point distribution in which less than 10 wt.% has a boiling point in the range of 200-400 °C.
Still further, the TOP-origin feedstock may have a boiling point distribution in which at least 10 wt.-% has a boiling point in the range of 100- 350 °C. ln comparison, TOP has a boiling point distribution in which less than 1 wt.% has a boiling point in the range of 100-350 °C.
The TOP-origin feedstock of the present invention may alternatively, or additionally, have an average molecular weight of less than 350 g/mol. ln comparison, tall oil pitch has an average molecularweight of substantially above 400 g/mol. Thus, the feedstock of the present invention provides a biobased feedstock having a similar molecular weight as fossil feedstocks, such as vacuum gas oil (VGO) and unconverted oil (UCO). The TOP-origin feedstock is thus better suited for catalytic cracking than other, high molecular weight feedstocks, such as for example TOP.
The TOP-origin feedstock of the present invention may alternatively, or additionally have a viscosity of less than 1500 cP at 50°C. ln comparison, tall oil pitch has a viscosity of at least 3000 cP at 50°C. The viscosity of tall oil pitch as well as the viscosity of the TOP-origin feedstock of the present invention can be determined using a Brookfield viscometer. The lower viscosity makes the TOP-origin feedstock easier to handle and feed to a reactor in the refinery than higher viscosity feedstocks, such as TOP.
Without wishing to be bound by any specific scientific theory, it is contemplated that the boiling point distribution, average molecular weight and viscosity of the TOP-origin feedstock are inter-related properties correlated with each other.
The inventors have surprisingly found that from a catalytic cracking process in which a TOP-origin feedstock as described above is utilized, a higher amount of liquid products can be obtained as compared to a corresponding process in which TOP is utilized. By providing the TOP-origin feedstock as described above in a co-process with petroleum-derived feedstock in an in catalytic cracking process, a larger fraction of the gasoline and diesel range products is produced, as compared to if TOP would be provided in a co-process with petroleum-derived feedstock in an in catalytic cracking process. ln the inventive process TOP-origin feedstock is combined with the petroleum derived feedstock either by introducing them jointly to the catalytic cracking unit or the TOP-origin feedstock is fed in a mixed feed stream or as a separate feed stream either before, after or before and after the introduction of the petroleum derived feedstock. The combined feedstock typically contains from 3 to 25 vol-% TOP-origin feedstock. ln some embodiments, the provision of the TOP-origin feedstock comprises providing tall oil pitch; heating said tall oil pitch a reactor to a temperature of at least 300 °C; maintaining the temperature in the reactor at 300° C or higher under 10-150 minutes to enable cracking/cleaving of high molecular weight components in the TOP to provide the TOP-origin feedstock as described above.
The TOP-origin feedstock may thus be obtained as a product of the method described in WO 2017/114715, in which a method for the treatment of tall oil pitch (TOP) is described. The method comprises heating the TOP in a reactor to a temperature of at least 300 °C; maintaining the temperature in the reactor at 300 °C or higher under a period of time sufficient to enable cracking/cleaving of high molecular weight components in the TOP. The residence time during the thermal treatment is generally in the range of 10- 150 minutes. The generated product comprises fatty acids and/or rosin acids, and/or derivatives thereof, and/or unsaponifiables and/or their derivatives, which has a boling point distribution in which at least 40 wt% has a boiling point in the range of 100-500 °C lower molecular weight compared to the high molecular weight components in the original TOP, and also lower viscosity than the original TOP. The generated product is clearly no longer tall oil pitch and it is suitable as the TOP-origin feedstock of the present invention.
Rosin acids are a resin acid known also under the names abietic acid and sylvic acid. ln some embodiments, the TOP-origin feedstock has an average molecular weight of less than 350 g/mol. Tall oil pitch has an average molecular weight of substantially above 400 g/mol. Thus, the feedstock of the present invention provides a biobased feedstock having a similar molecular weight as fossil feedstocks, such as vacuum gas oil (VGO) and unconverted oil (UCO). The TOP-origin feedstock is thus better suited for catalytic cracking than other, high molecular weight feedstocks, such as TOP. ln some embodiments, the TOP-origin feedstock of the present invention has a viscosity of less than 1500 cP at 50°C.ln comparison, tall oil pitch has a viscosity of at least 3000 cP at 50°C. The viscosity of tall oil pitch as well as the viscosity of the tall oil pitch origin feedstock of the present invention can be measured using a Brookfield viscometer. The lower viscosity makes the TOP-origin feedstock easier to handle and feed to a reactor in the refinery than higher viscosity feedstocks, such as TOP. ln some embodiments, the TOP-origin feedstock has a viscosity of less than 1000 cP at 50°C. ln some embodiments, the TOP-origin feedstock has an average molecular weight in the range of from 150 g/mo| to 340 g/mo|. ln some embodiments, the TOP-origin feedstock has an average molecular weight in the range of from 200 g/mo| to 330 g/mo|. ln some embodiments, the catalytic cracking unit is a f|uid catalytic cracking (FCC) unit. A powdered catalyst may be employed in the FCC unit. The catalyst particles are suspended in a rising flow of a heavy gas oil feed to form a fluidized bed. The feed is typically pre-heated and then sprayed into a base of the riser via feed nozzles to bring the feed in contact with the hot fluidized catalyst. The temperature of a FCC cracker is typically between 500° C and 800° C. lt has surprisingly been found that the combined feedstock of the present invention can be readily employed in current FCC units. ln some embodiments, the catalytical cracking is performed in the presence of a catalyst comprising a zeolitic molecular sieve, preferably having a large average pore size. Molecular sieves with a large pore size have pores with openings of greater than about 0.7 nm in effective diameter defined by greater than 10 and typically 12 membered rings. Suitable large pore molecular sieves include synthetic zeolites such as X-type and Y-type zeolites, mordenite, and faujasite. Exemplary molecule sieves are Y-type zeolites with low rare earth content. Low rare earth content denotes less than or equal to about 1.0 wt % rare earth oxide on the zeolitic portion of the catalyst. Catalyst additives may be added to the catalyst composition during operation. Medium pore sized molecular sieves such as MFI with openings of about 0.7 nm or less may be blended in with the large pore molecular sieves to increase production of lighter olefins, if desired. ln some cases, only medium pore sized molecular sieves may be used if the feed to the riser is an FCC product cut such as a naphtha stream. ln some embodiments, the temperature during the catalytical cracking is in the range of 500-800 ° C. ln some embodiments, the combined feedstock contains from 2 to 25 vo|% of the TOP-origin feedstock, preferably from 3 to 15 vol-% of the TOP- origin feedstock. ln some embodiments, the combined feedstock contains from 75 to 98 vo|% of the petroleum derived feedstock, preferably from 3 to 15 vo|% of the petroleum derived feedstock. ln some embodiments, the petroleum derived feedstock contains 80-100 vo|% of VGO. The petroleum derived feedstock may contain 20 vo|% or less of UCO. ln some embodiments, the petroleum derived feedstock contains 80-100 vo|% of UCO. The petroleum derived feedstock may contain 20 vo|% or less of VGO. ln some embodiments, the process further comprises fractionating the cracking product to provide at least a fuel component. ln some examples, after cracking, a cracking product leaving the cracking unit passes to a fractionation tower where it is separated into various fractions. The operation of a fractionation tower is well known in the art. The fractions formed in the tower are gas stream, fuel product, light oil and distillation bottom. The amount of each fraction formed will vary considerably depending on the nature of the feed. Typically 30% of the yield is gasoline product and 25% is diesel. The yields from combined feedstock including TOP-origin feedstock are at the same level as the yields from only fossil feedstock, and better than the yields from a combined feedstock of TOP and petroleum derived feedstock. ln some embodiments the process further comprises desulfurizing of any one of the feedstocks and or the cracking product, for example by hydrogenation. The hydrocarbon composition, and hence the octane levels, shall remain as they were before desulfurization of the recovered gasoline product.
According to another aspect of the present invention, there is provided a cracking product obtainable from a catalytic cracking process, in which a mixture of a petroleum derived feedstock and a TOP-origin feedstock comprising fatty acids and resin acids, and/or derivatives thereof, is used as a combined feedstock, wherein said TOP-origin feedstock has a boiling point distribution in which at least 40 wt% of the TOP-origin feedstock has a boiling point in the range of 100-500 °C.
The cracking product may be used directly as, or further processed to, a fuel component which is a hydrocarbon component suitable for fuel blending, in particularfor transportation fuel blending.
A gasoline component is a hydrocarbon component suitable for gasoline blending. lt may be used as a component when producing a gasoline meeting the quality requirements of EN228. The fuel or gasoline blend comprising the gasoline product of the invention is a biofuel or biogasoline. Biofuel refers to a renewable fuel oil, a biomass-derived fuel oil, a fuel oil prepared from the conversion of biomass or a mixture of fuel having a biomass derived component in blend with a mineral oil. Fuel refers herein to transportation fuels, which are fractions or cuts or hydrocarbons having distillation curves standardized for gasoline (0-210° C).
A diesel component is a hydrocarbon component suitable for diesel blending.
According to yet another aspect of the present invention, there is provided a use of a TOP-origin feedstock comprising fatty acids and resin acids, and/or derivatives thereof, and optionally unsaponifiables and/or derivatives thereof, in a fluid catalytic cracking process to obtain a cracking product, wherein said TOP-origin feedstock a boiling point distribution in which at least 40 wt% of the TOP-origin feedstock has a boiling point in the range of 100-500 °C. Embodiments and examples described in relation to the aspects above applies also to this use.
According to a further aspect, there is provided a use of a catalytic cracking unit for catalytically cracking a TOP-origin feedstock comprising fatty acids and resin acids, and/or derivatives thereof, wherein said TOP-origin feedstock has a boiling point distribution according to ASTM D7169, in which at least 40 wt% of the TOP-origin feedstock has a boiling point in the range of 100-500 °C to obtain a cracking product. Embodiments and examples described in relation to the aspects above are applicable applies also to this use.
Also provided is a process for producing a cracking product, comprising - providing a petroleum derived feedstock comprising vacuum gas oil (VGO) and/or unconverted oil (UCO); - providing a tall oil pitch-origin (TOP-origin) feedstock comprising fatty acids and resin acids, and/or derivatives thereof, wherein the TOP-origin feedstock has an average molecular weight of less than 350 g/mol; - combining the petroleum derived feedstock with the TOP-origin feedstock to provide a combined feedstock; - catalytically cracking the combined feedstock in a catalytic cracking unit to provide a cracking product.
Embodiments and examples described in relation to the aspects above applies also to this process.
Also provided is a process for producing a cracking product, comprising - providing a petroleum derived feedstock comprising vacuum gas oil (VGO) and/or unconverted oil (UCO); - providing a tall oil pitch-origin (TOP-origin) feedstock comprising fatty acids and resin acids, and/or derivatives thereof, wherein the TOP-origin feedstock of the present invention has a viscosity of less than 1500 cP at 50°C; - combining the petroleum derived feedstock with the TOP-origin feedstock to provide a combined feedstock; - catalytically cracking the combined feedstock in a catalytic cracking unit to provide a cracking product.
Embodiments and examples described in relation to the aspects above applies also to this process.
Examples 11 Five samples were prepared for five runs of FCC testing. ln each sample, vacuum gas oil (VGO) was diluted with: Sample 1: 5 wt-% Tall Oil Pitch (TOP) Sample 2: 10 wt-% TOP Sample 3: 20 wt-% TOP Sample 4: 5 wt-% TOP-origin feedstock (m-TOP) Sample 5: 10 wt-% m-TOP The TOP and m-TOP was provided by SunPine AB, Sweden. The 10 boiling point distribution of the TOP and m-TOP, determined according to standard test method ASTM D7169, are shown in Table 1. Samples 4 and 5 are samples according to the present invention. Samples 1, 2 and 3 are provided as comparative examples.
Table 1. Boiling point distribution Cutpoint [wt-%] Boiling point Boiling point (TOP) [°C] (m-TOP) [°C] Initial boiling point (0.5 wt.%) 367 124 5 wt% 399 250 10 wt% 408 325 20 wt% 473 374 30 wt% 515 399 40 wt% 551 433 50 wt% 581 448 60 wt% 587 490 70 wt% 598 546 80 wt% 652 615 90 wt% - - 95 wt% - - Final boiling point (99.5 wt%) - - Test runs was performed using an FCC MAT (Fluid Catalytic Cracking Micro Activity Test) unit. The reactor was operated under the conditions shown in Table 2. Samples of the cracking products were taken and analysed for different properties. The result of said analysis are presented in Table 3 12 below, in which the results for each cracking product are reported by reference to the sample used to obtain said product.
Table 2. Reactor conditions. 13 Property Value Catalyst/Oil range 1.5 - 4.0 Catalyst bed temperature 560 °C Injection time 12 s Catalyst 1.5-7.5 g Oil 2 cm3 WHSV 60-300 h* Oil Temperature 80 °C Receiver cooling system temperature 18 °C Table 3. Product analysis. Exchange Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 [wt-%] [wt-%] [wt-%] [wt-%] [wt-%] Hydrogen -0.15 -0.15 -0.10 -0.55 -0.25 H28 0.01 0.33 0.22 0.00 0.00 Dry Gas 5.67 4.45 3.33 0.31 4.09 Propane 5.37 3.06 1.90 -0.43 2.63 Propylene 13.22 10.05 5.57 2.72 6.04 i-butane 12.57 9.96 5.53 2.27 6.51 n-Butane 3.28 1.68 1.06 -0.63 1.42 Butene 2.63 0.21 0.16 0.22 0.52 Gasoline 29.89 41.99 42.88 66.98 41.85 LCO 6.99 10.58 19.29 17.37 18.82 HCO 4.61 4.87 7.39 -0.22 7.01 Coke 3.47 4.53 3.78 3.57 4.64 CO 1.40 2.12 2.11 1.60 1.81 C02 1.80 1.19 1.02 0.80 0.60 H20 9.24 5.14 5.85 5.99 4.31 Total 100.00 100.00 100.00 100.00 100.00 Table 4 shows the summarized amount of gasoline and diesel range gasoline and LCO. products of Table 3, i.e. the sum of the amount of i-butane, n-butane, butene, 14 Table 4. Summarized amount of diesel and gasoline rage products.
Exchange Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 [wt-%] [wt-%] [wt-%] [wt-%] [wt-%] Gasoline and 55.36 64.41 68.92 86.21 69.13 diesel range components
Claims (15)
1. A process for producing a cracking product, comprising - providing a petroleum derived feedstock comprising vacuum gas oil (VGO) and/or unconverted oil (UCO); - providing a tall oil pitch-origin (TOP-origin) feedstock comprising fatty acids and resin acids, and/or derivatives thereof, wherein said TOP-origin feedstock has a boiling point distribution according to ASTM D7169, in which at least 40 wt% of the TOP-origin feedstock has a boiling point in the range of 100-500 °C; - combining the petroleum derived feedstock with the TOP-origin feedstock to provide a combined feedstock; - catalytically cracking the combined feedstock in a catalytic cracking unit to provide a cracking product.
2. The process according to claim 1, wherein said TOP-origin feedstock has a viscosity of less than 1500 cP at 50°C, according to a measurement using a Brookfield viscometer, such as a viscosity of less than 1000 cP at 50°C
3. The process according to any one of claims 1-2, wherein said TOP- origin feedstock has an average molecular weight of less than 350 g/mol, such as an average molecular weight in the range of from 150 g/mol to 340 g/mol, preferably an average molecular weight in the range of from 200 g/mol to 330 g/mol
4. The process according to any one of the preceding claims, wherein the catalytic cracking unit is a fluid catalytic cracking (FCC) unit.
5. The process according to any one of the preceding claims, wherein the temperature during the catalytical cracking is in the range of 500-800° C.
6. The process according to any one of the preceding claims, wherein the catalytical cracking is performed in the presence of a catalyst comprising a zeolitic molecular sieve.
7. The process according to any one of the preceding claims, further comprising fractionating the cracking product to provide at least a fuel component.
8. The process according to any one of the preceding claims, wherein the combined feedstock contains from 2 to 25 vo|% of the TOP-origin feedstock, preferably from 3 to 15 vol-% of the TOP-origin feedstock.
9. The process according to any one of the preceding claims, wherein the combined feedstock contains 75-98 vo|% of the fossil feedstock, preferably 85-97 vo|% of the fossil feedstock.
10. The process according to any one of the preceding claims, wherein the petroleum derived feedstock contains 80-100 vo|% of VGO or 80-100 vo|% of UCO.
11. which a mixture of a petroleum derived feedstock and a tall oil pitch-origin A cracking product obtainable from a catalytic cracking process, in (TOP-origin) feedstock comprising fatty acids and resin acids, and/or derivatives thereof, is used as a combined feedstock, wherein said TOP- origin feedstock has a boiling point distribution according to ASTM D7169, in which at least 40 wt% of the TOP-origin feedstock has a boiling point in the range of 100-500 °C.
12. cracking process is further characterized by any one of claims 1- The cracking product according to claim 9, wherein the catalytic
13. and/or derivatives thereof, wherein said TOP-origin feedstock has a boiling Use of a TOP-origin feedstock comprising fatty acids and resin acids,point distribution according to ASTM D7169, in which at least 40 wt% of the TOP-origin feedstock has a boiiing point in the range of 100-500 °C, in a catalytic cracking process to obtain a cracking product.
14. feedstock comprising fatty acids and resin acids, and/or derivatives thereof, Use of a catalytic cracking unit for catalytically cracking a TOP-origin wherein said TOP-origin feedstock has a boiiing point distribution according to ASTM D7169, in which at least 40 wt% of the TOP-origin feedstock has a boiiing point in the range of 100-500 °C to obtain a cracking product.
15. cata|ytica| cracking is further characterized by any one of ciaims 1- The use according to any one of ciaims 11 or 12, wherein the
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US20140296594A1 (en) * | 2013-03-28 | 2014-10-02 | Shell Oil Company | Process for the fluid catalytic cracking of oxygenated hydrocarbon compounds from biological origin |
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WO2017114715A1 (en) * | 2015-12-31 | 2017-07-06 | Neste Corporation | A process for producing high octane gasoline component from a mixture of vgo and tall oil pitch |
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